CN116253721B - 一类n-(4-吲哚基)-n’-烷基咪唑盐及其应用 - Google Patents
一类n-(4-吲哚基)-n’-烷基咪唑盐及其应用 Download PDFInfo
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- CN116253721B CN116253721B CN202310027237.8A CN202310027237A CN116253721B CN 116253721 B CN116253721 B CN 116253721B CN 202310027237 A CN202310027237 A CN 202310027237A CN 116253721 B CN116253721 B CN 116253721B
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- Prior art keywords
- indolyl
- alkyl
- added
- ethyl
- imidazole
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- -1 4-indolyl Chemical group 0.000 claims abstract description 75
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 26
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 17
- 125000000217 alkyl group Chemical group 0.000 claims description 13
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims description 5
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 4
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 4
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 3
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 3
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 3
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 3
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 claims description 3
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 claims description 2
- 125000006179 2-methyl benzyl group Chemical group [H]C1=C([H])C(=C(C([H])=C1[H])C([H])([H])*)C([H])([H])[H] 0.000 claims description 2
- 125000001622 2-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C(*)C([H])=C([H])C2=C1[H] 0.000 claims description 2
- 125000006180 3-methyl benzyl group Chemical group [H]C1=C([H])C(=C([H])C(=C1[H])C([H])([H])[H])C([H])([H])* 0.000 claims description 2
- 125000004861 4-isopropyl phenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 125000006181 4-methyl benzyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1C([H])([H])[H])C([H])([H])* 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 claims description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- DWYMPOCYEZONEA-UHFFFAOYSA-L fluoridophosphate Chemical compound [O-]P([O-])(F)=O DWYMPOCYEZONEA-UHFFFAOYSA-L 0.000 claims description 2
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 claims description 2
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 claims description 2
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 claims description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 2
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 claims description 2
- 229940006460 bromide ion Drugs 0.000 claims 1
- ZZVUWRFHKOJYTH-UHFFFAOYSA-N diphenhydramine Chemical group C=1C=CC=CC=1C(OCCN(C)C)C1=CC=CC=C1 ZZVUWRFHKOJYTH-UHFFFAOYSA-N 0.000 claims 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 claims 1
- 229940006461 iodide ion Drugs 0.000 claims 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 11
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- 239000002243 precursor Substances 0.000 abstract description 8
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 138
- 239000000203 mixture Substances 0.000 description 41
- 238000002360 preparation method Methods 0.000 description 40
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 39
- 238000006243 chemical reaction Methods 0.000 description 38
- 239000007787 solid Substances 0.000 description 34
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 24
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 22
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 18
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 18
- 239000012074 organic phase Substances 0.000 description 15
- 239000000243 solution Substances 0.000 description 15
- ADLVDYMTBOSDFE-UHFFFAOYSA-N 5-chloro-6-nitroisoindole-1,3-dione Chemical compound C1=C(Cl)C([N+](=O)[O-])=CC2=C1C(=O)NC2=O ADLVDYMTBOSDFE-UHFFFAOYSA-N 0.000 description 13
- 238000010898 silica gel chromatography Methods 0.000 description 13
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 12
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 12
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 11
- 239000003208 petroleum Substances 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- 239000000706 filtrate Substances 0.000 description 10
- 238000010992 reflux Methods 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 9
- LUNUNJFSHKSXGQ-UHFFFAOYSA-N 4-Aminoindole Chemical class NC1=CC=CC2=C1C=CN2 LUNUNJFSHKSXGQ-UHFFFAOYSA-N 0.000 description 8
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 8
- ZRSNZINYAWTAHE-UHFFFAOYSA-N p-methoxybenzaldehyde Chemical compound COC1=CC=C(C=O)C=C1 ZRSNZINYAWTAHE-UHFFFAOYSA-N 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical group N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 7
- 239000005695 Ammonium acetate Chemical group 0.000 description 7
- 229940043376 ammonium acetate Drugs 0.000 description 7
- 235000019257 ammonium acetate Nutrition 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical class [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 6
- 239000005909 Kieselgur Substances 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 5
- AGEZXYOZHKGVCM-UHFFFAOYSA-N benzyl bromide Chemical compound BrCC1=CC=CC=C1 AGEZXYOZHKGVCM-UHFFFAOYSA-N 0.000 description 5
- 238000006482 condensation reaction Methods 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- WFQDTOYDVUWQMS-UHFFFAOYSA-N 1-fluoro-4-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(F)C=C1 WFQDTOYDVUWQMS-UHFFFAOYSA-N 0.000 description 4
- QSJXEFYPDANLFS-UHFFFAOYSA-N Diacetyl Chemical group CC(=O)C(C)=O QSJXEFYPDANLFS-UHFFFAOYSA-N 0.000 description 4
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 4
- PQJJJMRNHATNKG-UHFFFAOYSA-N ethyl bromoacetate Chemical compound CCOC(=O)CBr PQJJJMRNHATNKG-UHFFFAOYSA-N 0.000 description 4
- 239000000543 intermediate Substances 0.000 description 4
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 4
- 239000012312 sodium hydride Substances 0.000 description 4
- 229910000104 sodium hydride Inorganic materials 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 125000001041 indolyl group Chemical group 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- ZLCHAFWHKSRMMJ-UHFFFAOYSA-M sodium;methanol;perchlorate Chemical compound [Na+].OC.[O-]Cl(=O)(=O)=O ZLCHAFWHKSRMMJ-UHFFFAOYSA-M 0.000 description 3
- AETKQQBRKSELEL-UHFFFAOYSA-N (2E)-1-(2-hydroxyphenyl)-3-phenylprop-2-en-1-one Natural products OC1=CC=CC=C1C(=O)C=CC1=CC=CC=C1 AETKQQBRKSELEL-UHFFFAOYSA-N 0.000 description 2
- OGTSHGYHILFRHD-UHFFFAOYSA-N (4-fluorophenyl)-phenylmethanone Chemical compound C1=CC(F)=CC=C1C(=O)C1=CC=CC=C1 OGTSHGYHILFRHD-UHFFFAOYSA-N 0.000 description 2
- KJPRLNWUNMBNBZ-QPJJXVBHSA-N (E)-cinnamaldehyde Chemical compound O=C\C=C\C1=CC=CC=C1 KJPRLNWUNMBNBZ-QPJJXVBHSA-N 0.000 description 2
- AETKQQBRKSELEL-ZHACJKMWSA-N 2'-hydroxychalcone Chemical compound OC1=CC=CC=C1C(=O)\C=C\C1=CC=CC=C1 AETKQQBRKSELEL-ZHACJKMWSA-N 0.000 description 2
- VECNCSXBWOBBNA-UHFFFAOYSA-N Br.C=1C=CC=CC=1CC1=CC=CC=C1 Chemical compound Br.C=1C=CC=CC=1CC1=CC=CC=C1 VECNCSXBWOBBNA-UHFFFAOYSA-N 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229940117916 cinnamic aldehyde Drugs 0.000 description 2
- KJPRLNWUNMBNBZ-UHFFFAOYSA-N cinnamic aldehyde Natural products O=CC=CC1=CC=CC=C1 KJPRLNWUNMBNBZ-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 125000005594 diketone group Chemical group 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 2
- 238000007348 radical reaction Methods 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 239000013589 supplement Substances 0.000 description 2
- 125000006732 (C1-C15) alkyl group Chemical group 0.000 description 1
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 description 1
- SCCCFNJTCDSLCY-UHFFFAOYSA-N 1-iodo-4-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(I)C=C1 SCCCFNJTCDSLCY-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000007296 Stetter synthesis reaction Methods 0.000 description 1
- OKJPEAGHQZHRQV-UHFFFAOYSA-N Triiodomethane Natural products IC(I)I OKJPEAGHQZHRQV-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 238000007193 benzoin condensation reaction Methods 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- VILAVOFMIJHSJA-UHFFFAOYSA-N dicarbon monoxide Chemical compound [C]=C=O VILAVOFMIJHSJA-UHFFFAOYSA-N 0.000 description 1
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 1
- 125000005982 diphenylmethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 125000003754 ethoxycarbonyl group Chemical group C(=O)(OCC)* 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- 125000005928 isopropyloxycarbonyl group Chemical group [H]C([H])([H])C([H])(OC(*)=O)C([H])([H])[H] 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical group O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006452 multicomponent reaction Methods 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000012434 nucleophilic reagent Substances 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001603 reducing effect Effects 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 description 1
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000003557 thiazoles Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
- C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
- C07D403/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0244—Nitrogen containing compounds with nitrogen contained as ring member in aromatic compounds or moieties, e.g. pyridine
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/94—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems condensed with rings other than six-membered or with ring systems containing such rings
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
- B01J2231/4205—C-C cross-coupling, e.g. metal catalyzed or Friedel-Crafts type
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Indole Compounds (AREA)
Abstract
本发明公开了一类化学结构式如下的N‑(4‑吲哚基)‑N’‑烷基咪唑盐；本发明提供的N‑(4‑吲哚基)‑N’‑烷基咪唑盐可作为前体催化剂用于有机合成中，提高催化效率；
Description
技术领域
本发明属于化学合成与有机催化技术领域，涉及一类N-(4-吲哚基)-N’-烷基咪唑盐，此类化合物可作为有机催化剂用于有机合成。
背景技术
有机催化是现代合成化学的前沿分支之一，已广泛应用于制药、农用化学和材料等领域。近二十年来，氮杂环卡宾(N-heterocyclic carbene,NHC)逐步应用于有机合成中，显示出良好的催化效果。NHC是一类单线态卡宾，由于其氮杂环结构在空间结构和电子效应两方面的稳定作用，卡宾碳具有较强的亲核性。作为一类独特的有机催化剂，NHC可以与醛类化合物作用，形成Breslow中间体，从而使亲电性的羰基碳转化为亲核试剂，发生各种极性反转反应，如安息香缩合反应、Stetter反应、α,β-不饱和醛与各种亲电试剂的反应、亲核取代反应、多组分反应等。此外，由于Breslow中间体具有还原性，NHC也可用于催化一些自由基反应。NHC催化为碳碳键的构建、复杂天然化合物和药物的合成与修饰提供了新的方法和策略。
NHC催化剂一般由相应的前体如咪唑盐、噻唑盐、三氮唑盐等在反应体系中与碱作用形成。结构上，咪唑型NHC可分为咪唑母核、母核取代基、氮上侧链等单元。对于侧链单元，目前主要为取代苯基和烷基。由于苯基的结构多样性有限，所能得到的NHC结构类型较少。因此，通过在NHC侧链单元引入芳杂环等更多结构变化，发展适用于不同反应的新型催化剂，是NHC催化领域中有潜力的新方向。
发明内容
本发明提供了一类N-(4-吲哚基)-N’-烷基咪唑盐，该类化合物的化学结构通式如下：
式中：R1、R2、R3、R4、R5、R6、R7、R8选自氢、C1-C8的烷基、C6-C12的芳基；R9选自C1-C15的烷基或官能化烷基；n＝1-6；
X-为抗衡阴离子。
其中C1-C8的烷基选自甲基、乙基、丙基、2-丙基、环丙基、丁基、2-丁基、叔丁基、环丁基、戊基、3-戊基、环戊基、己基、环己基、庚基、4-庚基、环庚基、苄基、1-苯基-1-乙基。C6-C12的芳基选自苯基、2-甲基苯基、3-甲基苯基、4-甲基苯基、2,4-二甲基苯基、2,6-二甲基苯基、2,4,6-三甲基苯基、2-异丙基苯基、4-异丙基苯基、2,6-二异丙基苯基、1-萘基、2-萘基。
C1-C15的烷基选自甲基、乙基、丙基、2-丙基、环丙基、丁基、2-丁基、叔丁基、环丁基、戊基、3-戊基、环戊基、己基、环己基、庚基、4-庚基、环庚基；C1-C15的官能化烷基选自苄基、2-甲基苄基、3-甲基苄基、4-甲基苄基、2,6-二甲基苄基、2,4,6-三甲基苄基、1-苯基-1-乙基、二苯甲基、甲氧羰甲基、乙氧羰甲基、异丙氧羰甲基、(1-甲氧羰基)-1-乙基、(1-乙氧羰基)-1-乙基、(1-异丙氧羰基)-1-乙基、(2-甲氧羰基)-1-乙基、(2-乙氧羰基)-1-乙基、(2-异丙氧羰基)-1-乙基。
X-选自高氯酸根、氟硼酸根、氟磷酸根、氟离子、氯离子、溴离子、碘离子、对甲基苯磺酸根、甲磺酸根、三氟甲磺酸根、甲酸根、乙酸根。
N-(4-吲哚基)-N’-烷基咪唑盐的合成制备分为两个步骤：
第一步是多取代4-氨基吲哚(Yan,H.et al.,Tetrahedron Lett.2020,61,152450；Ye,Y.X.etal.,Tetrahedron Lett.2022,107,154125)与邻二酮、甲醛、乙酸铵缩合，得到N-(4-吲哚基)咪唑中间体；
第二步是N-(4-吲哚基)咪唑中间体与烷基或官能化烷基卤化物反应，得到相应的N-(4-吲哚基)-N’-烷基咪唑盐，随后进行抗衡阴离子的交换；
本发明另一目的是将上述N-(4-吲哚基)-N’-烷基咪唑盐作为前体催化剂应用于有机合成中，反应中，N-(4-吲哚基)-N’-烷基咪唑盐经碱作用形成咪唑型NHC，催化反应进行；
本发明的优点和技术效果：
1、对于本发明提供的N-(4-吲哚基)-N’-烷基咪唑盐，4-吲哚基侧链具有共轭体系大、电子云密度高的特点，有利于加速NHC与不饱和底物的反应，提高催化效率；
2、对于本发明提供的N-(4-吲哚基)-N’-烷基咪唑盐，由于吲哚单元结构多样性较为丰富，可根据有机催化反应的需要，对吲哚侧链的取代基进行微调和优化；
3.对于本发明提供的N-(4-吲哚基)-N’-烷基咪唑盐，由于吲哚侧链具有富电子的特点，在自由基反应中可作为电子供体，拓展反应机理类别。
具体实施方式
以下对本发明技术方案的具体实施方式详细描述，但并不构成对本发明保护范围的限定。本发明实施例中所使用的试剂均为市售的化学纯试剂。实施例中的原料多取代4-氨基吲哚按照文献方法制备(H.Yan et al.,Tetrahedron Lett.2020,61,152450；Y.X.Yeet al.,Tetrahedron Lett.2022,107,154125)；
实施例1：溴化N-(4-吲哚基)-N’-烷基咪唑盐10的制备
(1)N-(4-吲哚基)咪唑3制备
在干燥的圆底烧瓶中，依次加入多取代4-氨基吲哚1a(1.00g，4.63mmol)、丁二酮2a(332mg)、37％甲醛水溶液(0.36mL)、乙酸铵(892mg)、乙酸(2.21mL)、氯仿(8mL)，80℃下回流搅拌2h，反应完成后，冷却至室温，减压蒸除溶剂，加入乙酸乙酯和饱和碳酸钠溶液萃取两次，乙酸乙酯和水萃取一次，收集有机相用无水硫酸钠干燥，过滤，浓缩后硅胶柱层析(石油醚：乙酸乙酯＝2:1)，收集洗脱液，43℃减压蒸馏，获得N-(4-吲哚基)咪唑3(白色固体，745mg，63％)；
1H NMR(600MHz,CDCl3)δ7.39(s,1H),6.74(s,1H),3.94(s,3H),2.77(s,3H),2.68(q,J＝7.6Hz,2H),2.27(s,3H),1.97(s,3H),1.84(s,3H),1.52(s,3H),1.13(t,J＝7.6Hz,3H).
13C NMR(150MHz,CDCl3)δ140.6,135.7,134.7,132.8,126.1,125.9,124.7,124.6,121.3,104.7,32.4,20.3,17.5,16.1,14.1,12.9,8.4,7.7.
(2)溴化N-(4-吲哚基)-N’-烷基咪唑盐10的制备
将N-(4-吲哚基)咪唑3(500mg，1.7mmol)加入25mL圆底烧瓶中，加入乙酸乙酯(2mL)，加入苄溴(0.3mL)，65℃下加热回流1h，反应完成后，冷却至室温，过滤，所得固体依次用乙酸乙酯、四氢呋喃、甲醇洗涤后干燥，得到溴化N-(4-吲哚基)-N’-烷基咪唑盐10(白色固体，715mg，99％)。
1H NMR(600MHz,CDCl3)δ10.20(s,1H),7.43-7.36(m,4H),7.36-7.33(m,1H)6.75(s,1H),6.17(d,J＝15.0Hz,1H),5.80(d,J＝15.0Hz,1H),3.94(s,3H),2.77(s,3H),2.68(q,J＝7.2Hz,2H),2.26(s,3H),2.08(s,3H),1.90(s,3H),1.55(s,3H),1.15(t,J＝7.2Hz,3H).
13C NMR(150MHz,CDCl3)δ142.1,135.2,135.0,133.1,129.9,129.4,129.1,128.1,127.3,126.0,125.6,124.3,123.8,120.3,102.7,51.3,32.6,20.4,17.5,16.2,14.0,9.1,8.4.8.3.
实施例2：高氯酸N-(4-吲哚基)-N’-烷基咪唑盐11的制备
将溴化N-(4-吲哚基)-N’-烷基咪唑盐10(100mg，0.21mmol)加入5mL圆底烧瓶中，加入2mol/L的高氯酸钠的甲醇溶液1mL，室温反应1h，过滤，THF洗涤固体，干燥后得到高氯酸N-(4-吲哚基)-N’-烷基咪唑盐11(白色固体，103mg，99％)。
实施例3：溴化N-(4-吲哚基)-N’-烷基咪唑盐21的制备
(1)N-(4-吲哚基)咪唑3的制备同实施例1；
(2)溴化N-(4-吲哚基)-N’-烷基咪唑盐21的制备
将N-(4-吲哚基)咪唑3(500mg，1.7mmol)与溴代乙酸乙酯(0.28mL)加入到10mL圆底烧瓶中，然后加入乙酸乙酯(2mL)，65℃下加热回流1h，反应完成后，冷却至室温，过滤，所得固体依次用乙酸乙酯、四氢呋喃、甲醇洗涤后干燥，得到溴化N-(4-吲哚基)-N’-烷基咪唑盐21(白色固体，647mg，99％)。
1H NMR(600MHz,CDCl3)δ9.91(s,1H),6.69(s,1H),6.06(d,J＝18.0Hz,1H),5.47(d,J＝18.0Hz,1H),4.24(q,J＝7.2Hz,2H),3.90(s,3H),2.72(s,3H),2.64(q,J＝7.2Hz,2H),2.27(s,3H),2.02(s,3H),1.91(s,3H),1.58(s,3H),1.29(t,J＝7.2Hz,3H),1.10(t,J＝7.2Hz,3H).
13C NMR(150MHz,CDCl3)δ166.4,141.9,137.4,135.0,128.7,126.6,125.8,125.2,124.3,123.6,120.2,103.0,62.6,48.2,32.6,20.3,17.5,16.3,14.0,13.9,8.6,8.4,8.3.
实施例4：溴化N-(4-吲哚基)-N’-烷基咪唑盐12的制备
(1)N-(4-吲哚基)咪唑4的制备
在干燥的圆底烧瓶中，依次加入多取代4-氨基吲哚1b(1.00g，4.09mmol)、丁二酮(294mg)、37％甲醛水溶液(0.28mL)、乙酸铵(789mg)、乙酸(1.94mL)、氯仿(8mL)，80℃下回流搅拌2h，反应完成后，冷却至室温，减压蒸除溶剂，加入乙酸乙酯和饱和碳酸钠溶液萃取两次，乙酸乙酯和水萃取一次，有机相以无水硫酸钠干燥，过滤，浓缩后硅胶柱层析(石油醚:乙酸乙酯＝2：1)，收集洗脱液，43℃减压蒸馏，获得N-(4-吲哚基)咪唑4(白色固体，228mg，69％)；
1H NMR(600MHz,CDCl3)δ7.40(s,1H),6.75(s,1H),3.93(s,3H),2.78(s,3H),2.64-2.58(m,2H),2.27(s,3H),2.06-1.98(m,1H),1.93(s,3H),1.88-1.81(m,1H),1.83(s,3H),1.60-1.52(m,2H),1.01(t,J＝7.2Hz,3H),0.80(t,J＝7.2Hz,3H).
13C NMR(150MHz,CDCl3)δ139.4,135.6,134.9,133.0,126.5,125.7,124.8,124.5,124.2,121.5,112.6,32.6,26.5,23.4,20.5,17.2,17.0,16.2,14.2,12.9,8.5.
(2)溴化N-(4-吲哚基)-N’-烷基咪唑盐12的制备
将N-(4-吲哚基)咪唑4(500mg，1.5mmol)加入25mL圆底烧瓶中，加入乙酸乙酯(2mL)，加入苄溴(0.28mL)，65℃下加热回流1h，反应完成后，冷却至室温，过滤，所得固体依次用乙酸乙酯、四氢呋喃、甲醇洗涤后干燥，得到溴化N-(4-吲哚基)-N’-烷基咪唑盐12(白色固体，732mg，96％)；
1H NMR(600MHz,CDCl3)δ10.11(s,1H),7.45(bd,J＝7.2Hz,2H),7.38(t,J＝7.2Hz,2H),7.35(d,J＝7.2Hz,1H),6.76(s,1H),6.31(d,J＝15.0Hz,1H),5.65(d,J＝15.0Hz,1H),3.93(s,3H),2.77(s,3H),2.64-2.55(m,2H),2.29(s,3H),2.07(s,3H),2.07-2.02(m,1H),1.89(s,3H),1.77-1.70(m,1H),1.01(t,J＝7.2Hz,3H),0.90-0.85(m,2H),0.74(t,J＝7.2Hz,3H).
13C NMR(150MHz,CDCl3)δ140.5,136.6,135.3,133.6,129.1,129.0,128.7,128.2,126.6,126.0,125.7,123.7,123.2,120.3,110.6,51.1,32.7,26.4,23.2,20.4,17.5,17.4,16.7,14.1,9.3,8.4.
实施例5：高氯酸N-(4-吲哚基)-N’-烷基咪唑盐13的制备
溴化N-(4-吲哚基)-N’-烷基咪唑盐12(100mg，0.20mmol)加入到5mL圆底烧瓶中，加入2mol/L的高氯酸钠的甲醇溶液1mL，室温反应1h，过滤，THF洗涤固体，得到高氯酸N-(4-吲哚基)-N’-烷基咪唑盐13(白色固体，102mg，98％)。
实施例6：溴化N-(4-吲哚基)-N’-烷基咪唑盐22的制备
(1)N-(4-吲哚基)咪唑4的制备同实施例4步骤(1)；
(2)溴化N-(4-吲哚基)-N’-烷基咪唑盐22的制备
将N-(4-吲哚基)咪唑4(500mg，1.5mmol)与溴代乙酸乙酯(0.26mL)加入到10mL圆底烧瓶中，加入乙酸乙酯(2mL)，65℃加热回流1h，反应完成后，冷却至室温，过滤，所得固体依次用乙酸乙酯、四氢呋喃、甲醇洗涤后干燥，得到溴化N-(4-吲哚基)-N’-烷基咪唑盐22(白色固体，旋转异构体7:3混合物，621mg，98％)；
主异构体核磁共振数据如下：
1H NMR(600MHz,CDCl3)δ9.97(s,1H),6.72(s,1H),6.27(d,J＝18.0Hz,1H),5.28(d,J＝18.0Hz,1H),4.28(q,J＝7.2Hz,2H),3.89(s,3H),2.75(s,3H),2.63-2.56(m,1H),2.38(s,2H),2.28(s,3H),2.02(s,3H),1.95(s,3H),1.89-1.74(m,2H),1.60-1.50(m,1H),1.33(t,J＝7.2Hz,3H),1.13(t,J＝7.2Hz,3H),1.11(t,J＝7.2Hz,3H).
13C NMR(150MHz,CDCl3)δ166.3,137.3,135.9,134.6,128.2,127.0,125.8,125.7,123.4,122.8,120.0,115.5,62.7,48.3,32.3,23.4,23.1,22.8,20.6,17.4,16.7,14.0,12.7,8.6,8.3.
实施例7：溴化N-(4-吲哚基)-N’-烷基咪唑盐14的制备
(1)N-(4-吲哚基)咪唑5的制备
在干燥的圆底烧瓶中，依次加入多取代4-氨基吲哚1c(1.00g，4.34mmol)、丁二酮(311mg)、37％甲醛水溶液(0.30mL)、乙酸铵(837mg)、乙酸(2.10mL)、氯仿(8mL)，80℃下回流搅拌2h，反应完成后，冷却至室温，减压蒸除溶剂，加入乙酸乙酯和饱和碳酸钠溶液萃取两次，乙酸乙酯和水萃取一次，有机相以无水硫酸钠干燥，过滤，浓缩后硅胶柱层析(石油醚：乙酸乙酯＝2：1)，收集洗脱液，43℃减压蒸馏，获得N-(4-吲哚基)咪唑5(白色固体，439mg，66％)；
1H NMR(600MHz,CDCl3)δ7.41(s,1H),6.74(s,1H),3.91(s,3H),2.77(s,3H),2.39(s,3H),2.29(s,3H),1.93(s,3H),1.85(s,3H),1.85-1.80(m,1H),1.09(d,J＝7.2Hz,3H),1.06(d,J＝7.2Hz,3H).
13C NMR(150MHz,CDCl3)δ134.00,133.6,133.2,132.2,125.6,124.6,123.4,123.0,120.2,115.9,31.2,22.2,21.8,21.3,19.6,15.2,11.9,11.6,7.2.
(2)溴化N-(4-吲哚基)-N’-烷基咪唑盐14的制备
将N-(4-吲哚基)咪唑5(500mg,1.6mmol)加入25mL圆底烧瓶中，加入乙酸乙酯(2mL)，加入苄溴(0.29mL)，65℃下加热回流1h，反应完成后，冷却至室温，过滤，所得固体依次用乙酸乙酯、四氢呋喃、甲醇洗涤后干燥，得到溴化N-(4-吲哚基)-N’-烷基咪唑盐14(白色固体，766mg，99％)；
1H NMR(600MHz,CDCl3)δ10.07(s,1H),7.40-7.37(m,4H),7.36-7.33(m,1H),6.75(s,1H),6.37(d,J＝15.0Hz,1H),5.56(d,J＝15.0Hz,1H),3.91(s,3H),2.76(s,3H),2.39(s,3H),2.28(s,3H),2.06(s,3H),1.92(s,3H),1.72(septet,J＝7.2Hz,1H),1.09(d,J＝7.2Hz,6H).
13C NMR(150MHz,CDCl3)δ136.6,135.8,134.6,133.8,129.2,128.8,128.7,127.9,126.7,126.1,123.4,122.7,120.2,115.1,51.3,32.3,23.6,23.2,23.0,20.7,16.9,12.8,9.2,8.3.
实施例8：高氯酸N-(4-吲哚基)-N’-烷基咪唑盐15的制备
溴化N-(4-吲哚基)-N’-烷基咪唑盐14(100mg，0.22mmol)，加入到5mL圆底烧瓶中，加入2mol/L的高氯酸钠的甲醇溶液1mL，室温反应1h，过滤，THF洗涤固体，得到高氯酸N-(4-吲哚基)-N’-烷基咪唑盐15(白色固体，103mg，99％)。
实施例9：溴化N-(4-吲哚基)-N’-烷基咪唑盐18的制备
(1)N-(4-吲哚基)咪唑5的制备同实施例7步骤(1)；
(2)溴化N-(4-吲哚基)-N’-烷基咪唑盐18的制备
将N-(4-吲哚基)咪唑5(500mg，1.6mmol)加入到10mL圆底烧瓶中，加入二苯基溴甲烷(798mg)，加入乙腈(2mL)，80℃下回流反应24h，反应完成后，冷却至室温，减压蒸馏除去溶剂，硅胶柱层析分离(二氯甲烷:甲醇＝40:1)，得到溴化N-(4-吲哚基)-N’-烷基咪唑盐18(白色固体，764mg，85％)；
1H NMR(600MHz,CDCl3)δ8.07(s,1H),7.70(s,1H),7.45-7.42(m,2H),7.41-7.33(m,8H),7.21(s,1H),6.73(s,1H),3.89(s,3H),2.74(s,3H),2.44(s,3H),2.40(s,3H),1.97(s,3H),1.96(s,3H),1.87(septet,J＝7.2Hz,1H),1.22(d,J＝7.2Hz,3H),1.14(d,J＝7.2Hz,3H).
13C NMR(150MHz,CDCl3)δ136.4,135.9,135.5,134.5,132.9,130.2,129.9,129.4,129.3,129.2,129.0,128.7,128.2,125.7,123.8,122.4,119.9,115.0,64.9,32.4,23.6,23.2,22.9,20.6,16.5,12.7,10.7,8.3.
实施例10：溴化N-(4-吲哚基)-N’-烷基咪唑盐16的制备
(1)N-(4-吲哚基)咪唑6的制备
在干燥的圆底烧瓶中，依次加入多取代4-氨基吲哚1d(1.00g，3.42mmol)、邻二酮(245mg)、37％甲醛水溶液(0.24mL)、乙酸铵(658mg)、乙酸(1.71mL)、氯仿(8mL)，加热80℃回流搅拌2h。反应完成后，冷却至室温，减压蒸除溶剂，加入乙酸乙酯和饱和碳酸钠溶液萃取两次，乙酸乙酯和水萃取一次，有机相以无水硫酸钠干燥，过滤，浓缩后硅胶柱层析(石油醚：乙酸乙酯＝2：1)，收集洗脱液，43℃减压蒸馏，获得N-(4-吲哚基)咪唑6(白色固体，322mg，71％)；
1H NMR(600MHz,CDCl3)δ7.50-7.41(m,4H),7.32(bs,2H),6.84(s,1H),3.62(s,3H),2.80(s,3H),2.28(s,3H),2.00-1.94(m,1H),1.95(s,3H),1.90(s,3H),0.80(d,J＝7.2Hz,3H),0.73(d,J＝7.2Hz,3H).
13C NMR(150MHz,CDCl3)δ138.5,134.3,133.4,133.0,132.3,130.7,130.5,127.5,127.0,126.9,126.2,125.4,124.1,123.4,123.0,120.9,118.0,32.4,23.6,22.7,22.3,19.5,15.3,11.9,7.4.
(2)溴化N-(4-吲哚基)-N’-烷基咪唑盐16的制备
将N-(4-吲哚基)咪唑6(500mg,1.3mmol)加入25mL圆底烧瓶中，加入乙酸乙酯(2mL)，加入苄溴(0.24mL)，65℃加热回流1h，反应完成后，冷却至室温，过滤，所得固体依次用乙酸乙酯、四氢呋喃、甲醇洗涤后干燥，得到溴化N-(4-吲哚基)-N’-烷基咪唑盐16(白色固体，698mg，97％)；
1H NMR(600MHz,CDCl3)δ10.16(s,1H),7.44-7.40(m,3H),7.39-7.36(m,2H),7.32-7.26(m,5H),6.82(s,1H),6.29(d,J＝15.0Hz,1H),5.56(d,J＝15.0Hz,1H),3.59(s,3H),2.76(s,3H),2.27(s,3H),2.05(s,3H),1.95(s,3H),1.77(septet,J＝7.2Hz,1H),0.76(d,J＝7.2Hz,3H),0.68(d,J＝7.2Hz,3H).
13C NMR(150MHz,CDCl3)δ140.4,136.5,134.7,133.6,133.3,131.5,131.1,129.1,128.8,128.7,128.6,128.2,128.0,127.9,126.8,126.7,126.5,124.2,122.7,120.8,116.9,51.0,33.4,24.5,24.4,23.7,20.4,16.8,9.3,8.4.
实施例11：溴化N-(4-吲哚基)-N’-烷基咪唑盐19的制备
(1)N-(4-吲哚基)咪唑6的制备同实施例10步骤(1)；
(2)溴化N-(4-吲哚基)-N’-烷基咪唑盐19的制备
将N-(4-吲哚基)咪唑6(500mg，1.3mmol)加入到10mL圆底烧瓶中，加入二苯基溴甲烷(655mg)，加入乙腈(2mL)，80℃下回流反应24h，反应完成后，冷却至室温，减压蒸馏除去溶剂，硅胶柱层析分离(二氯甲烷:甲醇＝40:1)，得到溴化N-(4-吲哚基)-N’-烷基咪唑盐19(白色固体，713mg，87％)；
1H NMR(600MHz,CDCl3)δ8.11(s,1H),7.88(s,1H),7.49-7.44(m,5H),7.41-7.37(m,2H),7.37-7.33(m,6H),7.33-7.30(m,1H),7.26-7.23(m,1H),6.85(s,1H),3.61(s,3H),2.77(s,3H),2.42(s,3H),2.03(s,3H),2.02(s,1H),1.97(septet,J＝7.2Hz,1H),0.87(d,J＝7.2Hz,3H),0.85(d,J＝7.2Hz,3H).
13C NMR(150MHz,CDCl3)δ140.9,136.0,135.5,134.6,133.3,133.0,131.3,131.2,130.2,129.9,129.4,129.2,129.1,129.0,128.9,128.3,128.2,126.6,126.5,124.6,122.5,120.8,116.9,65.0,33.5,24.7,24.5,23.8,20.4,16.7,10.8,8.6.
实施例12：溴化N-(4-吲哚基)-N’-烷基咪唑盐23的制备
(1)N-(4-吲哚基)咪唑6的制备同实施例10步骤(1)；
(2)溴化N-(4-吲哚基)-N’-烷基咪唑盐23的制备
将N-(4-吲哚基)咪唑6(500mg，1.3mmol)与溴代乙酸乙酯(0.22mL)加入到10mL圆底烧瓶中，加入乙酸乙酯(2mL)，65℃下加热回流1h，反应完成后，冷却至室温，过滤，所得固体依次用乙酸乙酯、四氢呋喃、甲醇洗涤后干燥，得到溴化N-(4-吲哚基)-N’-烷基咪唑盐23(白色固体，802mg，98％)；
1H NMR(600MHz,CDCl3)δ10.13(s,1H),7.47-7.41(m,3H),7.35-7.32(m,1H),7.30-7.27(m,1H),6.83(s,1H),6.23(d,J＝18.0Hz,1H),5.33(d,J＝18.0Hz,1H),4.29-4.23(m,2H),3.61(s,3H),2.78(s,3H),2.28(s,3H),2.06(s,3H),2.01(s,3H),1.90(septet,J＝7.2Hz,1H),1.31(t,J＝7.2Hz,3H),0.86(d,J＝7.2Hz,3H),0.75(d,J＝7.2Hz,3H).
13C NMR(150MHz,CDCl3)δ166.3,140.5,137.7,134.8,133.4,131.7,131.1,128.8,128.3,128.2,128.0,127.0,126.7,126.4,124.3,122.8,120.7,117.5,62.7,48.3,33.5,24.7,24.3,23.6,20.5,16.8,14.0,8.6,8.5.
实施例13：高氯酸N-(4-吲哚基)-N’-烷基咪唑盐25的制备
(1)N-(4-吲哚基)咪唑6的制备同实施例10步骤(1)；
(2)高氯酸N-(4-吲哚基)-N’-烷基咪唑盐25的制备
将N-(4-吲哚基)咪唑6(500mg,1.5mmol)与碘甲烷(0.6mL)加入到10mL圆底烧瓶中，加入乙腈(2mL)，80℃下回流反应24h，得到的粗产物与高氯酸钠的甲醇溶液(2.0mol/L,0.4mL,0.80mmol)室温反应1h，得到高氯酸N-(4-吲哚基)-N’-烷基咪唑盐25(白色固体，584.6mg，98％)；
1H NMR(600MHz,CDCl3)δ9.60(s,1H),7.42-7.37(m,3H),7.28-7.23(m,2H),6.79(s,1H),4.16(s,3H),3.57(s,3H),2.73(s,3H),2.39(s,3H),2.02(s,3H),1.96(s,3H),1.67(septet,J＝7.2Hz,1H),0.83(d,J＝7.2Hz,3H),0.67(d,J＝7.2Hz,3H).
13C NMR(150MHz,CDCl3)δ140.3,135.4,134.6,133.1,131.3,131.0,128.7,128.5,128.0,127.9,127.2,126.5,126.2,124.2,122.7,120.4,116.8,35.0,33.3,24.8,24.2,23.3,20.3,16.9,9.0,8.4.
实施例14：溴化N-(4-吲哚基)-N’-烷基咪唑盐20的制备
(1)在干燥的圆底烧瓶中，依次加入多取代4-氨基吲哚1e(400mg，1.47mmol)、丁二酮(105mg)、37％甲醛水溶液(0.1mL)、乙酸铵(283mg)、乙酸(0.5mL)、氯仿(2mL)，加热80℃回流搅拌2h，反应完成后，冷却至室温，减压蒸除溶剂，加入乙酸乙酯和饱和碳酸钠溶液萃取两次，乙酸乙酯和水萃取一次，有机相以无水硫酸钠干燥，过滤，浓缩后硅胶柱层析(石油醚：乙酸乙酯＝2：1)，收集洗脱液，43℃减压蒸馏，获得N-(4-吲哚基)咪唑7(白色固体，346mg，67％)；
(2)溴化N-(4-吲哚基)-N’-烷基咪唑盐20的制备
将N-(4-吲哚基)咪唑7(500mg，1.4mmol)加入到10mL圆底烧瓶中，加入二苯基溴甲烷(704mg)，加入乙腈(2mL)，80℃下回流反应24h，反应完成后，冷却至室温，减压蒸馏除去溶剂，硅胶柱层析分离(二氯甲烷:甲醇＝40:1)，得到溴化N-(4-吲哚基)-N’-烷基咪唑盐20(白色固体，672mg，79％)；
1H NMR(600MHz,CDCl3)δ8.11(s,1H),7.76(s,1H),7.47-7.44(m,2H),7.41-7.33(m,8H),6.76(s,1H),3.87(s,3H),2.75(s,3H),2.71-2.67(m,2H),2.44(s,3H),2.03-1.96(m,1H),1.97(s,3H),1.96(s,3H),1.90-1.82(m,1H),1.21(d,J＝6.0Hz,3H),1.12(d,J＝6.0Hz,3H),0.96(d,J＝7.2Hz,6H).
13C NMR(150MHz,CDCl3)δ140.4,136.0,135.7,135.6,133.0,130.3,129.9,129.4,129.3,129.2,129.0,128.8,128.3,126.1,126.0,124.1,122.9,120.2,116.0,64.9,34.4,33.7,29.1,24.3,24.0,23.9,22.6,22.5,20.6,16.7,10.8,8.5.
实施例15：溴化N-(4-吲哚基)-N’-烷基咪唑盐17的制备
(1)N-(4-吲哚基)咪唑8的制备
在干燥的圆底烧瓶中，依次加入多取代4-氨基吲哚1a(500mg，2.31mmol)、环己基邻二酮2b(216mg)、37％甲醛水溶液(0.43mL)、乙酸铵(506mg)、乙酸(1.1mL)、氯仿(5mL)，80℃下回流搅拌2h，反应完成后，冷却至室温，减压蒸除溶剂，加入乙酸乙酯和饱和碳酸钠溶液萃取两次，乙酸乙酯和水萃取一次，有机相以无水硫酸钠干燥，过滤，浓缩后硅胶柱层析(石油醚：乙酸乙酯＝2：1)，收集洗脱液，43℃减压蒸馏，获得N-(4-吲哚基)咪唑8(白色固体，454mg，61％)；
1H NMR(600MHz,CDCl3)δ7.38(s,1H),6.73(s,1H),3.93(s,3H),2.77(s,3H),2.73-2.66(m,4H),2.16(t,J＝6.0Hz,2H),2.00(s,3H),1.86-1.80(m,2H),1.80-1.74(m,2H),1.54(s,3H),1.14(t,J＝7.2Hz,3H).
13C NMR(150MHz,CDCl3)δ140.6,136.0,135.8,134.7,128.1,126.0,125.8,125.7,124.4,121.3,104.7,32.4,24.4,23.6,23.1,20.7,20.4,17.5,16.2,14.1,7.8.
(2)溴化N-(4-吲哚基)-N’-烷基咪唑盐17的制备
将N-(4-吲哚基)咪唑8(500mg，1.6mmol)加入25mL圆底烧瓶中，加入乙酸乙酯(2mL)，加入苄溴(0.28mL)，65℃下加热回流1h，反应完成后，冷却至室温，过滤，所得固体依次用乙酸乙酯、四氢呋喃、甲醇洗涤后干燥，得到溴化N-(4-吲哚基)-N’-烷基咪唑盐17(白色固体,旋转异构体1:1混合物，726mg，95％)；
1H NMR(600MHz,CDCl3)δ10.13(m,J＝7.9,2.3Hz,1H),7.46-7.42(m,2H),7.38-7.30(m,3H),6.71(s,1H),6.10(d,J＝15.0,1H),5.70(d,J＝15.0,1H),3.91(s,3H),2.74(s,3H),2.68-2.58(m,3H),2.54-2.47(m,1H),2.17-2.12(m,2H),2.06(s,3H),1.86-1.81(m,2H),1.81-1.75(m,1H),1.74-1.67(m,1H),1.50(s,3H),1.12(t,J＝7.2Hz,3H).
13C NMR(150MHz,CDCl3)δ141.9,136.2,135.0,133.8,132.1,129.2,129.1,128.7,128.3,125.9,125.1,124.3,123.5,120.2,102.7,51.0,32.5,21.6,21.3,20.3,20.2,19.9,17.5,16.5,14.0,8.4.
实施例16：溴化N-(4-吲哚基)-N’-烷基咪唑盐24的制备
(1)N-(4-吲哚基)咪唑8的制备同实施例15步骤(1)；
(2)将N-(4-吲哚基)咪唑8(500mg，1.6mmol)与溴代乙酸乙酯(0.26mL)加入到10mL圆底烧瓶中，加入乙酸乙酯(2mL)，65℃下加热回流1h，反应完成后，冷却至室温，过滤，所得固体依次用乙酸乙酯、四氢呋喃、甲醇洗涤后干燥，得到溴化N-(4-吲哚基)-N’-烷基咪唑盐24(白色固体,615mg,97％)；
1H NMR(600MHz,CDCl3)δ9.90(s,1H),6.72(s,1H),6.07(d,J＝18.0Hz,1H),5.43(d,J＝18.0Hz,1H),4.27(q,J＝7.2Hz,2H),3.92(s,3H),2.75(s,3H),2.69-2.56(m,4H),2.26-2.16(m,2H),2.08(s,3H),1.96-1.90(m,2H),1.88-1.80(m,2H),1.62(s,3H),1.32(t,J＝7.2Hz,3H),1.13(t,J＝7.2Hz,3H).
13C NMR(150MHz,CDCl3)δ166.5,141.9 137.4,135.0,131.6,129.5,125.9,125.2,124.4,123.6,120.1,103.1,62.7,48.0,32.5,21.5,21.4,20.3,19.8,19.5,17.5,16.4,14.1,14.0,8.4.
实施例17：N-(4-吲哚基)-N’-烷基咪唑盐作为前体催化剂在4-氟硝基苯与4-甲氧基苯甲醛缩合反应中的应用
在干燥反应管中依次加入N-(4-吲哚基)-N’-烷基咪唑盐(0.10mmol)、4-甲氧基苯甲醛(1.0mmol)、氢化钠(1.0mmol)，氩气保护下加入DMF，冷却至-15℃，加入4-氟硝基苯(1.0mmol)，搅拌10min后，移至0℃下反应2h，反应液以硅藻土过滤，乙酸乙酯冲洗，收集合并滤液，滤液用水萃取三次，收集合并有机相后，用无水硫酸钠干燥，过滤，浓缩，浓缩物经硅胶柱层析分离(石油醚：乙酸乙酯＝2:1)，收集洗脱液，43℃减压蒸馏，得到相应产物，催化活性评价结果见下表：
实施例18：N-(4-吲哚基)-N’-烷基咪唑盐作为前体催化剂在4-碘硝基苯与4-甲氧基苯甲醛缩合反应中的应用
在干燥反应管中依次加入N-(4-吲哚基)-N’-烷基咪唑盐(0.30mmol)、4-甲氧基苯甲醛(1.0mmol)、氢化钠(1.0mmol)，氩气保护下加入DMF，冷却至-15℃，加入4-碘硝基苯(1.0mmol)，搅拌10min后，移至0℃下反应2h；反应液以硅藻土过滤，乙酸乙酯冲洗，收集合并滤液，滤液用水萃取三次，收集合并有机相后，有机相以无水硫酸钠干燥，过滤，浓缩后经硅胶柱层析分离(石油醚：乙酸乙酯＝20:1)得到相应产物；催化活性评价结果见下表：
实施例19：N-(4-吲哚基)-N’-烷基咪唑盐作为前体催化剂在4-氟硝基苯与苯甲醛缩合反应中的应用
在干燥反应管中依次加入N-(4-吲哚基)-N’-烷基咪唑盐(0.30mmol)、苯甲醛(1.0mmol)、氢化钠(1.0mmol)，氩气保护下加入DMF，冷却至-15℃。加入4-氟硝基苯(1.0mmol)，搅拌10分钟后，移至0℃反应2h；反应液以硅藻土过滤，乙酸乙酯冲洗，收集合并滤液，滤液用水萃取三次，收集合并有机相后，有机相以无水硫酸钠干燥，过滤，浓缩后经硅胶柱层析分离(石油醚：乙酸乙酯＝20:1)得到相应产物；催化活性评价结果见下表；
实施例20：N-(4-吲哚基)-N’-烷基咪唑盐作为前体催化剂在4-氟苯基苯基酮与苯甲醛缩合反应中的应用
在干燥反应管中依次加入N-(4-吲哚基)-N’-烷基咪唑盐(0.10mmol)、苯甲醛(1.0mmol)、氢化钠(1.0mmol)，氩气保护下加入DMF，冷却至0℃。加入4-氟苯基苯基酮(1.0mmol)，搅拌10分钟后，移至室温搅拌30分钟，后加热至80℃反应1.5h。反应液以硅藻土过滤，乙酸乙酯冲洗，收集合并滤液，滤液用水萃取三次，收集合并有机相后，有机相以无水硫酸钠干燥，过滤，浓缩后经硅胶柱层析分离(石油醚：乙酸乙酯＝80:1)得到相应产物；催化活性评价结果见下表；
实施例21：N-(4-吲哚基)-N’-烷基咪唑盐作为前体催化剂在1-(2-羟基苯基)-3-苯基丙-2-烯-1-酮与肉桂醛缩合反应中的应用
在干燥反应管中依次加入N-(4-吲哚基)-N’-烷基咪唑盐(0.10mmol)、1-(2-羟基苯基)-3-苯基丙-2-烯-1-酮(1.0mmol)、肉桂醛(1.0mmol)，氩气保护下加入DME(1.5mL)、DBU(30uL)，室温反应24h，反应液以硅藻土过滤，乙酸乙酯冲洗，收集合并滤液，滤液用水萃取三次，收集合并有机相后，有机相以无水硫酸钠干燥，过滤，浓缩后经硅胶柱层析分离(石油醚：乙酸乙酯＝30:1)得到相应产物；催化活性评价结果见下表；
以上所述仅是本发明的优选实施方式。应当指出，对于本技术领域的普通技术人员，在不脱离本发明方法的前提下，还可进行若干改进和补充，这些可能的改进和补充也应视为本发明的保护范围。
Claims (3)
1.化学结构通式如下式所示的N-(4-吲哚基)-N’-烷基咪唑盐：
；
式中：R1选自C1-C8的烷基、C6-C12的芳基；
R2选自C1-C4的烷基、苯基、2-甲基苯基、3-甲基苯基、4-甲基苯基、2,4-二甲基苯基、2,6-二甲基苯基、2,4,6-三甲基苯基、2-异丙基苯基、4-异丙基苯基、2,6-二异丙基苯基、1-萘基、2-萘基；
R3、R4分别选自C1-C8的烷基；
R5、R6分别选自氢、甲基；
R7、R8选自氢、甲基；
R9选自C1-C15的烷基、C1-C15的官能化烷基；其中C1-C15的官能化烷基选自苄基、2-甲基苄基、3-甲基苄基、4-甲基苄基、2,6-二甲基苄基、2,4,6-三甲基苄基、1-苯基-1-乙基、二苯甲基、甲氧羰甲基、乙氧羰甲基、异丙氧羰甲基、(1-甲氧羰基)-1-乙基、(1-乙氧羰基)-1-乙基、(1-异丙氧羰基)-1-乙基；
n=1-6；
X-选自高氯酸根、氟硼酸根、氟磷酸根、氟离子、氯离子、溴离子、碘离子、对甲基苯磺酸根、甲磺酸根、三氟甲磺酸根、甲酸根、乙酸根。
2.根据权利要求1所述的N-(4-吲哚基)-N’-烷基咪唑盐，其特征在于：C1-C8的烷基选自甲基、乙基、丙基、2-丙基、环丙基、丁基、2-丁基、叔丁基、环丁基、戊基、3-戊基、环戊基、己基、环己基、庚基、4-庚基、环庚基；
C1-C4的烷基选自甲基、乙基、丙基、2-丙基、环丙基、丁基、2-丁基、异丁基、叔丁基、环丁基。
3.权利要求1所述的N-(4-吲哚基)-N’-烷基咪唑盐作为前体催化剂在有机合成中的应用。
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