CN103342705A - Method for synthesis of pyrrolo[1,2-a]quinoxaline derivatives - Google Patents
Method for synthesis of pyrrolo[1,2-a]quinoxaline derivatives Download PDFInfo
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- CN103342705A CN103342705A CN2013102390661A CN201310239066A CN103342705A CN 103342705 A CN103342705 A CN 103342705A CN 2013102390661 A CN2013102390661 A CN 2013102390661A CN 201310239066 A CN201310239066 A CN 201310239066A CN 103342705 A CN103342705 A CN 103342705A
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- Prior art keywords
- tetralyl
- formaldehyde
- pyrroles
- phenyl
- quinoxaline
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- 238000000034 method Methods 0.000 title claims abstract description 19
- 238000003786 synthesis reaction Methods 0.000 title abstract description 4
- IEOUSWADWJLLCH-UHFFFAOYSA-N pyrrolo[1,2-a]quinoxaline Chemical class C1=NC2=CC=CC=C2N2C1=CC=C2 IEOUSWADWJLLCH-UHFFFAOYSA-N 0.000 title abstract 5
- 230000015572 biosynthetic process Effects 0.000 title abstract 3
- 238000006243 chemical reaction Methods 0.000 claims abstract description 86
- -1 2-formyl azole compound Chemical class 0.000 claims abstract description 54
- 239000000126 substance Substances 0.000 claims abstract description 9
- 239000003960 organic solvent Substances 0.000 claims abstract description 5
- 239000011261 inert gas Substances 0.000 claims abstract description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 204
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 75
- 150000003233 pyrroles Chemical class 0.000 claims description 50
- 229910052757 nitrogen Inorganic materials 0.000 claims description 38
- 239000001257 hydrogen Substances 0.000 claims description 36
- 229910052739 hydrogen Inorganic materials 0.000 claims description 36
- 150000003252 quinoxalines Chemical class 0.000 claims description 17
- 229910052740 iodine Inorganic materials 0.000 claims description 15
- 239000011630 iodine Substances 0.000 claims description 15
- 229910052731 fluorine Inorganic materials 0.000 claims description 13
- 239000011737 fluorine Substances 0.000 claims description 13
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 229910052736 halogen Inorganic materials 0.000 claims description 8
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 3
- 229910021589 Copper(I) bromide Inorganic materials 0.000 claims description 3
- ONIBWKKTOPOVIA-BYPYZUCNSA-N L-Proline Chemical group OC(=O)[C@@H]1CCCN1 ONIBWKKTOPOVIA-BYPYZUCNSA-N 0.000 claims description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- 125000006276 2-bromophenyl group Chemical group [H]C1=C([H])C(Br)=C(*)C([H])=C1[H] 0.000 claims description 2
- 125000004198 2-fluorophenyl group Chemical group [H]C1=C([H])C(F)=C(*)C([H])=C1[H] 0.000 claims description 2
- 125000006304 2-iodophenyl group Chemical group [H]C1=C([H])C(I)=C(*)C([H])=C1[H] 0.000 claims description 2
- 125000006275 3-bromophenyl group Chemical group [H]C1=C([H])C(Br)=C([H])C(*)=C1[H] 0.000 claims description 2
- 125000004180 3-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C(F)=C1[H] 0.000 claims description 2
- 125000006305 3-iodophenyl group Chemical group [H]C1=C([H])C(I)=C([H])C(*)=C1[H] 0.000 claims description 2
- 125000004800 4-bromophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Br 0.000 claims description 2
- 125000001255 4-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1F 0.000 claims description 2
- 125000006306 4-iodophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1I 0.000 claims description 2
- PNWSHHILERSSLF-UHFFFAOYSA-N 4-methylbenzene-1,3-dicarboxylic acid Chemical compound CC1=CC=C(C(O)=O)C=C1C(O)=O PNWSHHILERSSLF-UHFFFAOYSA-N 0.000 claims description 2
- PMZBHPUNQNKBOA-UHFFFAOYSA-N 5-methylbenzene-1,3-dicarboxylic acid Chemical compound CC1=CC(C(O)=O)=CC(C(O)=O)=C1 PMZBHPUNQNKBOA-UHFFFAOYSA-N 0.000 claims description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 claims description 2
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- 239000004914 cyclooctane Substances 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 125000000636 p-nitrophenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)[N+]([O-])=O 0.000 claims description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N perisophthalic acid Natural products OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-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
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 claims description 2
- 238000004821 distillation Methods 0.000 abstract description 37
- 238000001035 drying Methods 0.000 abstract description 37
- 238000000605 extraction Methods 0.000 abstract description 37
- 238000001816 cooling Methods 0.000 abstract description 36
- 238000002360 preparation method Methods 0.000 abstract description 35
- 239000002994 raw material Substances 0.000 abstract description 35
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
- 239000000758 substrate Substances 0.000 abstract description 4
- 238000003756 stirring Methods 0.000 abstract description 2
- 239000003446 ligand Substances 0.000 abstract 2
- 150000004982 aromatic amines Chemical class 0.000 abstract 1
- 230000003197 catalytic effect Effects 0.000 abstract 1
- 239000011259 mixed solution Substances 0.000 abstract 1
- 230000001681 protective effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 abstract 1
- 229910052723 transition metal Inorganic materials 0.000 abstract 1
- 239000012856 weighed raw material Substances 0.000 abstract 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Substances O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 258
- XSCHRSMBECNVNS-UHFFFAOYSA-N quinoxaline Chemical compound N1=CC=NC2=CC=CC=C21 XSCHRSMBECNVNS-UHFFFAOYSA-N 0.000 description 128
- 239000000047 product Substances 0.000 description 39
- 238000001953 recrystallisation Methods 0.000 description 36
- 239000007787 solid Substances 0.000 description 36
- 238000005406 washing Methods 0.000 description 35
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 34
- 238000001819 mass spectrum Methods 0.000 description 34
- 238000001228 spectrum Methods 0.000 description 34
- 150000003254 radicals Chemical class 0.000 description 30
- UBPDKIDWEADHPP-UHFFFAOYSA-N 2-iodoaniline Chemical compound NC1=CC=CC=C1I UBPDKIDWEADHPP-UHFFFAOYSA-N 0.000 description 27
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 20
- ZSKGQVFRTSEPJT-UHFFFAOYSA-N pyrrole-2-carboxaldehyde Chemical compound O=CC1=CC=CN1 ZSKGQVFRTSEPJT-UHFFFAOYSA-N 0.000 description 16
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 8
- XWIYUCRMWCHYJR-UHFFFAOYSA-N 1h-pyrrolo[3,2-b]pyridine Chemical class C1=CC=C2NC=CC2=N1 XWIYUCRMWCHYJR-UHFFFAOYSA-N 0.000 description 4
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 4
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 150000002460 imidazoles Chemical class 0.000 description 4
- 150000002475 indoles Chemical class 0.000 description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 4
- GETTZEONDQJALK-UHFFFAOYSA-N (trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1 GETTZEONDQJALK-UHFFFAOYSA-N 0.000 description 3
- NEOLWKPYXMBCON-UHFFFAOYSA-N n-fluoro-2-iodoaniline Chemical compound FNC1=CC=CC=C1I NEOLWKPYXMBCON-UHFFFAOYSA-N 0.000 description 3
- 229940074386 skatole Drugs 0.000 description 3
- CTWQGTOWGFCWNW-UHFFFAOYSA-N 1,3-dimethylpyrrole Chemical class CC=1C=CN(C)C=1 CTWQGTOWGFCWNW-UHFFFAOYSA-N 0.000 description 2
- UQNRTIQURQZGKL-UHFFFAOYSA-N 1-(2-nitrophenyl)pyrrole Chemical class [O-][N+](=O)C1=CC=CC=C1N1C=CC=C1 UQNRTIQURQZGKL-UHFFFAOYSA-N 0.000 description 2
- 150000005356 1-phenylpyrroles Chemical class 0.000 description 2
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 2
- AOPBDRUWRLBSDB-UHFFFAOYSA-N 2-bromoaniline Chemical compound NC1=CC=CC=C1Br AOPBDRUWRLBSDB-UHFFFAOYSA-N 0.000 description 2
- GDMZHPUPLWQIBD-UHFFFAOYSA-N 2-pyrrol-1-ylaniline Chemical class NC1=CC=CC=C1N1C=CC=C1 GDMZHPUPLWQIBD-UHFFFAOYSA-N 0.000 description 2
- GXWNSJYVSIJRLS-UHFFFAOYSA-N 6-bromo-8-methylimidazo[1,2-a]pyrazine Chemical compound CC1=NC(Br)=CN2C=CN=C12 GXWNSJYVSIJRLS-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 0 Cc1c(C=C(*2)NO)c2ccc1 Chemical compound Cc1c(C=C(*2)NO)c2ccc1 0.000 description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- MRLVFVTVXSKAMX-UHFFFAOYSA-N Methyl 4-amino-3-iodobenzoate Chemical class COC(=O)C1=CC=C(N)C(I)=C1 MRLVFVTVXSKAMX-UHFFFAOYSA-N 0.000 description 2
- UQFQONCQIQEYPJ-UHFFFAOYSA-N N-methylpyrazole Chemical class CN1C=CC=N1 UQFQONCQIQEYPJ-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- YNBADRVTZLEFNH-UHFFFAOYSA-N methyl nicotinate Chemical compound COC(=O)C1=CC=CN=C1 YNBADRVTZLEFNH-UHFFFAOYSA-N 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- CPNGPNLZQNNVQM-UHFFFAOYSA-N pteridine Chemical compound N1=CN=CC2=NC=CN=C21 CPNGPNLZQNNVQM-UHFFFAOYSA-N 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- LMLICLRBZPFXMK-UHFFFAOYSA-N 1-(2-nitrophenyl)pyrrole-2-carbaldehyde Chemical compound [O-][N+](=O)C1=CC=CC=C1N1C(C=O)=CC=C1 LMLICLRBZPFXMK-UHFFFAOYSA-N 0.000 description 1
- ZLKHNURELCONBB-UHFFFAOYSA-N 2,5-diethoxyoxolane Chemical compound CCOC1CCC(OCC)O1 ZLKHNURELCONBB-UHFFFAOYSA-N 0.000 description 1
- HERGPIKZUJHAPU-UHFFFAOYSA-N 2-bromo-n-fluoroaniline Chemical compound FNC1=CC=CC=C1Br HERGPIKZUJHAPU-UHFFFAOYSA-N 0.000 description 1
- MMWNKXIFVYQOTK-UHFFFAOYSA-N 2-bromopyridine-3-carboxylic acid Chemical compound OC(=O)C1=CC=CN=C1Br MMWNKXIFVYQOTK-UHFFFAOYSA-N 0.000 description 1
- QISSVLCQDNIJCS-UHFFFAOYSA-N 2-fluoro-1h-indole Chemical class C1=CC=C2NC(F)=CC2=C1 QISSVLCQDNIJCS-UHFFFAOYSA-N 0.000 description 1
- KEYRTRGLKSAGJN-UHFFFAOYSA-N 2-iodopyridine-3-carboxylic acid Chemical compound OC(=O)C1=CC=CN=C1I KEYRTRGLKSAGJN-UHFFFAOYSA-N 0.000 description 1
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 1
- ZCTJXWVTLAHGAJ-UHFFFAOYSA-N 2-pyrrol-1-ylbenzonitrile Chemical compound N#CC1=CC=CC=C1N1C=CC=C1 ZCTJXWVTLAHGAJ-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- RHJLTOVSJKKHLY-UHFFFAOYSA-N 4-bromo-2-(trifluoromethyl)pyrimidine Chemical compound FC(F)(F)C1=NC=CC(Br)=N1 RHJLTOVSJKKHLY-UHFFFAOYSA-N 0.000 description 1
- FOUBPRFOENCSCV-UHFFFAOYSA-N 4-iodo-2-(trifluoromethyl)pyrimidine Chemical compound C1=CC(I)=NC(=N1)C(F)(F)F FOUBPRFOENCSCV-UHFFFAOYSA-N 0.000 description 1
- AWLDDDPIAFHCFV-UHFFFAOYSA-N 5-phenyl-1h-pyrrole-2-carbaldehyde Chemical class N1C(C=O)=CC=C1C1=CC=CC=C1 AWLDDDPIAFHCFV-UHFFFAOYSA-N 0.000 description 1
- 229930008564 C01BA04 - Sparteine Natural products 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- RUHKUUFAKLLDEY-UHFFFAOYSA-N FC(C1=CC=CC=C1)(F)F.[Br] Chemical compound FC(C1=CC=CC=C1)(F)F.[Br] RUHKUUFAKLLDEY-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- QWXLFOQRYNAVKU-UHFFFAOYSA-N O=Cc([nH]c1c2)cc1ccc2I Chemical compound O=Cc([nH]c1c2)cc1ccc2I QWXLFOQRYNAVKU-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 208000036142 Viral infection Diseases 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- SLRCCWJSBJZJBV-UHFFFAOYSA-N alpha-isosparteine Natural products C1N2CCCCC2C2CN3CCCCC3C1C2 SLRCCWJSBJZJBV-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- YAVXLTMRALFZIS-UHFFFAOYSA-N piperidine-2-carbonitrile Chemical compound N#CC1CCCCN1 YAVXLTMRALFZIS-UHFFFAOYSA-N 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 230000003381 solubilizing effect Effects 0.000 description 1
- SLRCCWJSBJZJBV-AJNGGQMLSA-N sparteine Chemical compound C1N2CCCC[C@H]2[C@@H]2CN3CCCC[C@H]3[C@H]1C2 SLRCCWJSBJZJBV-AJNGGQMLSA-N 0.000 description 1
- 229960001945 sparteine Drugs 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Abstract
The invention relates to a method for synthesis of pyrrolo[1,2-a]quinoxaline derivatives and belongs to the technical field of chemical preparation. The method comprises the following steps that 2-halogenated arylamine and a 2-formyl azole compound as raw materials are weighed according to a mole ratio of 1-2: 1; the weighed raw materials are dissolved in an organic solvent; a transition metal salt, a ligand and an alkaline medium are added into the solution; the mixed solution undergo a reaction in an inert gas protective atmosphere at a temperature of 100-110 DEG C with stirring for 15-20h to produce the pyrrolo[1,2-a]quinoxaline derivative; and the pyrrolo[1,2-a]quinoxaline derivative is subjected to cooling, extraction, drying and reduced pressure distillation to form a pure product. The method for synthesis of the pyrrolo[1,2-a]quinoxaline derivatives has the advantages that 1, reaction conditions are mild, catalytic activity is high, a reaction yield is high and can reach to 90%, product selectivity is high, and a substrate expanding rang is wide; and 2, through a catalysis system, an expensive ligand is avoided, a reaction temperature is reduced, a cost is low, safety and convenience are obtained, and the pollution produced by the reaction system on the environment is low.
Description
Technical field
The present invention relates to the organic synthesis field, be specifically related to the method for a kind of synthetic pyrroles [1,2-a] quinoxaline derivatives.
Background technology
The pyrroles [1,2-a] quinoxaline derivatives is a kind of important benzopyrazines heterocyclic compounds, there is higher thermostability and electron affinity energy, quinoxaline compounds, because its inner distinctive molecular conjugation structure is many important skeletons that the important biomolecule active compound is arranged, also is widely used in fluorescence probe material simultaneously.Traditional synthetic pyrroles [1,2-a] method of quinoxaline derivatives is through two steps: at first by aryl 1,2-diamine compounds and 2,5-diethoxy tetrahydrofuran (THF) generates 1-2-aminophenyl pyrroles under the condition of heating, then add formic acid, reflux 10～13h obtains product, and productive rate is 28%(Cheeseman et al.Chem.Ind, 1965,1382.).
In recent years, the method for synthetic pyrroles [1,2-a] quinoxaline derivatives that many bibliographical informations arranged: such as people such as Kobayashi, reported and used BF
3(OEt
2) catalysis 1-2-Cyanophenylpyrrole and alkane ketone under the existence of methylene dichloride, 0 ℃ of reaction obtain pyrroles [1,2-a] quinoxaline derivatives (Kobayashi et al.Chem.Lett, 1998,551-552.); Harrak has reported that in 2007 1-2-nitrophenyl pyrroles is at phosphorus oxychloride and N, under the existence of dinethylformamide, reaction first generates 1-2-nitrophenyl-1H-pyrrole-2-aldehyde, then obtain pyrroles [1 through intramolecular C-N linked reaction, 2-a] quinoxaline derivatives (Harrak et al.Arkivoc, 2007,4,251-259.); Jonathan at 2009 annual reports by pyrrole-2-aldehyde and 2-Iodoaniline at CuI, K
3pO
4, NMP and sparteine catalysis under, 130 ℃ are stirred 24h and obtain pyrroles [1,2-a] quinoxaline derivatives (Jonathan T.Reeves, J.Org.Chem.2010,75,992 – 994.); Use AlCl
3/ BtH/THF mixed solvent catalysis 1-2-aminophenyl pyrrole derivative and corresponding aldehyde stir at normal temperatures 1～2h obtain pyrroles [1,2-a] quinoxaline derivatives (Akhilesh et al.Eur.J.Org.Chem, 2011,4,6998-7010.); Maria in 2012 reported 1-2-nitrophenyl pyrroles with corresponding alcohol under the existence of fe and hydrochloric acid, in air, reflux obtain pyrroles [1,2-a] quinoxaline derivatives (Maria et al.Org.Lett, 2012,4,251-259.).
But, above-mentioned the whole bag of tricks all exists some defects, reactions steps is more loaded down with trivial details, condition is harsher, productive rate is lower, aftertreatment is more difficult, use some virose solvents, especially need complicated part, fancy price, stronger toxicity and the dependence of complex substrate has seriously been restricted to its industrial applications in a lot of fields.
Summary of the invention
The object of the present invention is to provide the method for a kind of synthetic pyrroles [1,2-a] quinoxaline derivatives.The method is low-cost, productive rate is high, the substrate suitability is wide.
For achieving the above object; the technical solution used in the present invention is: a kind of synthetic pyrroles [1; 2-a] method of quinoxaline derivatives, take 2-halogen arylamine and 2-formyl radical azole compounds as synthetic pyrroles [1, the 2-a] quinoxaline derivatives of reactant: specifically comprise the following steps:
By 2-halogen arylamine, with 2-formyl radical azole compounds amount of substance ratio, be 1～2:1, get 2-halogen arylamine and 2-formyl radical azole compounds is dissolved in organic solvent, add mantoquita, part, alkaline medium, under protection of inert gas, 100～110 ℃ are stirred reaction in 15～20 hours and obtain pyrroles [1,2-a] quinoxaline derivatives;
Reaction process is as follows:
The structural formula of preferred 2-halogen arylamine described above is as follows:
2-halogen arylamine is selected from: adjacent Iodoaniline
o-bromoaniline
2-amino-3-iodine pyridine
2-amino-3-bromopyridine
5-amino-4-iodine pyrimidine
5-amino-4-bromo pyrimi piperidine
4-amino-3-iodine phenylfluoroform
4-amino-3-ioxynil
4-amino-3-iodo-benzoic acid methyl esters
the fluoro-2-Iodoaniline of 5-
4-amino-3-5 bromine benzotrifluoride
4-amino-3-bromine trifluorobenzonitrile
4-amino-3-methyl-bromobenzoate
the fluoro-2-bromaniline of 5-
the iodo-5-5-flumethiazine of 2-amino-3-
the iodo-nicotinic acid nitrile of 6-amino-5-
6-amino-5-iodine nicotinic acid methyl ester
the fluoro-3-iodine pyridine of 6--2-amine
the bromo-2-chlorin-5-trifluoro picoline of 3-
the bromo-nicotinic acid nitrile of 6-amino-5-
6-amino-5-bromo-nicotinic acid methyl esters
the bromo-6-fluorine pyridine of 3--2-amine
the iodo-2-trifluoromethyl pyrimidine of 4--5-amine
the bromo-2-trifluoromethyl pyrimidine of 4--5-amine
5-amido-4-bromo pyrimi piperidine-2-nitrile
methyl 5-amido-4 bromo pyrimi piperidines-2-carboxyl
methyl 5-amido-4 iodine pyrimidines-2-carboxyl
the fluoro-4-iodine pyrimidine of 2--5-amido
or the fluoro-4-bromo pyrimi piperidine of 2--5-amido
in a kind of.
The structural formula of preferred above-mentioned 2-formyl radical azole compounds is as follows:
wherein Z can be selected from respectively: a kind of in carbon or nitrogen, Het can be selected from respectively: phenyl, the 2-aminomethyl phenyl, the 2-p-methoxy-phenyl, the 2-fluorophenyl, the 2-chloro-phenyl-, the 2-bromophenyl, the 2-iodophenyl, the 2-benzoylphenyl, the 2-nitrophenyl, the 3-aminomethyl phenyl, the 3-p-methoxy-phenyl, the 3-fluorophenyl, the 3-chloro-phenyl-, the 3-bromophenyl, the 3-iodophenyl, the 3-benzoylphenyl, the 3-nitrophenyl, the 4-aminomethyl phenyl, the 4-p-methoxy-phenyl, the 4-fluorophenyl, the 4-chloro-phenyl-, the 4-bromophenyl, the 4-iodophenyl, the 4-benzoylphenyl, the 4-nitrophenyl, the 5-aminomethyl phenyl, the 5-p-methoxy-phenyl, the 5-fluorophenyl, the 5-chloro-phenyl-, the 5-bromophenyl, the 5-iodophenyl, the 5-benzoylphenyl, the 5-nitrophenyl, 1,2,3,4-tetralyl, the 5-methyl isophthalic acid, 2,3,4-tetralyl, 5-methoxyl group-1,2,3, the 4-tetralyl, 5-is fluoro-1,2,3, the 4-tetralyl, 5-is chloro-1,2,3, the 4-tetralyl, 5-is bromo-1,2,3, the 4-tetralyl, 5-is iodo-1,2,3, the 4-tetralyl, 5-benzoyl-1,2,3, the 4-tetralyl, 5-nitro-1,2,3, the 4-tetralyl, the 6-methyl isophthalic acid, 2,3,4-tetralyl, 6-methoxyl group-1,2,3, the 4-tetralyl, 6-is fluoro-1,2,3, the 4-tetralyl, 6-is chloro-1,2,3, the 4-tetralyl, 6-is bromo-1,2,3, the 4-tetralyl, 6-is iodo-1,2,3, the 4-tetralyl, 6-benzoyl-1,2,3, the 4-tetralyl, 6-nitro-1,2,3, the 4-tetralyl, the 7-methyl isophthalic acid, 2,3,4-tetralyl, 7-methoxyl group-1,2,3, the 4-tetralyl, 7-is fluoro-1,2,3, the 4-tetralyl, 7-is chloro-1,2,3, the 4-tetralyl, 7-is bromo-1,2,3, the 4-tetralyl, 7-is iodo-1,2,3, the 4-tetralyl, 7-benzoyl-1,2,3, the 4-tetralyl, 7-nitro-1,2,3, a kind of in 4-tetralyl or 4,5,6,7,8,9-hexahydro--1H-cyclooctane base.
2-formoxyl azole compounds is selected from: pyrrole-2-aldehyde
Imidazoles-2-formaldehyde
Pyrazoles-2-formaldehyde
3,5-dimethyl-2-pyrrole aldehyde
3-methyl-pyrazoles-5-formaldehyde
4-methyl-imidazoles-2-formaldehyde
5-phenyl-pyrrole-2-aldehyde
4-phenyl-pyrrole-2-aldehyde
3-phenyl-pyrrole-2-aldehyde
Indoles-2 formaldehyde
4-methyl-indoles-2 formaldehyde
5-methyl-indoles-2 formaldehyde
6-methyl-indoles-2 formaldehyde
7-methyl-indoles-2 formaldehyde
4-methoxyl group-indoles-2 formaldehyde
5-methoxyl group-indoles-2 formaldehyde
6-methoxyl group-indoles-2 formaldehyde
7-methoxyl group-indoles-2 formaldehyde
4-is fluorine-based-indoles-2 formaldehyde
5-is fluorine-based-indoles-2 formaldehyde
6-is fluorine-based-indoles-2 formaldehyde
7-is fluorine-based-indoles-2 formaldehyde
4-chloro-indoles-2 formaldehyde
5-chloro-indoles-2 formaldehyde
6-chloro-indoles-2 formaldehyde
7-chloro-indoles-2 formaldehyde
4-bromo-indoles-2 formaldehyde
5-bromo-indoles-2 formaldehyde
6-bromo-indoles-2 formaldehyde
7-bromo-indoles-2 formaldehyde
4-iodo-indoles-2 formaldehyde
5-iodo-indoles-2 formaldehyde
6-iodo-indoles-2 formaldehyde
7-iodo-indoles-2 formaldehyde
4-nitro-indoles-2 formaldehyde
5-nitro-indoles-2 formaldehyde
6-nitro-indoles-2 formaldehyde
7-nitro-indoles-2 formaldehyde
Benzimidazolyl-2 radicals formaldehyde
4-nitro-benzimidazolyl-2 radicals formaldehyde
5-nitro-benzimidazolyl-2 radicals formaldehyde
6-nitro-benzimidazolyl-2 radicals formaldehyde
4-iodo-benzimidazolyl-2 radicals formaldehyde
5-iodo-benzimidazolyl-2 radicals formaldehyde
6-iodo-benzimidazolyl-2 radicals formaldehyde
7-iodo-benzimidazolyl-2 radicals formaldehyde
4-bromo-benzimidazolyl-2 radicals formaldehyde
5-bromo-benzimidazolyl-2 radicals formaldehyde
6-bromo-benzimidazolyl-2 radicals formaldehyde
7-bromo-benzimidazolyl-2 radicals formaldehyde
4-chloro-benzimidazolyl-2 radicals formaldehyde
5-chloro-benzimidazolyl-2 radicals formaldehyde
6-chloro-benzimidazolyl-2 radicals formaldehyde
7-chloro-benzimidazolyl-2 radicals formaldehyde
4-is fluorine-based-benzimidazolyl-2 radicals formaldehyde
5-is fluorine-based-benzimidazolyl-2 radicals formaldehyde
6-is fluorine-based-benzimidazolyl-2 radicals formaldehyde
7-is fluorine-based-benzimidazolyl-2 radicals formaldehyde
4-methyl-benzimidazolyl-2 radicals formaldehyde
5-methyl-benzimidazolyl-2 radicals formaldehyde
6-methyl-benzimidazolyl-2 radicals formaldehyde
7-methyl-benzimidazolyl-2 radicals formaldehyde
4-methoxyl group-benzimidazolyl-2 radicals formaldehyde
5-methoxyl group-benzimidazolyl-2 radicals formaldehyde
6-methoxyl group-benzimidazolyl-2 radicals formaldehyde
7-methoxyl group-benzimidazolyl-2 radicals formaldehyde
4,5-dihydro-benzindole-2-formaldehyde
6-methyl-4,5-dihydro-benzindole-2-formaldehyde
7-methyl-4,5-dihydro-benzindole-2-formaldehyde
8-methyl-4,5-dihydro-benzindole-2-formaldehyde
9-methyl-4,5-dihydro-benzindole-2-formaldehyde
6-methoxyl group-4,5-dihydro-benzindole-2-formaldehyde
7-methoxyl group-4,5-dihydro-benzindole-2-formaldehyde
8-methoxyl group-4,5-dihydro-benzindole-2-formaldehyde
9-methoxyl group-4,5-dihydro-benzindole-2-formaldehyde
Or 4,5,6,7,8,9-hexahydro-1H-cyclooctane-pyrrole-2-aldehyde
In a kind of.
Described alkaline medium is phosphate radical metal-salt, carbonate metal-salt or hydroxide radical metal-salt, and molecular formula is (M)
3pO
4, (M)
2cO
3or M (OH), wherein metal M is selected from a kind of of caesium (Cs), sodium (Na) or potassium (K); More preferably alkaline medium is K
3pO
4, CS
2cO
3, K
2cO
3or a kind of in NaOH; Alkaline medium is 2～3:1 with the ratio of the amount of substance of 2-formyl radical azole compounds.
Preferred described mantoquita is CuI, CuBr, Cu
2o or Cu
2a kind of in Cl.Preferred described part is L-PROLINE, 2, a kind of in 2-dipyridyl, oxine or 1,10-phenanthroline.
Preferably the add-on of mantoquita is that mantoquita and 2-formyl radical azole compounds amount of substance ratio are 0.1～0.2:1; Part and 2-formyl radical azole compounds amount of substance ratio are 0.2～0.3:1.
Preferred described organic solvent is a kind of in acetonitrile, dimethyl formamide, dimethyl sulfoxide (DMSO) (DMSO) or toluene.The add-on of solvent is generally the solubilizing reaction thing and gets final product.
Preferred described rare gas element is nitrogen or argon gas.
In technique scheme, reaction needs inert nitrogen gas or argon shield, and 100～110 ℃ are stirred end in 15～20 hours, and system obtains product through cooling, extraction, drying, underpressure distillation, after recrystallization, can obtain highly purified product.
Beneficial effect:
1. due to alkaline medium, the application of part and reactant 2-formyl radical azole compounds and 2-halogen arylamine, this reaction can be carried out at lower temperature, and reaction conditions is simple, gentleness, and reaction yield is high, can reach 90% productive rate.
2. take phosphate radical metal-salt, carbonate metal-salt or hydroxide radical metal-salt is alkaline medium, and reaction system adds cheap part can obtain target product, has solved the increase problem of final product Financial cost, has reduced the pollution to environment; Product can complete aftertreatment through overcooling, extraction, drying, underpressure distillation, washing, recrystallization, and aftertreatment is simple, convenient.
3. above-mentioned set up catalyst system, suitability is extensive, and the transformation efficiency of substrate and the productive rate of product are all higher, have expanded the industrial applications in a lot of fields.
Embodiment
Below in conjunction with embodiment, the invention will be further described, but embodiment does not limit the present invention in any way:
Embodiment 1:
The present embodiment is the synthetic of pyrroles [1,2-a] quinoxaline, with 2-Iodoaniline, pyrroles-2 formaldehyde, K
3pO
4, CuI, dimethyl formamide, 2, the 2-dipyridyl is raw material, its reaction formula is as follows:
Preparation method: add 0.215mmol pyrroles-2 formaldehyde in the 25ml eggplant-shape bottle, 0.215mmol2-Iodoaniline, 0.645mmolK
3pO
4, 0.0215mmol CuI, 0.043mmol2, the 2-dipyridyl, then add the 1.5ml dimethyl formamide, and nitrogen protection, 110 ℃ are stirred 20 hours, and solution colour becomes transparent color, has product to generate.
Reaction solution is filtered and obtains white solid after cooling, extraction, drying, underpressure distillation, washing, recrystallization.
Productive rate 89%, this pyrroles [1,2-a] quinoxaline fusing point is 131-133 ℃; Nucleus magnetic hydrogen spectrum (500Hz, CDCl
3): δ 8.79 (s, 1H), 7.94 (d, J=7.95Hz, 1H), 7.89 (s, 1H), 7.82 (d, J=8.15Hz, 1H), 7.51-7.48 (m, 1H), 7.44-7.41 (m, 1H), 6.88-6.86 (m, 2H); High resolution mass spectrum: m/z (%), calcd for C
11h
9n
2(M
*) 169.0760, found:169.0769.
Embodiment 2:
The present embodiment is the synthetic of pyrroles [1,2-a] quinoxaline, with 2-Iodoaniline, pyrroles-2 formaldehyde, K
3pO
4, CuI, dimethyl formamide, 2, the 2-dipyridyl is raw material, its reaction formula is as follows:
Preparation method: add 0.215mmol pyrroles-2 formaldehyde in the 25ml eggplant-shape bottle, 0.215mmol2-Iodoaniline, 0.645mmolK
3pO
4, 0.0215mmol CuI, 0.043mmol2, the 2-dipyridyl, then add the 1.5ml dimethyl formamide, and argon shield, 110 ℃ are stirred 20 hours, and solution colour becomes transparent color, has product to generate.
Reaction solution is filtered and obtains white solid after cooling, extraction, drying, underpressure distillation, washing, recrystallization.
Productive rate 89%, this pyrroles [1,2-a] quinoxaline fusing point is 131-133 ℃; Nucleus magnetic hydrogen spectrum (500Hz, CDCl
3): δ 8.79 (s, 1H), 7.94 (d, J=7.95Hz, 1H), 7.89 (s, 1H), 7.82 (d, J=8.15Hz, 1H), 7.51-7.48 (m, 1H), 7.44-7.41 (m, 1H), 6.88-6.86 (m, 2H); High resolution mass spectrum: m/z (%), calcd for C
11h
9n
2(M
*) 169.0760, found:169.0769.
Embodiment 3:
The present embodiment is the synthetic of pyrroles [1,2-a] quinoxaline, with 2-Iodoaniline, pyrroles-2 formaldehyde, K
3pO
4, CuI, dimethyl formamide, 2, the 2-dipyridyl is raw material, its reaction formula is as follows:
Preparation method: add 0.215mmol pyrroles-2 formaldehyde in the 25ml eggplant-shape bottle, 0.215mmol2-Iodoaniline, 0.645mmolCs
2cO
3, 0.0215mmol CuI, 0.043mmol2, the 2-dipyridyl, then add the 1.5ml dimethyl formamide, and nitrogen protection, 110 ℃ are stirred 20 hours, and solution colour becomes transparent color, has product to generate.
Reaction solution is filtered and obtains white solid after cooling, extraction, drying, underpressure distillation, washing, recrystallization.
Productive rate 80%, this pyrroles [1,2-a] quinoxaline fusing point is 131-133 ℃; Nucleus magnetic hydrogen spectrum (500Hz, CDCl
3): δ 8.79 (s, 1H), 7.94 (d, J=7.95Hz, 1H), 7.89 (s, 1H), 7.82 (d, J=8.15Hz, 1H), 7.51-7.48 (m, 1H), 7.44-7.41 (m, 1H), 6.88-6.86 (m, 2H); High resolution mass spectrum: m/z (%), calcd for C
11h
9n
2(M
*) 169.0760, found:169.0769.
Embodiment 4:
The present embodiment is the synthetic of pyrroles [1,2-a] quinoxaline, with 2-Iodoaniline, pyrroles-2 formaldehyde, K
3pO
4, CuI, dimethyl formamide, 2, the 2-dipyridyl is raw material, its reaction formula is as follows:
Preparation method: add 0.215mmol pyrroles-2 formaldehyde in the 25ml eggplant-shape bottle; 0.215mmol2-Iodoaniline; 0.645mmolNaOH, 0.0215mmol CuI, 0.043mmol2; the 2-dipyridyl; add again the 1.5ml dimethyl formamide, nitrogen protection, 110 ℃ are stirred 20 hours; solution colour becomes transparent color, has product to generate.
Reaction solution is filtered and obtains white solid after cooling, extraction, drying, underpressure distillation, washing, recrystallization.
Productive rate 85%, this pyrroles [1,2-a] quinoxaline fusing point is 131-133 ℃; Nucleus magnetic hydrogen spectrum (500Hz, CDCl
3): δ 8.79 (s, 1H), 7.94 (d, J=7.95Hz, 1H), 7.89 (s, 1H), 7.82 (d, J=8.15Hz, 1H), 7.51-7.48 (m, 1H), 7.44-7.41 (m, 1H), 6.88-6.86 (m, 2H); High resolution mass spectrum: m/z (%), calcd for C
11h
9n
2(M
*) 169.0760, found:169.0769.
Embodiment 5:
The present embodiment is the synthetic of pyrroles [1,2-a] quinoxaline, with 2-Iodoaniline, pyrroles-2 formaldehyde, K
3pO
4, CuI, dimethyl formamide, 2, the 2-dipyridyl is raw material, its reaction formula is as follows:
Preparation method: add 0.215mmol pyrroles-2 formaldehyde in the 25ml eggplant-shape bottle, 0.215mmol2-Iodoaniline, 0.645mmolK
3pO
4, 0.0215mmol CuBr, 0.043mmol2, the 2-dipyridyl, then add the 1.5ml dimethyl formamide, and nitrogen protection, 110 ℃ are stirred 20 hours, and solution colour becomes transparent color, has product to generate.
Reaction solution is filtered and obtains white solid after cooling, extraction, drying, underpressure distillation, washing, recrystallization.
Productive rate 56%, this pyrroles [1,2-a] quinoxaline fusing point is 131-133 ℃; Nucleus magnetic hydrogen spectrum (500Hz, CDCl
3): δ 8.79 (s, 1H), 7.94 (d, J=7.95Hz, 1H), 7.89 (s, 1H), 7.82 (d, J=8.15Hz, 1H), 7.51-7.48 (m, 1H), 7.44-7.41 (m, 1H), 6.88-6.86 (m, 2H); High resolution mass spectrum: m/z (%), calcd for C
11h
9n
2(M
*) 169.0760, found:169.0769.
Embodiment 6:
The present embodiment is the synthetic of pyrroles [1,2-a] quinoxaline, with 2-Iodoaniline, pyrroles-2 formaldehyde, K
3pO
4, CuI, dimethyl formamide, 2, the 2-dipyridyl is raw material, its reaction formula is as follows:
Preparation method: add 0.215mmol pyrroles-2 formaldehyde in the 25ml eggplant-shape bottle, 0.215mmol2-Iodoaniline, 0.645mmolK
3pO
4, 0.0215mmol Cu
2cl, 0.043mmol2, the 2-dipyridyl, then add the 1.5ml dimethyl formamide, and nitrogen protection, 110 ℃ are stirred 20 hours, and solution colour becomes transparent color, has product to generate.
Reaction solution is filtered and obtains white solid after cooling, extraction, drying, underpressure distillation, washing, recrystallization.
Productive rate 37%, this pyrroles [1,2-a] quinoxaline fusing point is 131-133 ℃; Nucleus magnetic hydrogen spectrum (500Hz, CDCl
3): δ 8.79 (s, 1H), 7.94 (d, J=7.95Hz, 1H), 7.89 (s, 1H), 7.82 (d, J=8.15Hz, 1H), 7.51-7.48 (m, 1H), 7.44-7.41 (m, 1H), 6.88-6.86 (m, 2H); High resolution mass spectrum: m/z (%), calcd for C
11h
9n
2(M
*) 169.0760, found:169.0769.
Embodiment 7:
The present embodiment is the synthetic of pyrroles [1,2-a] quinoxaline, with 2-Iodoaniline, pyrroles-2 formaldehyde, K
3pO
4, CuI, dimethyl formamide, 2, the 2-dipyridyl is raw material, its reaction formula is as follows:
Preparation method: add 0.215mmol pyrroles-2 formaldehyde in the 25ml eggplant-shape bottle, 0.215mmol2-Iodoaniline, 0.645mmolK
3pO
4, 0.0215mmol CuI, the 0.043mmol L-PROLINE, then add the 1.5ml dimethyl formamide, and nitrogen protection, 110 ℃ are stirred 20 hours, and solution colour becomes transparent color, has product to generate.
Reaction solution is filtered and obtains white solid after cooling, extraction, drying, underpressure distillation, washing, recrystallization.
Productive rate 76%, this pyrroles [1,2-a] quinoxaline fusing point is 131-133 ℃; Nucleus magnetic hydrogen spectrum (500Hz, CDCl
3): δ 8.79 (s, 1H), 7.94 (d, J=7.95Hz, 1H), 7.89 (s, 1H), 7.82 (d, J=8.15Hz, 1H), 7.51-7.48 (m, 1H), 7.44-7.41 (m, 1H), 6.88-6.86 (m, 2H); High resolution mass spectrum: m/z (%), calcd for C
11h
9n
2(M
*) 169.0760, found:169.0769.
Embodiment 8:
The present embodiment is the synthetic of pyrroles [1,2-a] quinoxaline, with 2-Iodoaniline, pyrroles-2 formaldehyde, K
3pO
4, CuI, dimethyl formamide, 2, the 2-dipyridyl is raw material, its reaction formula is as follows:
Preparation method: add 0.215mmol pyrroles-2 formaldehyde in the 25ml eggplant-shape bottle, 0.215mmol2-Iodoaniline, 0.645mmolK
3pO
4, 0.0215mmol CuI, the 0.043mmol8-hydroxyquinoline, then add the 1.5ml dimethyl formamide, and nitrogen protection, 110 ℃ are stirred 20 hours, and solution colour becomes transparent color, has product to generate.
Reaction solution is filtered and obtains white solid after cooling, extraction, drying, underpressure distillation, washing, recrystallization.
Productive rate 67%, this pyrroles [1,2-a] quinoxaline fusing point is 131-133 ℃; Nucleus magnetic hydrogen spectrum (500Hz, CDCl
3): δ 8.79 (s, 1H), 7.94 (d, J=7.95Hz, 1H), 7.89 (s, 1H), 7.82 (d, J=8.15Hz, 1H), 7.51-7.48 (m, 1H), 7.44-7.41 (m, 1H), 6.88-6.86 (m, 2H); High resolution mass spectrum: m/z (%), calcd for C
11h
9n
2(M
*) 169.0760, found:169.0769.
Embodiment 9:
The present embodiment is the synthetic of pyrroles [1,2-a] quinoxaline, with 2-Iodoaniline, pyrroles-2 formaldehyde, K
3pO
4, CuI, dimethyl formamide, 2, the 2-dipyridyl is raw material, its reaction formula is as follows:
Preparation method: add 0.215mmol pyrroles-2 formaldehyde in the 25ml eggplant-shape bottle, 0.215mmol2-Iodoaniline, 0.645mmolK
3pO
4, 0.0215mmol CuI, 0.043mmol2, the 2-dipyridyl, then add 1.5ml DMSO, and nitrogen protection, 110 ℃ are stirred 20 hours, and solution colour becomes transparent color, has product to generate.
Reaction solution is filtered and obtains white solid after cooling, extraction, drying, underpressure distillation, washing, recrystallization.
Productive rate 82%, this pyrroles [1,2-a] quinoxaline fusing point is 131-133 ℃; Nucleus magnetic hydrogen spectrum (500Hz, CDCl
3): δ 8.79 (s, 1H), 7.94 (d, J=7.95Hz, 1H), 7.89 (s, 1H), 7.82 (d, J=8.15Hz, 1H), 7.51-7.48 (m, 1H), 7.44-7.41 (m, 1H), 6.88-6.86 (m, 2H); High resolution mass spectrum: m/z (%), calcd for C
11h
9n
2(M
*) 169.0760, found:169.0769.
Embodiment 10:
The present embodiment is the synthetic of pyrroles [1,2-a] quinoxaline, with 2-Iodoaniline, pyrroles-2 formaldehyde, K
3pO
4, CuI, dimethyl formamide, 2, the 2-dipyridyl is raw material, its reaction formula is as follows:
Preparation method: add 0.215mmol pyrroles-2 formaldehyde in the 25ml eggplant-shape bottle, 0.215mmol2-Iodoaniline, 0.645mmolK
3pO
4, 0.0215mmol CuI, 0.043mmol2, the 2-dipyridyl, then add 1.5ml toluene, and nitrogen protection, 110 ℃ are stirred 20 hours, and solution colour becomes transparent color, has product to generate.
Reaction solution is filtered and obtains white solid after cooling, extraction, drying, underpressure distillation, washing, recrystallization.
Productive rate 79%, this pyrroles [1,2-a] quinoxaline fusing point is 131-133 ℃; Nucleus magnetic hydrogen spectrum (500Hz, CDCl
3): δ 8.79 (s, 1H), 7.94 (d, J=7.95Hz, 1H), 7.89 (s, 1H), 7.82 (d, J=8.15Hz, 1H), 7.51-7.48 (m, 1H), 7.44-7.41 (m, 1H), 6.88-6.86 (m, 2H); High resolution mass spectrum: m/z (%), calcd for C
11h
9n
2(M
*) 169.0760, found:169.0769.
Embodiment 11:
The present embodiment is the synthetic of pyrroles [1,2-a] quinoxaline, with 2-Iodoaniline, pyrroles-2 formaldehyde, K
3pO
4, CuI, dimethyl formamide, 2, the 2-dipyridyl is raw material, its reaction formula is as follows:
Preparation method: add 0.215mmol pyrroles-2 formaldehyde in the 25ml eggplant-shape bottle, 0.215mmol2-Iodoaniline, 0.645mmolK
3pO
4, 0.0215mmol CuI, 0.043mmol2, the 2-dipyridyl, then add the 1.5ml dimethyl formamide, and nitrogen protection, 100 ℃ are stirred 20 hours, and solution colour becomes transparent color, has product to generate.
Reaction solution is filtered and obtains white solid after cooling, extraction, drying, underpressure distillation, washing, recrystallization.
Productive rate 76%, this pyrroles [1,2-a] quinoxaline fusing point is 131-133 ℃; Nucleus magnetic hydrogen spectrum (500Hz, CDCl
3): δ 8.79 (s, 1H), 7.94 (d, J=7.95Hz, 1H), 7.89 (s, 1H), 7.82 (d, J=8.15Hz, 1H), 7.51-7.48 (m, 1H), 7.44-7.41 (m, 1H), 6.88-6.86 (m, 2H); High resolution mass spectrum: m/z (%), calcd for C
11h
9n
2(M
*) 169.0760, found:169.0769.
Embodiment 12:
The present embodiment is the synthetic of pyrroles [1,2-a] quinoxaline, with 2-Iodoaniline, pyrroles-2 formaldehyde, K
3pO
4, CuI, dimethyl formamide, 2, the 2-dipyridyl is raw material, its reaction formula is as follows:
Preparation method: add 0.215mmol pyrroles-2 formaldehyde in the 25ml eggplant-shape bottle, 0.215mmol2-Iodoaniline, 0.645mmolK
3pO
4, 0.0215mmol CuI, 0.043mmol2, the 2-dipyridyl, then add the 1.5ml dimethyl formamide, and nitrogen protection, 110 ℃ are stirred 15 hours, and solution colour becomes transparent color, has product to generate.
Reaction solution is filtered and obtains white solid after cooling, extraction, drying, underpressure distillation, washing, recrystallization.
Productive rate 75%, this pyrroles [1,2-a] quinoxaline fusing point is 131-133 ℃; Nucleus magnetic hydrogen spectrum (500Hz, CDCl
3): δ 8.79 (s, 1H), 7.94 (d, J=7.95Hz, 1H), 7.89 (s, 1H), 7.82 (d, J=8.15Hz, 1H), 7.51-7.48 (m, 1H), 7.44-7.41 (m, 1H), 6.88-6.86 (m, 2H); High resolution mass spectrum: m/z (%), calcd for C
11h
9n
2(M
*) 169.0760, found:169.0769.
Embodiment 13:
The present embodiment is the synthetic of pyrroles [1,2-a] quinoxaline, with 2-Iodoaniline, pyrroles-2 formaldehyde, K
3pO
4, CuI, dimethyl formamide, 2, the 2-dipyridyl is raw material, its reaction formula is as follows:
Preparation method: add 0.215mmol pyrroles-2 formaldehyde in the 25ml eggplant-shape bottle, 0.43mmol2-Iodoaniline, 0.645mmolK
3pO
4, 0.0215mmol CuI, 0.043mmol2, the 2-dipyridyl, then add the 1.5ml dimethyl formamide, and nitrogen protection, 110 ℃ are stirred 20 hours, and solution colour becomes transparent color, has product to generate.
Reaction solution is filtered and obtains white solid after cooling, extraction, drying, underpressure distillation, washing, recrystallization.
Productive rate 89%, this pyrroles [1,2-a] quinoxaline fusing point is 131-133 ℃; Nucleus magnetic hydrogen spectrum (500Hz, CDCl
3): δ 8.79 (s, 1H), 7.94 (d, J=7.95Hz, 1H), 7.89 (s, 1H), 7.82 (d, J=8.15Hz, 1H), 7.51-7.48 (m, 1H), 7.44-7.41 (m, 1H), 6.88-6.86 (m, 2H); High resolution mass spectrum: m/z (%), calcd for C
11h
9n
2(M
*) 169.0760, found:169.0769.
Embodiment 14:
The present embodiment is the synthetic of pyrroles [1,2-a] quinoxaline, with 2-Iodoaniline, pyrroles-2 formaldehyde, K
3pO
4, CuI, dimethyl formamide, 2, the 2-dipyridyl is raw material, its reaction formula is as follows:
Preparation method: add 0.215mmol pyrroles-2 formaldehyde in the 25ml eggplant-shape bottle, 0.215mmol2-Iodoaniline, 0.43mmolK
3pO
4, 0.0215mmol CuI, 0.043mmol2, the 2-dipyridyl, then add the 1.5ml dimethyl formamide, and nitrogen protection, 110 ℃ are stirred 20 hours, and solution colour becomes transparent color, has product to generate.
Reaction solution is filtered and obtains white solid after cooling, extraction, drying, underpressure distillation, washing, recrystallization.
Productive rate 65%, this pyrroles [1,2-a] quinoxaline fusing point is 131-133 ℃; Nucleus magnetic hydrogen spectrum (500Hz, CDCl
3): δ 8.79 (s, 1H), 7.94 (d, J=7.95Hz, 1H), 7.89 (s, 1H), 7.82 (d, J=8.15Hz, 1H), 7.51-7.48 (m, 1H), 7.44-7.41 (m, 1H), 6.88-6.86 (m, 2H); High resolution mass spectrum: m/z (%), calcd for C
11h
9n
2(M
*) 169.0760, found:169.0769.
Embodiment 15:
The present embodiment is the synthetic of pyrroles [1,2-a] quinoxaline, with 2-Iodoaniline, pyrroles-2 formaldehyde, K
3pO
4, CuI, dimethyl formamide, 2, the 2-dipyridyl is raw material, its reaction formula is as follows:
Preparation method: add 0.215mmol pyrroles-2 formaldehyde in the 25ml eggplant-shape bottle, 0.215mmol2-Iodoaniline, 0.645mmolK
3pO
4, 0.043mmol CuI, 0.043mmol2, the 2-dipyridyl, then add the 1.5ml dimethyl formamide, and nitrogen protection, 110 ℃ are stirred 20 hours, and solution colour becomes transparent color, has product to generate.
Reaction solution is filtered and obtains white solid after cooling, extraction, drying, underpressure distillation, washing, recrystallization.
Productive rate 89%, this pyrroles [1,2-a] quinoxaline fusing point is 131-133 ℃; Nucleus magnetic hydrogen spectrum (500Hz, CDCl
3): δ 8.79 (s, 1H), 7.94 (d, J=7.95Hz, 1H), 7.89 (s, 1H), 7.82 (d, J=8.15Hz, 1H), 7.51-7.48 (m, 1H), 7.44-7.41 (m, 1H), 6.88-6.86 (m, 2H); High resolution mass spectrum: m/z (%), calcd for C
11h
9n
2(M
*) 169.0760, found:169.0769.
Embodiment 16:
The present embodiment is the synthetic of pyrroles [1,2-a] quinoxaline, with 2-Iodoaniline, pyrroles-2 formaldehyde, K
3pO
4, CuI, dimethyl formamide, 2, the 2-dipyridyl is raw material, its reaction formula is as follows:
Preparation method: add 0.215mmol pyrroles-2 formaldehyde in the 25ml eggplant-shape bottle, 0.215mmol2-Iodoaniline, 0.645mmolK
3pO
4, 0.0215mmol CuI, 0.064mmol2, the 2-dipyridyl, then add the 1.5ml dimethyl formamide, and nitrogen protection, 110 ℃ are stirred 20 hours, and solution colour becomes transparent color, has product to generate.
Reaction solution is filtered and obtains white solid after cooling, extraction, drying, underpressure distillation, washing, recrystallization.
Productive rate 89%, this pyrroles [1,2-a] quinoxaline fusing point is 131-133 ℃; Nucleus magnetic hydrogen spectrum (500Hz, CDCl
3): δ 8.79 (s, 1H), 7.94 (d, J=7.95Hz, 1H), 7.89 (s, 1H), 7.82 (d, J=8.15Hz, 1H), 7.51-7.48 (m, 1H), 7.44-7.41 (m, 1H), 6.88-6.86 (m, 2H); High resolution mass spectrum: m/z (%), calcd for C
11h
9n
2(M
*) 169.0760, found:169.0769.
Embodiment 17:
The present embodiment is the synthetic of pyrroles [1,2-a] quinoxaline, with 2-bromaniline, pyrroles-2 formaldehyde, K
3pO
4, CuI, dimethyl formamide, 2, the 2-dipyridyl is raw material, its reaction formula is as follows:
Preparation method: add 0.215mmol pyrroles-2 formaldehyde in the 25ml eggplant-shape bottle, 0.215mmol2-bromaniline, 0.645mmolK
3pO
4, 0.0215mmol CuI, 0.043mmol2, the 2-dipyridyl, then add the 1.5ml dimethyl formamide, and nitrogen protection, 110 ℃ are stirred 20 hours, and solution colour becomes transparent color, has product to generate.
Reaction solution is filtered and obtains white solid after cooling, extraction, drying, underpressure distillation, washing, recrystallization.
Productive rate 46%, this pyrroles [1,2-a] quinoxaline fusing point is 131-133 ℃; Nucleus magnetic hydrogen spectrum (500Hz, CDCl
3): δ 8.79 (s, 1H), 7.94 (d, J=7.95Hz, 1H), 7.89 (s, 1H), 7.82 (d, J=8.15Hz, 1H), 7.51-7.48 (m, 1H), 7.44-7.41 (m, 1H), 6.88-6.86 (m, 2H); High resolution mass spectrum: m/z (%), calcd for C
11h
9n
2(M
*) 169.0760, found:169.0769.
Embodiment 18:
The present embodiment is the synthetic of imidazoles [1,2-a] quinoxaline, with 2-bromaniline, imidazoles-2-formaldehyde, K
3pO
4, CuI, dimethyl formamide, 2, the 2-dipyridyl is raw material, its reaction formula is as follows:
Preparation method: add 0.215mmol imidazoles-2-formaldehyde in the 25ml eggplant-shape bottle, 0.215mmol2-bromaniline, 0.645mmolK
3pO
4, 0.0215mmol CuI, 0.043mmol2, the 2-dipyridyl, then add the 1.5ml dimethyl formamide, and nitrogen protection, 110 ℃ are stirred 20 hours, and solution colour becomes transparent color, has product to generate.
Reaction solution is filtered and obtains white solid after cooling, extraction, drying, underpressure distillation, washing, recrystallization.
Productive rate 31%, this imidazoles [1,2-a] quinoxaline fusing point is 124-126 ℃; Nucleus magnetic hydrogen spectrum (300Hz, CDCl
3); δ 9.13 (s, 1H), 8.15-8.13 (m, 2H), 7.93-7.91 (m, 1H), 7.83 (s, 1H), 7.70-7.66 (m, 1H), 7.63-7.59 (m, 1H); High resolution mass spectrum: m/z (%), calcd for C
10h
8n
3(M
*) 170.0712, found:170.0724.
Embodiment 19:
The present embodiment is the synthetic of 1,3-dimethyl-pyrroles [1,2-a] quinoxaline, with 2-Iodoaniline, 3, and 5-dimethyl-2-pyrrole aldehyde, K
3pO
4, CuI, dimethyl formamide, 2, the 2-dipyridyl is raw material, its reaction formula is as follows:
Preparation method: add 0.215mmol3 in the 25ml eggplant-shape bottle, 5-dimethyl-2-pyrrole aldehyde, 0.215mmol2-Iodoaniline, 0.645mmol K
3pO
4, 0.0215mmol CuI, 0.043mmol2, the 2-dipyridyl, then add the 1.5ml dimethyl formamide, and nitrogen protection, 110 ℃ are stirred 20 hours, and solution colour becomes transparent color, has product to generate.
Reaction solution is filtered and obtains white solid after cooling, extraction, drying, underpressure distillation, washing, recrystallization.
Productive rate 83%, this 1,3-dimethyl-pyrroles [1,2-a] quinoxaline fusing point is 65-69 ℃; Nucleus magnetic hydrogen spectrum (500Hz, CDCl
3); δ 8.64 (s, 1H), 8.13 (d, J=7.4Hz, 1H), 7.88 (d, J=7.0Hz, 1H), 7.41-7.33 (m, 2H), 6.39 (s, 1H), 2.86 (s, 3H), 2.41 (s, 3H); High resolution mass spectrum: m/z (%), calcd for C
13h
13n
2(M
*) 197.1073, found:197.1086.
Embodiment 20:
The present embodiment is the synthetic of imidazoles [1,2-a] quinoxaline, with 2-Iodoaniline, imidazoles-2-formaldehyde, K
3pO
4, CuI, dimethyl formamide, 2, the 2-dipyridyl is raw material, its reaction formula is as follows:
Preparation method: add 0.215mmol imidazoles-2-formaldehyde in the 25ml eggplant-shape bottle, 0.215mmol2-Iodoaniline, 0.645mmolK
3pO
4, 0.0215mmol CuI, 0.043mmol2, the 2-dipyridyl, then add the 1.5ml dimethyl formamide, and nitrogen protection, 110 ℃ are stirred 20 hours, and solution colour becomes transparent color, has product to generate.
Reaction solution is filtered and obtains white solid after cooling, extraction, drying, underpressure distillation, washing, recrystallization.
Productive rate 90%, this imidazoles [1,2-a] quinoxaline fusing point is 124-126 ℃; Nucleus magnetic hydrogen spectrum (300Hz, CDCl
3); δ 9.13 (s, 1H), 8.15-8.13 (m, 2H), 7.93-7.91 (m, 1H), 7.83 (s, 1H), 7.70-7.66 (m, 1H), 7.63-7.59 (m, 1H); High resolution mass spectrum: m/z (%), calcd for C
10h
8n
3(M
*) 170.0712, found:170.0724.
Embodiment 21:
The present embodiment is the synthetic of benzoglyoxaline [1,2-a] quinoxaline, with 2-Iodoaniline, benzimidazolyl-2 radicals formaldehyde, K
3pO
4, CuI, dimethyl formamide, 2, the 2-dipyridyl is raw material, its reaction formula is as follows:
Preparation method: add 0.215mmol benzimidazolyl-2 radicals formaldehyde in the 25ml eggplant-shape bottle, 0.215mmol2-Iodoaniline, 0.645mmol K
3pO
4, 0.0215mmol CuI, 0.043mmol2, the 2-dipyridyl, then add the 1.5ml dimethyl formamide, and argon shield, 110 ℃ are stirred 20 hours, and solution colour becomes transparent color, has product to generate.
Reaction solution is filtered and obtains white solid after cooling, extraction, drying, underpressure distillation, washing, recrystallization.
Productive rate 84%, this benzoglyoxaline [1,2-a] quinoxaline fusing point is 182-184 ℃; Nucleus magnetic hydrogen spectrum (300Hz, CDCl
3): δ 9.20 (s, 1H), 8.35 (d, J=8.1Hz, 1H), 8.28 (d; J=7.4Hz, 1H), 8.12 (d, J=7.8Hz, 1H), 8.06 (d; J=7.3Hz, 1H), 7.72-7.69 (m, 1H), 7.58-7.52 (m, 3H); High resolution mass spectrum: m/z (%), calcd for C
14h
10n
3(M
*) 219.0797, found:219.0789.
Embodiment 22:
The present embodiment is the synthetic of indoles [1,2-a] quinoxaline, with 2-Iodoaniline, indoles-2 formaldehyde, K
3pO
4, CuI, dimethyl formamide, 2, the 2-dipyridyl is raw material, its reaction formula is as follows:
Preparation method: add 0.215mmol indoles-2 formaldehyde in the 25ml eggplant-shape bottle, 0.215mmol2-Iodoaniline, 0.645mmolK
3pO
4, 0.0215mmol CuI, 0.043mmol2, the 2-dipyridyl, then add the 1.5ml dimethyl formamide, and nitrogen protection, 110 ℃ are stirred 20 hours, and solution colour becomes transparent color, has product to generate.
Reaction solution is filtered and obtains white solid after cooling, extraction, drying, underpressure distillation, washing, recrystallization.
Productive rate 87%, this indoles [1,2-a] quinoxaline fusing point is 109-112 ℃; Nucleus magnetic hydrogen spectrum (300Hz, CDCl
3): δ 8.94 (s, 1H), 8.44 (m, 2H), 7.98 (m, 2H), 7.62 (t, J=7.7Hz, 1H), 7.56 (t, J=7.5Hz, 1H), 7.47-7.42 (m, 2H), 7.15 (s, 1H); High resolution mass spectrum: m/z (%), calcd for C
15h
11n
2(M
*) 219.0916, found:219.0933.
Embodiment 23:
The present embodiment is the synthetic of 9-methoxy-Indole [1,2-a] quinoxaline, with 2-Iodoaniline, 5-methoxyl group-indoles-2 formaldehyde, K
3pO
4, CuI, dimethyl formamide, 2, the 2-dipyridyl is raw material, its reaction formula is as follows:
Preparation method: add 0.215mmol5-methoxyl group-indoles-2 formaldehyde in the 25ml eggplant-shape bottle, 0.215mmol2-Iodoaniline, 0.645mmol K
3pO
4, 0.0215mmol CuI, 0.043mmol2, the 2-dipyridyl, then add the 1.5ml dimethyl formamide, and nitrogen protection, 110 ℃ are stirred 20 hours, and solution colour becomes transparent color, has product to generate.
Reaction solution is filtered and obtains white solid after cooling, extraction, drying, underpressure distillation, washing, recrystallization.
Productive rate 86%, this 9-methoxy-Indole [1,2-a] quinoxaline fusing point is 133-135 ℃; Nucleus magnetic hydrogen spectrum (300Hz, CDCl
3): δ 8.89 (s, 1H), 8.35 (d, J=8.3Hz, 1H); (8.27 d, J=8.3Hz, 1H), 7.97 (d; J=7.8Hz, 1H), 7.58 (t, J=7.8Hz; 1H), 7.41 (t, J=7.7Hz, 1H); (7.28 broads, 1H), 7.18-7.16 (m, 1H); (7.03 s, 1H), 3.92 (s, 3H); High resolution mass spectrum: m/z (%), calcd for C
16h
13n
2o(M
*) 249.1022, found:249.1028.
Embodiment 24:
The present embodiment is the synthetic of 8,9,10,11,12,13-hexahydro--1H-cyclooctane-pyrroles [1,2-a] quinoxaline, with 2-Iodoaniline, 4,5,6,7,8, and 9-hexahydro--1H-cyclooctane-pyrrole-2-aldehyde, K
3pO
4, CuI, dimethyl formamide, 2, the 2-dipyridyl is raw material, its reaction formula is as follows:
Preparation method: add 0.215mmol4 in the 25ml eggplant-shape bottle, 5,6,7,8,9-hexahydro--1H-cyclooctane-pyrrole-2-aldehyde, 0.215mmol2-Iodoaniline, 0.645mmol K
3pO
4, 0.0215mmol CuI, 0.043mmol2, the 2-dipyridyl, then add the 1.5ml dimethyl formamide, and nitrogen protection, 110 ℃ are stirred 20 hours, and solution colour becomes transparent color, has product to generate.
Reaction solution is filtered and obtains white solid after cooling, extraction, drying, underpressure distillation, washing, recrystallization.
Productive rate 79%, this 8,9,10,11,12,13-hexahydro--1H-cyclooctane-pyrroles [1,2-a] quinoxaline is the soft type solid; Nucleus magnetic hydrogen spectrum (300Hz, CDCl
3): δ 8.64 (s, 1H), 8.17 (dd, J=8.4,1.2Hz; 1H), 7.94 (dd, J=7.8,1.8Hz, 1H); (7.47-7.36 m, 2H), 6.70 (s, 1H); (3.40-3.37 m, 2H), 2.82-2.79 (m, 2H); (1.99-1.92 m, 2H), 1.73-1.67 (m, 2H); (1.58-1.52 m, 2H), 1.38-1.32 (m, 2H); High resolution mass spectrum: m/z (%), calcd for C
17h
19n
2o(M
*) 251.1542, found:251.1566.
Embodiment 25:
The present embodiment is 11-methoxyl group-8,9-dihydrobenzo indoles [1,2-a] quinoxaline synthetic, and with 2-Iodoaniline, 7-methoxyl group-4,5-dihydro-benzindole-2-formaldehyde, K
3pO
4, CuI, dimethyl formamide, 2, the 2-dipyridyl is raw material, its reaction formula is as follows:
Preparation method: add 0.215mmol7-methoxyl group-4 in the 25ml eggplant-shape bottle, 5-dihydro-benzindole-2-formaldehyde, 0.215mmol2-Iodoaniline, 0.645mmol K
3pO
4, 0.0215mmol CuI, 0.043mmol2, the 2-dipyridyl, then add the 1.5ml dimethyl formamide, and nitrogen protection, 110 ℃ are stirred 20 hours, and solution colour becomes transparent color, has product to generate.
Reaction solution is filtered and obtains white solid after cooling, extraction, drying, underpressure distillation, washing, recrystallization.
Productive rate 85%, these 11-methoxyl group-8,9-dihydrobenzo indoles [1,2-a] quinoxaline fusing point is 174-178 ℃; Nucleus magnetic hydrogen spectrum (300Hz, CDCl
3): δ 8.71 (s, 1H), 8.19 (d, J=8.3Hz, 1H), 7.94 (d; J=8.0Hz, 1H), 7.64 (d, J=8.6Hz, 1H); (7.42 t, J=7.2Hz, 1H), 7.34 (t, J=7.8Hz; 1H), 6.93-6.92 (m, 1H), 6.83-6.80 (m, 1H); (6.78 s, 1H), 3.87 (s, 3H), 2.97 (t; J=6.5Hz, 2H), 2.81 (t, J=7.3Hz, 2H); High resolution mass spectrum: m/z (%), calcd for C
20h
17n
2o (M*) 301.1335, found:301.1349.
Embodiment 26:
The present embodiment is the synthetic of 1-phenyl-pyrroles [1,2-a] quinoxaline, with 2-Iodoaniline, 5 – phenyl-pyrrole-2-aldehydes, K
3pO
4, CuI, dimethyl formamide, 2, the 2-dipyridyl is raw material, its reaction formula is as follows:
Preparation method: add 0.215mmol5 – phenyl-pyrrole-2-aldehyde in the 25ml eggplant-shape bottle, 0.215mmol2-Iodoaniline, 0.645mmol K
3pO
4, 0.0215mmol CuI, 0.043mmol2, the 2-dipyridyl, then add the 1.5ml dimethyl formamide, and nitrogen protection, 110 ℃ are stirred 20 hours, and solution colour becomes transparent color, has product to generate.
Reaction solution is filtered and obtains white solid after cooling, extraction, drying, underpressure distillation, washing, recrystallization.
Productive rate 81%, this 1-phenyl-pyrroles [1,2-a] quinoxaline is the soft type solid; Nucleus magnetic hydrogen spectrum (500Hz, CDCl
3): δ 8.70 (s, 1H), 7.82 (d, J=8.0Hz; 1H), 7.40-7.35 (m, 5H), 7.29 (d; J=8.5Hz, 1H), 7.22 (t, J=7.7Hz; 1H), 7.00 (t, J=8.1Hz, 1H); (6.84 d, J=4.0Hz, 1H); (6.64 d, J=4.0Hz, 1H); High resolution mass spectrum: m/z (%), calcd for C
17h
13n
2(M
*) 245.1073, found:245.1094.
Embodiment 27:
The present embodiment is the synthetic of the fluoro-indoles of 9-[1,2-a] quinoxaline, with 2-Iodoaniline, the fluoro-3-skatole of 5--2-formaldehyde, K
3pO
4, CuI, dimethyl formamide, 2, the 2-dipyridyl is raw material, its reaction formula is as follows:
Preparation method: add the fluoro-3-skatole of 0.215mmol5--2-formaldehyde in the 25ml eggplant-shape bottle, 0.215mmol2-Iodoaniline, 0.645mmol K
3pO
4, 0.0215mmol CuI, 0.043mmol2, the 2-dipyridyl, then add the 1.5ml dimethyl formamide, and nitrogen protection, 110 ℃ are stirred 20 hours, and solution colour becomes transparent color, has product to generate.
Reaction solution is filtered and obtains white solid after cooling, extraction, drying, underpressure distillation, washing, recrystallization.
Productive rate 81%, the fluoro-7-skatole of this 9-[1,2-a] quinoxaline fusing point is 170-171 ℃; Nucleus magnetic hydrogen spectrum (400Hz, CDCl
3): δ 8.88 (s, 1H), 8.25-8.21 (m, 2H); (7.93 dd, J=7.9,1.4Hz, 1H); (7.56-7.52 m, 1H), 7.45 (dd; J=8.9,2.6Hz, 1H); (7.40-7.36 m, 1H), 7.27-7.22 (m; 1H), 2.57 (s, 3H); High resolution mass spectrum: m/z (%), calcd for C
16h
12f N
2o(M
*) 251.0979, found:251.0958.
Embodiment 28:
The present embodiment is the synthetic of 2-methyl-pyrazoles [1,5-a] quinoxaline, with 2-Iodoaniline, 3-methyl-pyrazoles-5-formaldehyde, K
3pO
4, CuI, dimethyl formamide, 2, the 2-dipyridyl is raw material, its reaction formula is as follows:
Preparation method: add 0.215mmol3-methyl-pyrazoles-5-formaldehyde in the 25ml eggplant-shape bottle, 0.215mmol2-Iodoaniline, 0.645mmol K
3pO
4, 0.0215mmol CuI, 0.043mmol2, the 2-dipyridyl, then add the 1.5ml dimethyl formamide, and nitrogen protection, 110 ℃ are stirred 20 hours, and solution colour becomes transparent color, has product to generate.
Reaction solution is filtered and obtains white solid after cooling, extraction, drying, underpressure distillation, washing, recrystallization.
Productive rate 89%, this 2-methyl-pyrazoles [1,5-a] quinoxaline fusing point is 89-91 ℃; Nucleus magnetic hydrogen spectrum (400Hz, CDCl
3): δ 8.95 (s, 1H), 8.43 (dd, J=8.3,1.0Hz, 1H), 8.04 (dd, J=8.1,1.0Hz, 1H), 7.68-7.63 (m, 1H), 7.55-7.51 (m, 1H), 6.64 (s, 1H), 2.59 (s, 3H); High resolution mass spectrum: m/z (%), calcd for C
11h
10n
3o(M
*) 184.0869, found:184.0886.
Embodiment 29:
The present embodiment is the synthetic of pyrido pyrroles [1,2-a] pyrazine, with 2-amino-3-iodine pyridine, pyrrole-2-aldehyde, K
3pO
4, CuI, dimethyl formamide, 2, the 2-dipyridyl is raw material, its reaction formula is as follows:
Preparation method: add 0.215mmol pyrroles-2 formaldehyde in the 25ml eggplant-shape bottle, 0.215mmol2-amino-3-iodine pyridine, 0.645mmol K
3pO
4, 0.0215mmol CuI, 0.043mmol2, the 2-dipyridyl, then add the 1.5ml dimethyl formamide, and nitrogen protection, 110 ℃ are stirred 20 hours, and solution colour becomes transparent color, has product to generate.
Reaction solution is filtered and obtains white solid after cooling, extraction, drying, underpressure distillation, washing, recrystallization.
Productive rate 76%, this pyrido pyrroles [1,2-a] pyrazine fusing point is 170-172 ℃; Nucleus magnetic hydrogen spectrum (300Hz, CDCl
3): δ 9.01 (s, 1H), 8.76-8.74 (m, 1H), 8.22-8.19 (m, 1H), 7.97-7.96 (m, 1H), 7.45 (dd, J=8.2,4.6Hz, 1H), 6.96-6.92 (m, 2H); High resolution mass spectrum: m/z (%), calcd for C
10h
8n
3(M
*) 170.0712, found:170.0729.
Embodiment 30:
The present embodiment is the synthetic of pyrido pyrroles [1,2-h] pteridine, with 5-amino-4-iodine pyrimidine, pyrrole-2-aldehyde, K
3pO
4, CuI, dimethyl formamide, 2, the 2-dipyridyl is raw material, its reaction formula is as follows:
Preparation method: add 0.215mmol pyrroles-2 formaldehyde in the 25ml eggplant-shape bottle, 0.215mmol5-amino-4-iodine pyrimidine, 0.645mmol K
3pO
4, 0.0215mmol CuI, 0.043mmol2, the 2-dipyridyl, then add the 1.5ml dimethyl formamide, and nitrogen protection, 110 ℃ are stirred 20 hours, and solution colour becomes transparent color, has product to generate.
Reaction solution is filtered and obtains white solid after cooling, extraction, drying, underpressure distillation, washing, recrystallization.
Productive rate 80%, this pyrido pyrroles [1,2-h] pteridine fusing point is 122-123 ℃; Nucleus magnetic hydrogen spectrum (300Hz, CDCl
3): δ 9.24 (s, 1H), 9.06 (s, 1H), 8.82 (s, 1H), 8.34-8.33 (m, 1H), 7.05-7.04 (m, 1H), 6.99-6.97 (m, 1H); High resolution mass spectrum: m/z (%), calcd for C
9h
7n
4(M
*) 171.0665, found:171.0676.
Embodiment 31:
The present embodiment is the synthetic of 8-trifluoromethyl pyrpole [1,2-a] quinoxaline, with 4-amino-3-iodine phenylfluoroform, pyrrole-2-aldehyde, K
3pO
4, CuI, dimethyl formamide, 2, the 2-dipyridyl is raw material, its reaction formula is as follows:
Preparation method: add 0.215mmol pyrroles-2 formaldehyde in the 25ml eggplant-shape bottle, 0.215mmol4-amino-3-iodine phenylfluoroform, 0.645mmol K
3pO
4, 0.0215mmol CuI, 0.043mmol2, the 2-dipyridyl, then add the 1.5ml dimethyl formamide, and nitrogen protection, 110 ℃ are stirred 20 hours, and solution colour becomes transparent color, has product to generate.
Reaction solution is filtered and obtains white solid after cooling, extraction, drying, underpressure distillation, washing, recrystallization.
Productive rate 83%, this 8-trifluoromethyl pyrpole [1,2-a] quinoxaline fusing point is 133-134 ℃; Nucleus magnetic hydrogen spectrum (300Hz, CDCl
3): δ 8.85 (s, 1H), 8.09 (s, 1H), 8.05-8.03 (m, 1H), 7.98-7.96 (m, 1H), 7.67-7.65 (m, 1H), 6.97-6.96 (m, 1H), 6.94-6.92 (m, 1H); High resolution mass spectrum: m/z (%), calcd for C
12h
8f
3n
2(M
*) 237.0634, found:237.0650.
Embodiment 32:
The present embodiment is the synthetic of 8-formonitrile HCN pyrroles [1,2-a] quinoxaline, with 4-amino-3-ioxynil, pyrrole-2-aldehyde, K
3pO
4, CuI, dimethyl formamide, 2, the 2-dipyridyl is raw material, its reaction formula is as follows:
Preparation method: add 0.215mmol pyrroles-2 formaldehyde in the 25ml eggplant-shape bottle, 0.215mmol4-amino-3-ioxynil, 0.645mmol K
3pO
4, 0.0215mmol CuI, 0.043mmol2, the 2-dipyridyl, then add the 1.5ml dimethyl formamide, and nitrogen protection, 110 ℃ are stirred 20 hours, and solution colour becomes transparent color, has product to generate.
Reaction solution is filtered and obtains white solid after cooling, extraction, drying, underpressure distillation, washing, recrystallization.
Productive rate 90%, this 8-formonitrile HCN pyrroles [1,2-a] quinoxaline fusing point is 273-275 ℃; Nucleus magnetic hydrogen spectrum (400Hz, d-6DMSO): δ 9.15 (s, 1H), 9.01 (d; J=1.5Hz, 1H), 8.76-8.74 (m; 1H), 8.05 (d, J=8.4Hz; 1H), 7.94 (dd, J=8.4; 1.6Hz, 1H), 7.31-7.29 (m; 1H), 7.13 (m, 1H); High resolution mass spectrum: m/z (%), calcd for C
12h
8n
3(M
*) 194.0712, found:194.0728.
Embodiment 33:
The present embodiment is the synthetic of 8-methyl-formiate pyrroles [1,2-a] quinoxaline, with 4-amino-3-iodo-benzoic acid methyl esters, pyrrole-2-aldehyde, K
3pO
4, CuI, dimethyl formamide, 2, the 2-dipyridyl is raw material, its reaction formula is as follows:
Preparation method: add 0.215mmol pyrroles-2 formaldehyde in the 25ml eggplant-shape bottle, 0.215mmol4-amino-3-iodo-benzoic acid methyl esters, 0.645mmol K
3pO
4, 0.0215mmol CuI, 0.043mmol2, the 2-dipyridyl, then add the 1.5ml dimethyl formamide, and nitrogen protection, 110 ℃ are stirred 20 hours, and solution colour becomes transparent color, has product to generate.
Reaction solution is filtered and obtains white solid after cooling, extraction, drying, underpressure distillation, washing, recrystallization.
Productive rate 81%, this 8-methyl-formiate pyrroles [1,2-a] quinoxaline fusing point is 235-240 ℃; Nucleus magnetic hydrogen spectrum (400Hz, d-6DMSO): δ 8.95 (s, 1H), 8.78-8.77 (m, 1H), 8.64-8.63 (m; 1H), 8.00 (dd, J=8.4,1.5Hz, 1H), 7.93 (d; J=8.4Hz, 1H), 7.06 (m, 1H), 6.97-6.95 (m, 1H); High resolution mass spectrum: m/z (%), calcd for C
12h
9n
2o
2(M
*) 213.0658, found:213.0670.
Embodiment 34:
The present embodiment is the synthetic of 7-fluorine pyrroles [1,2-a] quinoxaline, with the fluoro-2-Iodoaniline of 5-, pyrrole-2-aldehyde, K
3pO
4, CuI, dimethyl formamide, 2, the 2-dipyridyl is raw material, its reaction formula is as follows:
Preparation method: add 0.215mmol pyrroles-2 formaldehyde in the 25ml eggplant-shape bottle, the fluoro-2-Iodoaniline of 0.215mmol5-, 0.645mmol K
3pO
4, 0.0215mmol CuI, 0.043mmol2, the 2-dipyridyl, then add the 1.5ml dimethyl formamide, and nitrogen protection, 110 ℃ are stirred 20 hours, and solution colour becomes transparent color, has product to generate.
Reaction solution is filtered and obtains white solid after cooling, extraction, drying, underpressure distillation, washing, recrystallization.
Productive rate 87%, this 7-fluorine pyrroles [1,2-a] quinoxaline fusing point is 166-167 ℃; Nucleus magnetic hydrogen spectrum (400Hz, CDCl
3): δ 8.78 (s, 1H), 7.86 (broad s, 1H), 7.78 (dd, J=9.0,5.0Hz, 1H), 7.61 (dd, J=9.4,2.7Hz, 1H), 7.26-7.21 (m, 1H), 6.90-6.85 (m, 2H); High resolution mass spectrum: m/z (%), calcd for C
11h
8fN
2(M
*) 187.0666, found:187.0680.
Claims (7)
1. a synthetic pyrroles [1; 2-a] method of quinoxaline derivatives; it is characterized in that: getting 2-halogen arylamine is that 1～2:1 is dissolved in organic solvent with 2-formyl radical azole compounds by the amount of substance ratio; add mantoquita, part, alkaline medium; under protection of inert gas; 100～110 ℃ are stirred reaction in 15～20 hours and obtain pyrroles [1,2-a] quinoxaline derivatives.
2. method according to claim 1, is characterized in that described mantoquita is CuI, CuBr, Cu
2o or Cu
2a kind of in Cl; Alkaline medium is K
3pO
4, CS
2cO
3, K
2cO
3or a kind of in NaOH; Described part is L-PROLINE, 2, a kind of in 2-dipyridyl, oxine or 1,10-phenanthroline.
3. method according to claim 1, the add-on that it is characterized in that mantoquita is that mantoquita and 2-formyl radical azole compounds amount of substance ratio are 0.1～0.2:1; Alkaline medium and 2-formyl radical azole compounds amount of substance ratio are 2～3:1; Part and 2-formyl radical azole compounds amount of substance ratio are 0.2～0.3:1.
4. method according to claim 1, is characterized in that described organic solvent is a kind of in acetonitrile, dimethyl formamide, dimethyl sulfoxide (DMSO) or toluene.
5. method according to claim 1, is characterized in that described rare gas element is nitrogen or argon gas.
6. method according to claim 1 is characterized in that the structural formula of described 2-formyl radical azole compounds is as follows:
7. method according to claim 1, it is characterized in that: the structural formula of described 2-halogen arylamine is as follows:
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