CN115557888B - Method for preparing quinoline derivative by photocatalysis of N-aryl glycinate - Google Patents
Method for preparing quinoline derivative by photocatalysis of N-aryl glycinate Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 23
- 125000002943 quinolinyl group Chemical class N1=C(C=CC2=CC=CC=C12)* 0.000 title claims abstract description 12
- 238000007146 photocatalysis Methods 0.000 title claims abstract description 10
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 92
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims abstract description 51
- -1 ester compound Chemical class 0.000 claims abstract description 23
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000004440 column chromatography Methods 0.000 claims abstract description 18
- 229940027991 antiseptic and disinfectant quinoline derivative Drugs 0.000 claims abstract description 14
- 239000003504 photosensitizing agent Substances 0.000 claims abstract description 13
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Natural products NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000004471 Glycine Substances 0.000 claims abstract description 8
- 239000002253 acid Substances 0.000 claims abstract description 8
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 11
- 239000007800 oxidant agent Substances 0.000 claims description 10
- 230000001590 oxidative effect Effects 0.000 claims description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical group CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 239000007810 chemical reaction solvent Substances 0.000 claims description 6
- 150000002148 esters Chemical class 0.000 claims description 6
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 6
- 229930187593 rose bengal Natural products 0.000 claims description 5
- 229940081623 rose bengal Drugs 0.000 claims description 5
- STRXNPAVPKGJQR-UHFFFAOYSA-N rose bengal A Natural products O1C(=O)C(C(=CC=C2Cl)Cl)=C2C21C1=CC(I)=C(O)C(I)=C1OC1=C(I)C(O)=C(I)C=C21 STRXNPAVPKGJQR-UHFFFAOYSA-N 0.000 claims description 5
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 5
- VSANUNLQSRKIQA-UHFFFAOYSA-K trichlororuthenium hexahydrate Chemical compound O.O.O.O.O.O.Cl[Ru](Cl)Cl VSANUNLQSRKIQA-UHFFFAOYSA-K 0.000 claims description 5
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 4
- 229940125904 compound 1 Drugs 0.000 claims description 4
- 229940125782 compound 2 Drugs 0.000 claims description 4
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 4
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 3
- SEACYXSIPDVVMV-UHFFFAOYSA-L eosin Y Chemical compound [Na+].[Na+].[O-]C(=O)C1=CC=CC=C1C1=C2C=C(Br)C(=O)C(Br)=C2OC2=C(Br)C([O-])=C(Br)C=C21 SEACYXSIPDVVMV-UHFFFAOYSA-L 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- 108010004729 Phycoerythrin Proteins 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical group CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 125000001153 fluoro group Chemical group F* 0.000 claims description 2
- PYLWMHQQBFSUBP-UHFFFAOYSA-N monofluorobenzene Chemical compound FC1=CC=CC=C1 PYLWMHQQBFSUBP-UHFFFAOYSA-N 0.000 claims description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 2
- IICCLYANAQEHCI-UHFFFAOYSA-N 4,5,6,7-tetrachloro-3',6'-dihydroxy-2',4',5',7'-tetraiodospiro[2-benzofuran-3,9'-xanthene]-1-one Chemical compound O1C(=O)C(C(=C(Cl)C(Cl)=C2Cl)Cl)=C2C21C1=CC(I)=C(O)C(I)=C1OC1=C(I)C(O)=C(I)C=C21 IICCLYANAQEHCI-UHFFFAOYSA-N 0.000 claims 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000000543 intermediate Substances 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 abstract 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 32
- IFOFOLBASOSMKE-UHFFFAOYSA-N 2-methoxycarbonylpent-3-ynoic acid Chemical compound CC#CC(C(=O)O)C(=O)OC IFOFOLBASOSMKE-UHFFFAOYSA-N 0.000 description 14
- 150000003248 quinolines Chemical class 0.000 description 10
- MLSGRWDEDYJNER-UHFFFAOYSA-N ethyl 2-anilinoacetate Chemical compound CCOC(=O)CNC1=CC=CC=C1 MLSGRWDEDYJNER-UHFFFAOYSA-N 0.000 description 9
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 8
- 238000005160 1H NMR spectroscopy Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- BXPNTXBBAVYAMD-UHFFFAOYSA-N phenyl 2-aminoacetate Chemical compound NCC(=O)OC1=CC=CC=C1 BXPNTXBBAVYAMD-UHFFFAOYSA-N 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 4
- 238000012544 monitoring process Methods 0.000 description 3
- 238000007363 ring formation reaction Methods 0.000 description 3
- AZJPTIGZZTZIDR-UHFFFAOYSA-L rose bengal Chemical compound [K+].[K+].[O-]C(=O)C1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1C1=C2C=C(I)C(=O)C(I)=C2OC2=C(I)C([O-])=C(I)C=C21 AZJPTIGZZTZIDR-UHFFFAOYSA-L 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- VQGHOUODWALEFC-UHFFFAOYSA-N 2-phenylpyridine Chemical compound C1=CC=CC=C1C1=CC=CC=N1 VQGHOUODWALEFC-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- XUGNJOCQALIQFG-UHFFFAOYSA-N 2-ethenylquinoline Chemical class C1=CC=CC2=NC(C=C)=CC=C21 XUGNJOCQALIQFG-UHFFFAOYSA-N 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- DHMQDGOQFOQNFH-UHFFFAOYSA-M Aminoacetate Chemical compound NCC([O-])=O DHMQDGOQFOQNFH-UHFFFAOYSA-M 0.000 description 1
- MJBPUQUGJNAPAZ-UHFFFAOYSA-N Butine Natural products O1C2=CC(O)=CC=C2C(=O)CC1C1=CC=C(O)C(O)=C1 MJBPUQUGJNAPAZ-UHFFFAOYSA-N 0.000 description 1
- 238000006681 Combes synthesis reaction Methods 0.000 description 1
- 238000007108 Doebner-von Miller reaction Methods 0.000 description 1
- 238000010766 Gould–Jacobs reaction Methods 0.000 description 1
- 238000006153 Pfitzinger synthesis reaction Methods 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- 238000005614 Skraup synthesis reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000005899 aromatization reaction Methods 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 238000010523 cascade reaction Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- IINNWAYUJNWZRM-UHFFFAOYSA-L erythrosin B Chemical compound [Na+].[Na+].[O-]C(=O)C1=CC=CC=C1C1=C2C=C(I)C(=O)C(I)=C2OC2=C(I)C([O-])=C(I)C=C21 IINNWAYUJNWZRM-UHFFFAOYSA-L 0.000 description 1
- HLYTZTFNIRBLNA-LNTINUHCSA-K iridium(3+);(z)-4-oxopent-2-en-2-olate Chemical compound [Ir+3].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O HLYTZTFNIRBLNA-LNTINUHCSA-K 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- SZJUWKPNWWCOPG-UHFFFAOYSA-N methyl 2-anilinoacetate Chemical compound COC(=O)CNC1=CC=CC=C1 SZJUWKPNWWCOPG-UHFFFAOYSA-N 0.000 description 1
- CARILLOXVAEKID-UHFFFAOYSA-N n-methyl-2-phenylaniline Chemical compound CNC1=CC=CC=C1C1=CC=CC=C1 CARILLOXVAEKID-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 230000005588 protonation Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- VJMOXMZXJOIGDB-UHFFFAOYSA-N trimethyl quinoline-2,3,4-tricarboxylate Chemical compound COC(=O)c1nc2ccccc2c(C(=O)OC)c1C(=O)OC VJMOXMZXJOIGDB-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
- C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
- C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D215/48—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
- C07D215/54—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen attached in position 3
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for preparing quinoline derivatives by photocatalysis of N-aryl glycine ester, which comprises the following steps: dissolving an N-aryl glycine ester compound and a butynedicarboxylic acid ester compound in a dimethyl sulfoxide solvent, adding a photosensitizer and dicumyl peroxide, reacting for 24 hours at room temperature under the condition of blue light irradiation, and separating by column chromatography after the reaction is finished to obtain a quinoline derivative. The preparation method has the advantages of low-cost and easily-obtained raw materials, mild reaction system, simple operation and high yield. The quinoline derivatives have wide application and can be used as useful synthetic intermediates.
Description
Technical Field
The invention belongs to the field of organic synthetic chemistry, and relates to a method for preparing quinoline derivatives by photocatalysis of N-aryl glycinate, in particular to a method for preparing quinoline derivatives by an addition cyclization reaction of N-aryl glycinate compounds and butine dicarboxylic acid ester compounds in the presence of an oxidant and a photosensitizer and under the irradiation of blue light LEDs.
Background
Quinoline and its derivatives are nitrogen-containing heterocycles widely existing in nature, have wide biological activities, are important synthetic intermediates in the field of organic synthesis, and are widely applied in other industrial fields, so that their synthetic methods are attracting attention. Traditional quinoline skeleton synthesis methods such as Skraup reaction, combes reaction, conrad-Limbach reaction, doebner-VonMiller reaction, gould-Jacobs reaction, friedlander reaction, povavov reaction, pfitzinger reaction and the like are more severe in reaction conditions, more side reactions and more serious in pollution. Recently, a number of reports have been made on the preparation of quinoline derivatives by photocatalytic reaction, such as: (1) Zhang et al reported a method for producing quinoline derivatives by a tandem reaction of glycinate and non-activated olefins by visible light catalytic oxidative dehydrogenation coupling/aromatization (J.org.chem., 2016,81,12433-12442.), but the reaction required a synergistic effect of copper salt and photocatalyst to react, and the reaction system was relatively complex. (2) Jiang et al also reported the use of visible light to induce dual synergistic catalysis of chiral phosphoric acid and DPZ photosensitizers, allowing a variety of alpha-branched 2-vinylpyridine and 2-vinylquinoline compounds to undergo redox, free radical conjugated addition, and protonation processes with glycine, respectively, and finally obtaining a variety of chiral 3- (2-pyridine/quinoline) -3-substituted amine compounds in high yields (j.am.chem.soc., 2018,140,6083-6087.). In the reaction, the synergistic effect of cobalt salt, an additive and a photocatalyst is needed to react, the reaction system is complex, the separation is difficult, the substrate applicability is poor, and the large-scale popularization and application are difficult.
Thus, there remains a need to develop and optimize new methods for preparing polysubstituted quinoline derivatives.
Disclosure of Invention
The invention aims to provide a simple preparation method of quinoline derivatives mainly aiming at the defects and the shortcomings of the prior art.
The invention uses N-aryl glycine ester compounds and butynedicarboxylic acid ester compounds as raw materials, and the N-aryl glycine ester compounds and the butynedicarboxylic acid ester compounds react for 24 hours at room temperature in the presence of an oxidant and a photosensitizer in a dimethyl sulfoxide solution and under the irradiation of a blue light LED, and the quinoline derivatives are generated through addition cyclization reaction. The reaction method has the advantages of cheap and easily obtained raw materials, mild reaction conditions, no need of transition metal, simple post-treatment process, wide product expansion range and good industrialization potential.
The synthetic route principle of the invention is as follows:
Wherein R 1 is H, or is fluorine, chlorine, bromine, methyl, ethyl, propyl, butyl, isopropyl, tert-butyl, methoxy, ethoxy, trifluoromethyl, substituted phenyl, which may be substituted at ortho, meta, para and multi-position of the benzene ring; r 2 represents methyl, ethyl, propyl, butyl, isopropyl, tert-butyl, benzyl; r 3 represents methyl, ethyl, propyl, butyl, isopropyl, tert-butyl, phenyl, benzyl; the light source is a blue light LED lamp; the oxidant is di-tert-butyl peroxide or benzoyl peroxide, dicumyl peroxide or tert-butyl hydroperoxide; the photosensitizer is terpyridyl ruthenium chloride hexahydrate or one of iridium acetylacetonate (2-phenylpyridine), erythrosin B, eosin Y and rose bengal; the reaction solvent is acetonitrile or one of dimethyl sulfoxide, N, N-dimethylformamide, 1, 4-dioxane, chlorobenzene, toluene, fluorobenzene and tetrahydrofuran.
In order to achieve the aim, the invention adopts the following technical scheme to synthesize the compound:
Sequentially adding an N-aryl glycine ester compound 1, a butynedicarboxylic acid ester compound 2, an oxidant, a photosensitizer and a reaction solvent into a reaction tube, and after the addition, placing the reaction tube under blue light (blue LED) irradiation for reaction for 24 hours at room temperature. And (3) after the reaction is finished, performing rapid column chromatography separation to obtain the quinoline derivative 3.
The reaction light source in the method adopts a 24W blue light LED lamp.
Dicumyl peroxide is selected as the oxidant in the method.
The photosensitizer described in the above method is selected from rose bengal as the reacting photosensitizer.
The organic solvent in the method adopts dimethyl sulfoxide as the reaction solvent.
The ratio of the amounts of the N-methyl biphenyl-2-amine compound 1, the butynedicarboxylic acid ester compound 2, the oxidant and the photosensitizer in the method is 1:2:2:0.1.
Compared with the prior art route, the invention has the following advantages:
(1) The method has the advantages of wide substrate application range, mild reaction conditions, simple post-treatment process, high product yield and wide product expansion range.
(2) The method is simple, green, efficient and superior to the synthesis method reported in the prior literature, transition metal catalysis is not needed, and the N-aryl glycine ester compound and the butynedicarboxylic acid ester compound are subjected to addition cyclization reaction under blue light irradiation to prepare the quinoline derivative.
Detailed Description
The invention will be described in further detail with reference to specific examples, but the scope of the invention claimed is not limited thereto.
Implementation example 1: 0.018g (0.1 mmol) ethyl N-phenylglycinate 1a,0.028g (0.2 mmol) methyl butynedicarboxylate 2a, 0.006g (0.01 mmol) terpyridyl ruthenium chloride hexahydrate, 0.054g (0.2 mmol) dicumyl peroxide, 2mL DMSO were added sequentially to a 10mL reaction tube, and the reaction was magnetically stirred for 24h under 24W blue LED irradiation, and TLC monitored the progress of the reaction. After the reaction, column chromatography was carried out to obtain 2-ethoxycarbonyl-3, 4-dimethoxycarbonyl quinoline 3a as a yellow oil (22 mg) in a yield of 68％.1H NMR(400Hz,CDCl3)(δ,ppm)8.31(d,J＝8.4Hz,1H),8.06(d,J＝8.0Hz,1H),7.91(m,1H),7.76(m,1H),4.54(q,J＝7.2Hz,2H),4.08(s,3H),3.98(s,3H),1.47(t,J＝7.2Hz,3H).13C NMR(100MHz,CDCl3,ppm)166.02,165.91,165.42,148.43,147.70,140.22,132.18,130.60,130.00,125.64,123.71,122.74,77.36,77.04,76.72,62.77,53.37,53.23,14.16. according to the reaction principle of example 1 as follows:
Implementation example 2: 0.018g (0.1 mmol) ethyl N-phenylglycinate 1a,0.028g (0.2 mmol) methyl butynedicarboxylate 2a, 0.006g (0.01 mmol) terpyridyl ruthenium chloride hexahydrate, 0.048g (0.2 mmol) benzoyl peroxide, 2mL DMSO were added sequentially to a 10mL reaction tube, and the reaction was magnetically stirred for 24h under 24W blue LED irradiation, followed by TLC monitoring. After the completion of the reaction, the mixture was separated by column chromatography to give 2-ethoxycarbonyl-3, 4-dimethoxycarbonyl-quinoline 3a as a yellow oil (20 mg) in a yield of 62%. The reaction principle of example 2 is as follows:
Implementation example 3: 0.018g (0.1 mmol) ethyl N-phenylglycinate 1a,0.028g (0.2 mmol) methyl butynedicarboxylate 2a, 0.006g (0.01 mmol) terpyridyl ruthenium chloride hexahydrate, 0.054g (0.2 mmol) potassium persulfate, 2mL DMSO were added sequentially to a 10mL reaction tube, and the reaction was magnetically stirred for 24h under 24W blue LED irradiation, followed by TLC monitoring. After the completion of the reaction, the mixture was separated by column chromatography to give 2-ethoxycarbonyl-3, 4-dimethoxycarbonyl-quinoline 3a as a yellow oil (21 mg) in a yield of 65%. The reaction principle of example 3 is as follows:
Implementation example 4: 0.018g (0.1 mmol) ethyl N-phenylglycinate 1a,0.028g (0.2 mmol) methyl butynedicarboxylate 2a, 0.008g (0.01 mmol) phycoerythrin B, 0.054g (0.2 mmol) dicumyl peroxide and 2mL DMSO are added into a 10mL reaction tube in sequence, under the irradiation of 24W blue LED, the reaction is magnetically stirred for 24h, and TLC monitors the reaction progress. After the reaction, the mixture was separated by column chromatography to give 2-ethoxycarbonyl-3, 4-dimethoxycarbonyl-quinoline 3a as a yellow oil (23 mg) in a yield of 72%. The reaction principle of example 4 is as follows:
Implementation example 5: 0.018g (0.1 mmol) ethyl N-phenylglycinate 1a,0.028g (0.2 mmol) methyl butynedicarboxylate 2a, 0.007g (0.01 mmol) eosin Y, 0.054g (0.2 mmol) dicumyl peroxide, 2mL DMSO were added sequentially to a 10mL reaction tube, the reaction was magnetically stirred for 24h under 24W blue LED irradiation, and TLC monitored. After the completion of the reaction, the mixture was separated by column chromatography to give 2-ethoxycarbonyl-3, 4-dimethoxycarbonyl-quinoline 3a as a yellow oil (22 mg) in a yield of 70%. The reaction principle of example 5 is as follows:
Implementation example 6: 0.018g (0.1 mmol) ethyl N-phenylglycinate 1a,0.028g (0.2 mmol) methyl butynedicarboxylate 2a, 0.010g (0.01 mmol) Rose bengal (Rose B), 0.054g (0.2 mmol) dicumyl peroxide, 2mL DMSO were added sequentially to a 10mL reaction tube, the reaction was magnetically stirred for 24h under 24W blue LED irradiation, and TLC monitored. After the completion of the reaction, the mixture was separated by column chromatography to give 2-ethoxycarbonyl-3, 4-dimethoxycarbonyl-quinoline 3a as a yellow oil (25 mg) in 78% yield. The reaction principle of example 6 is as follows:
implementation example 7: 0.018g (0.1 mmol) ethyl N-phenylglycinate 1a,0.028g (0.2 mmol) methyl butynedicarboxylate 2a, 0.010g (0.01 mmol) Rose B, 0.054g (0.2 mmol) dicumyl peroxide, 2mL tetrahydrofuran were added sequentially to a 10mL reaction tube, and the reaction was magnetically stirred for 24h under 24W blue LED irradiation, followed by TLC monitoring. After the completion of the reaction, the mixture was separated by column chromatography to give 2-ethoxycarbonyl-3, 4-dimethoxycarbonyl-quinoline 3a as a yellow oil (7 mg) in a yield of 23%. The reaction principle of example 7 is as follows:
Implementation example 8: 0.018g (0.1 mmol) ethyl N-phenylglycinate 1a,0.028g (0.2 mmol) methyl butynedicarboxylate 2a, 0.010g (0.01 mmol) Rose B, 0.054g (0.2 mmol) dicumyl peroxide, 2mL acetonitrile were sequentially added to a 10mL reaction tube, and the reaction was magnetically stirred for 24h under 24W blue LED irradiation, and TLC monitored. After the completion of the reaction, the mixture was separated by column chromatography to give 3a, 13mg of 2-ethoxycarbonyl-3, 4-dimethoxycarbonyl-quinoline in a yield of 42%. The reaction principle of example 8 is as follows:
Implementation example 9: 0.019g (0.1 mmol) of ethyl N- (4-methyl-) phenylglycinate 1B,0.028g (0.2 mmol) of methyl butynedicarboxylate 2a, 0.010g (0.01 mmol) of Rose B, 0.054g (0.2 mmol) of dicumyl peroxide and 2mL of DMSO are sequentially added into a 10mL reaction tube, the reaction is magnetically stirred for 24h under the irradiation of a 24W blue LED, and TLC monitors the progress of the reaction. After the reaction, column chromatography was carried out to obtain 6-methyl-2-ethoxycarbonyl-3, 4-dimethoxycarbonylquinoline 3b as a yellow oil (29.5 mg) in a yield of 89％.1H NMR(400MHz,CDCl3,ppm)δ8.19(d,J＝8.8Hz,1H),7.79(s,1H),7.73(dd,J＝8.8,2.0Hz,1H),4.53(q,J＝7.2Hz,2H),4.08(s,3H),3.97(s,3H),2.60(s,3H),1.46(t,J＝7.2Hz,3H).13C NMR(100MHz,CDCl3,ppm)δ166.20,165.51,147.33,146.40,140.76,139.30,134.58,130.27,124.29,123.80,122.89,119.82,77.37,77.05,76.73,62.69,53.33,53.18,22.12,14.17. according to the reaction principle of example 9 as follows:
Implementation example 10: 0.021g (0.1 mmol) of ethyl N- (3, 5-dimethyl-) phenylglycinate 1c,0.028g (0.2 mmol) of methyl butynedicarboxylate 2a, 0.010g (0.01 mmol) of Rose B, 0.054g (0.2 mmol) of dicumyl peroxide and 2mL of DMSO are sequentially added into a 10mL reaction tube, the reaction is magnetically stirred for 24h under the irradiation of a 24W blue LED, and TLC monitors the reaction progress. After the reaction, column chromatography was carried out to obtain 5, 7-dimethyl-2-ethoxycarbonyl-3, 4-dimethoxycarbonylquinoline 3c as a yellow oil (29.7 mg) in a yield of 86％.1H NMR(400MHz,CDCl3,ppm)δ7.95(s,1H),7.39(s,1H),4.51(q,J＝7.2Hz,2H),4.04(s,3H),3.95(s,3H),2.63(s,3H),2.55(s,3H),1.46(t,J＝7.2Hz,3H).13C NMR(100MHz,CDCl3,ppm)δ168.50,166.20,165.59,149.20,147.75,142.47,140.07,134.93,134.43,128.57,121.82,120.86,77.36,77.05,76.73,62.61,53.19,53.15,21.62,20.69,14.18. according to the following reaction principle of example 10:
Implementation example 11: 0.026g (0.1 mmol) ethyl N- (4-bromo-) phenylglycinate 1d,0.028g (0.2 mmol) methyl butynedicarboxylate 2a, 0.010g (0.01 mmol) Rose B, 0.054g (0.2 mmol) dicumyl peroxide, 2mL DMSO were added sequentially to a 10mL reaction tube, the reaction was magnetically stirred for 24h under 24W blue LED irradiation, and TLC monitored the progress of the reaction. After the reaction, column chromatography was carried out to obtain 3d, 24.1mg, of 2-ethoxycarbonyl-3, 4-dimethoxycarbonyl-6-bromoquinoline as a white solid, which was used in the following reaction principle of example 11 in a yield of 61％.1H NMR(400MHz,CDCl3,ppm)δ8.26(d,J＝2.0Hz,1H),8.16(d,J＝9.2Hz,1H),7.97(dd,J＝8.8Hz,2.0Hz,1H),4.53(q,J＝7.2Hz,2H),4.08(s,3H),3.98(s,3H),1.47(t,J＝7.2Hz,3H).13C NMR(100MHz,CDCl3,ppm)δ165.75,165.41,165.03,148.37,146.26,138.68,135.78,132.09,127.88,124.94,124.84,124.22,77.37,77.05,76.74,62.93,53.60,53.35,14.15.:
Implementation example 12: 0.020g (0.1 mmol) ethyl N- (4-fluoro-) phenylglycinate 1e,0.028g (0.2 mmol) methyl butynedicarboxylate 2a, 0.010g (0.01 mmol) Rose B, 0.054g (0.2 mmol) dicumyl peroxide, 2mL DMSO were added sequentially to a 10mL reaction tube, the reaction was magnetically stirred for 24h under 24W blue LED irradiation, and TLC monitored the progress of the reaction. After the reaction, column chromatography was carried out to obtain 2-ethoxycarbonyl-3, 4-dimethoxycarbonyl-6-fluoroquinoline 3e as a pale yellow solid (24.8 mg) with a yield of 74％.1H NMR(400MHz,CDCl3,ppm)δ8.33(dd,J＝9.2,5.2Hz,1H),7.78(dd,J＝9.6,2.4Hz,1H),7.68(m,J＝8.4,2.4Hz,1H),4.54(q,J＝7.2Hz,2H),4.07(s,3H),3.99(s,3H),1.47(t,J＝7.2Hz,3H).13C NMR(100MHz,CDCl3,ppm)δ166.00,165.48,163.84,161.32,147.27,144.84,138.70,133.46,125.12,124.61,122.78,109.65,77.36,77.05,76.73,62.88,53.52,53.32,14.16. according to the following reaction principle of example 12:
Implementation example 13: 0.022g (0.1 mmol) of ethyl N- (4-chloro-) phenylglycinate 1f,0.028g (0.2 mmol) of methyl butynedicarboxylate 2a, 0.010g (0.01 mmol) of Rose B, 0.054g (0.2 mmol) of dicumyl peroxide and 2mL of DMSO are sequentially added into a 10mL reaction tube, the reaction is magnetically stirred for 24h under the irradiation of a 24W blue LED, and the TLC monitors the progress of the reaction. After the reaction, column chromatography was carried out to obtain 2-ethoxycarbonyl-3, 4-dimethoxycarbonyl-6-chloroquinoline 3f as a pale yellow solid (26.4 mg) in a yield of 75％.1H NMR(400Hz,CDCl3)(δ,ppm)8.24(d,J＝9.2Hz,1H),8.09(d,J＝2.4Hz,1H),7.84(dd,J＝8.8,2.0Hz,1H),4.53(q,J＝7.2Hz,2H),4.08(s,3H),3.98(s,3H),1.47(t,J＝7.2Hz,3H);13C NMR(100MHz,CDCl3)δ165.76,165.39,164.99,148.25,146.06,138.74,136.51,133.17,132.09,129.31,124.56,121.04,77.36,77.04,76.72,62.89,53.55,53.31,14.14. according to the reaction principle of example 13 as follows:
Implementation example 14: 0.017g (0.1 mmol) of methyl N-phenylglycinate 1g,0.028g (0.2 mmol) of methyl butynedicarboxylate 2a, 0.010g (0.01 mmol) of Rose B, 0.054g (0.2 mmol) of dicumyl peroxide and 2mL of DMSO are sequentially added into a 10mL reaction tube, the reaction is magnetically stirred for 24h under the irradiation of a 24W blue LED, and the TLC monitors the reaction progress. After the reaction, 3g of 2-methoxycarbonyl-3, 4-dimethoxycarbonyl quinoline was obtained by column chromatography, 16.7mg of yellow solid was obtained, and the reaction principle of the embodiment 14 was carried out with a yield of 55％.1H NMR(500Hz,CDCl3)(δ,ppm)8.30(dt,J＝8.4,0.8Hz,1H),8.07(dt,J＝8.4,1.0Hz,1H),7.91(m,1H),7.76(m,1H),4.07(d,J＝1.6Hz,6H),3.98(s,3H);13C NMR(100MHz,CDCl3)δ165.95,165.89,165.71,147.76,147.63,140.04,132.21,130.58,130.15,125.67,123.83,123.18,77.37,77.05,76.73,53.51,53.38,53.31. as follows:
Implementation example 15: 0.018g (0.1 mmol) of ethyl N-phenylglycinate 1h,0.045g (0.2 mmol) of tert-butyl butynedicarboxylate 2B, 0.010g (0.01 mmol) of Rose B, 0.054g (0.2 mmol) of dicumyl peroxide and 2mL of DMSO are sequentially added into a 10mL reaction tube, the reaction is magnetically stirred for 24h under the irradiation of a 24W blue LED, and TLC monitors the reaction progress. After the reaction, separating by column chromatography to obtain 2-ethoxycarbonyl-3, 4-di-tert-butoxycarbonyl quinoline 3h, 20.9mg of yellow solid, the yield 52％.1H NMR(400Hz,CDCl3)(δ,ppm)8.25(dd,J＝8.5,1.3,0.6Hz,1H),8.00(dd,J＝8.4,1.4,0.7Hz,1H),7.85(m,1H),7.72(m,1H),4.54(q,J＝7.2Hz,2H),1.70(s,9H),1.62(s,9H),1.47(t,J＝7.2Hz,3H);13C NMR(100MHz,CDCl3)δ165.89,165.00,164.23,149.16,147.34,141.93,131.58,130.37,129.43,125.36,123.88,122.92,84.53,83.72,77.36,77.04,76.73,62.49,28.15,27.92,14.17., the reaction principle of the embodiment 15 is as follows:
Claims (6)
1. A method for preparing quinoline derivatives by photocatalysis of N-aryl glycinate, which is characterized by comprising the following steps: dissolving an N-aryl glycine ester compound 1 and a butynedicarboxylic acid ester compound 2 in a reaction solvent, adding an oxidant and a photosensitizer, reacting for 24 hours at room temperature under the irradiation of a blue light LED, and separating by column chromatography after the reaction is finished to obtain a target product quinoline derivative 3, wherein the reaction formula is as follows:
Wherein R 1 is H, or is fluorine, chlorine, bromine, methyl, ethyl, propyl, butyl, isopropyl, tertiary butyl, methoxy, ethoxy, trifluoromethyl, substituted phenyl, R 1 is positioned at the ortho, meta or para position of amino on the benzene ring; r 2 represents methyl, ethyl, propyl, butyl, isopropyl, tert-butyl, benzyl; r 3 represents methyl, ethyl, propyl, butyl, isopropyl, tert-butyl, phenyl, benzyl; the light source is a blue light LED lamp; the oxidant is di-tert-butyl peroxide or benzoyl peroxide, dicumyl peroxide or tert-butyl hydroperoxide; the photosensitizer is one of terpyridyl ruthenium chloride hexahydrate, phycoerythrin B, eosin Y and rose bengal; the reaction solvent is acetonitrile or one of dimethyl sulfoxide, N, N-dimethylformamide, 1, 4-dioxane, chlorobenzene, toluene, fluorobenzene and tetrahydrofuran.
2. The method for preparing quinoline derivatives 3 by photocatalysis of N-aryl glycinate according to claim 1, wherein a 24W blue light LED lamp is selected as the reaction light source.
3. The method for preparing quinoline derivatives 3 from N-arylglycinate by photocatalysis according to claim 1, wherein dicumyl peroxide is selected as the reaction oxidant.
4. The method for preparing quinoline derivatives 3 from N-arylglycinate by photocatalysis according to claim 1, wherein rose bengal is selected as the reaction photosensitizer.
5. The method for preparing quinoline derivatives 3 from N-arylglycinate by photocatalysis according to claim 1, wherein dimethyl sulfoxide is selected as the reaction solvent.
6. The method for preparing quinoline derivatives 3 from N-arylglycine esters through photocatalysis according to claim 1, wherein the ratio of the amounts of the N-arylglycine ester compound 1, the butynedicarboxylic acid ester compound 2, the oxidant and the photosensitizer is 1:2:2:0.1.
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| CN106380446A (en) * | 2016-08-30 | 2017-02-08 | 南阳师范学院 | Synthesis method of quinoline-2-formic acid ester derivatives |
| CN108484498A (en) * | 2018-05-18 | 2018-09-04 | 西北师范大学 | The method of synthesis of quinoline class compound is reacted using dual oxide dehydrocyclization |
| CN113444041A (en) * | 2021-06-29 | 2021-09-28 | 安徽理工大学 | Method for synthesizing polysubstituted quinoline compound through photocatalysis |
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| CN106380446A (en) * | 2016-08-30 | 2017-02-08 | 南阳师范学院 | Synthesis method of quinoline-2-formic acid ester derivatives |
| CN108484498A (en) * | 2018-05-18 | 2018-09-04 | 西北师范大学 | The method of synthesis of quinoline class compound is reacted using dual oxide dehydrocyclization |
| CN113444041A (en) * | 2021-06-29 | 2021-09-28 | 安徽理工大学 | Method for synthesizing polysubstituted quinoline compound through photocatalysis |
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| Acid-promoted iron-catalysed dehydrogenative [4 + 2] cycloaddition for the synthesis of quinolines under air;Jinfei Yang等;RSC Adv.;20180910(第8期);31603-31607 * |
| Hui Xu，Guan-Wu Wang.Solvent-Free Mechanosynthesis of Polysubstituted 1,2- Dihydroquinolines from Anilines and Alkyne Esters.J. Org. Chem..2022,第87卷8480−8491. * |
| Iron-Catalyzed Oxidative Tandem Reactions with TEMPO Oxoammonium Salts: Synthesis of Dihydroquinazolines and Quinolines;Renate Rohlmann等;J. Org. Chem.;20130524;第78卷;6050−6064 * |
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