CN115557888A - Method for preparing quinoline derivative by photocatalysis of N-aryl glycine ester - Google Patents
Method for preparing quinoline derivative by photocatalysis of N-aryl glycine ester Download PDFInfo
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- CN115557888A CN115557888A CN202211387768.XA CN202211387768A CN115557888A CN 115557888 A CN115557888 A CN 115557888A CN 202211387768 A CN202211387768 A CN 202211387768A CN 115557888 A CN115557888 A CN 115557888A
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- 238000000034 method Methods 0.000 title claims abstract description 27
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Natural products NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 239000004471 Glycine Substances 0.000 title claims abstract description 18
- 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 101
- 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 25
- 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 17
- 239000003504 photosensitizing agent Substances 0.000 claims abstract description 13
- 229940027991 antiseptic and disinfectant quinoline derivative Drugs 0.000 claims abstract description 8
- 238000000926 separation method Methods 0.000 claims abstract description 7
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 10
- 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
- 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
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 6
- 239000007810 chemical reaction solvent Substances 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
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 6
- JFJNVIPVOCESGZ-UHFFFAOYSA-N 2,3-dipyridin-2-ylpyridine Chemical group N1=CC=CC=C1C1=CC=CN=C1C1=CC=CC=N1 JFJNVIPVOCESGZ-UHFFFAOYSA-N 0.000 claims description 5
- 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
- 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
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 claims description 2
- 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
- CGKQZIULZRXRRJ-UHFFFAOYSA-N Butylone Chemical compound CCC(NC)C(=O)C1=CC=C2OCOC2=C1 CGKQZIULZRXRRJ-UHFFFAOYSA-N 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 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
- DBNYWRKRZTXMCU-UHFFFAOYSA-N iridium;2-phenylpyridine Chemical compound [Ir].C1=CC=CC=C1C1=CC=CC=N1.C1=CC=CC=C1C1=CC=CC=N1 DBNYWRKRZTXMCU-UHFFFAOYSA-N 0.000 claims description 2
- PYLWMHQQBFSUBP-UHFFFAOYSA-N monofluorobenzene Chemical compound FC1=CC=CC=C1 PYLWMHQQBFSUBP-UHFFFAOYSA-N 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- VSANUNLQSRKIQA-UHFFFAOYSA-K trichlororuthenium hexahydrate Chemical compound O.O.O.O.O.O.Cl[Ru](Cl)Cl VSANUNLQSRKIQA-UHFFFAOYSA-K 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
- OALHHIHQOFIMEF-UHFFFAOYSA-N 3',6'-dihydroxy-2',4',5',7'-tetraiodo-3h-spiro[2-benzofuran-1,9'-xanthene]-3-one Chemical compound O1C(=O)C2=CC=CC=C2C21C1=CC(I)=C(O)C(I)=C1OC1=C(I)C(O)=C(I)C=C21 OALHHIHQOFIMEF-UHFFFAOYSA-N 0.000 claims 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims 1
- 150000002148 esters Chemical class 0.000 claims 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000002253 acid Substances 0.000 abstract description 2
- 239000000543 intermediate Substances 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 abstract 1
- 239000002904 solvent Substances 0.000 abstract 1
- IFOFOLBASOSMKE-UHFFFAOYSA-N 2-methoxycarbonylpent-3-ynoic acid Chemical compound CC#CC(C(=O)O)C(=O)OC IFOFOLBASOSMKE-UHFFFAOYSA-N 0.000 description 13
- 150000003248 quinolines Chemical class 0.000 description 10
- GMDJMLOOHULQEV-UHFFFAOYSA-N 2-(n-ethylanilino)acetic acid Chemical compound OC(=O)CN(CC)C1=CC=CC=C1 GMDJMLOOHULQEV-UHFFFAOYSA-N 0.000 description 9
- 239000007787 solid Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 3
- 229940068911 chloride hexahydrate Drugs 0.000 description 3
- VOAPTKOANCCNFV-UHFFFAOYSA-N hexahydrate;hydrochloride Chemical compound O.O.O.O.O.O.Cl VOAPTKOANCCNFV-UHFFFAOYSA-N 0.000 description 3
- 230000008569 process Effects 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
- 229910052707 ruthenium Inorganic materials 0.000 description 3
- ZGUNAGUHMKGQNY-ZETCQYMHSA-N L-alpha-phenylglycine zwitterion Chemical compound OC(=O)[C@@H](N)C1=CC=CC=C1 ZGUNAGUHMKGQNY-ZETCQYMHSA-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
- 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 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- DVYVBENBIMEAJZ-UHFFFAOYSA-N 2-(n-methylanilino)acetic acid Chemical compound OC(=O)CN(C)C1=CC=CC=C1 DVYVBENBIMEAJZ-UHFFFAOYSA-N 0.000 description 1
- 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
- 238000006681 Combes synthesis 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
- 230000002153 concerted effect Effects 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
- 230000009977 dual effect Effects 0.000 description 1
- MLSGRWDEDYJNER-UHFFFAOYSA-N ethyl 2-anilinoacetate Chemical compound CCOC(=O)CNC1=CC=CC=C1 MLSGRWDEDYJNER-UHFFFAOYSA-N 0.000 description 1
- KDKYADYSIPSCCQ-UHFFFAOYSA-N ethyl acetylene Natural products CCC#C KDKYADYSIPSCCQ-UHFFFAOYSA-N 0.000 description 1
- 238000003818 flash chromatography Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 150000004702 methyl esters Chemical class 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
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-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
- 238000007086 side reaction Methods 0.000 description 1
- 238000001308 synthesis method 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
Landscapes
- 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 the N-aryl glycine ester compound and the butynedicarboxylic acid ester compound in a dimethyl sulfoxide solvent, adding a photosensitizer and dicumyl peroxide, reacting at room temperature for 24 hours under the condition of blue light irradiation, and after the reaction is finished, performing column chromatography separation to obtain the quinoline derivative. The preparation method has the advantages of cheap and easily-obtained raw materials, mild reaction system, simple operation and high yield. Quinoline derivatives have a wide range of applications and are also useful as synthetic intermediates.
Description
Technical Field
The invention belongs to the field of organic synthetic chemistry, and relates to a method for preparing a quinoline derivative by photocatalysis of N-aryl glycine ester, in particular to a method for preparing a quinoline derivative by an addition cyclization reaction of an N-aryl glycine ester compound and a butyne dicarboxylic acid ester compound in the presence of an oxidant and a photosensitizer and under the irradiation of a blue light LED.
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 have wide application in other industrial fields, so the synthetic method thereof is concerned. The traditional quinoline skeleton synthesizing method includes Skraup reaction, combes reaction, conrad-Limbach reaction, doebner-VonMuller reaction, gould-Jacobs reaction, friedlander reaction, povavov reaction, pfitzinger reaction and the like, and the reaction conditions are harsh, side reactions are more, and pollution is serious. Recently, numerous documents report methods for preparing quinoline derivatives by photocatalytic reaction, such as: (1) Zhang et al reported a method (j.org.chem., 2016,81,12433-12442.) of producing quinoline derivatives by a visible light catalytic oxidative dehydrogenation coupling/aromatization tandem reaction of glycine ester and unactivated olefin, but the reaction requires a synergistic effect of copper salt and a photocatalyst to be able to react, and the reaction system is relatively complex. (2) Jiang et al also reported that a variety of alpha-branched 2-vinylpyridine and 2-vinylquinoline compounds were subjected to redox, radical conjugate addition, and protonation processes with glycine, respectively, using visible light-induced dual concerted catalysis of chiral phosphoric acid and DPZ photosensitizer, and finally a variety of chiral 3- (2-pyridine/quinoline) -3-substituted amine compounds were obtained in high yield (J.Am.Chem.Soc., 2018,140, 6083-6087.). In the reaction, the reaction can be carried out only by the synergistic action of the cobalt salt, the additive and the photocatalyst, the reaction system is complex, the separation is difficult, the substrate applicability is poor, and the large-scale popularization and application are difficult.
Therefore, there is still a need to develop and optimize new methods for preparing polysubstituted quinoline derivatives.
Disclosure of Invention
The present invention is directed to provide a method for preparing quinoline derivatives, which overcomes the drawbacks and shortcomings of the prior art.
The invention uses N-aryl glycine ester compounds and butynedioic acid ester compounds as raw materials, and reacts 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 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 using 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 is 1 Is represented by H, or is fluorine, chlorine, bromine, methyl, ethyl, propyl, butyl, isopropyl, tert-butyl, methoxy, ethoxy, tri-butylFluoromethyl, substituted phenyl, these substituents can be substituted at ortho, meta, para and multi-position of the phenyl ring; r 2 Expressed as methyl, ethyl, propyl, butyl, isopropyl, tert-butyl, benzyl; r 3 Expressed as methyl, ethyl, propyl, butyl, isopropyl, tert-butyl, phenyl, benzyl; using a blue LED lamp as a light source; the oxidant is di-tert-butyl peroxide, or one of benzoyl peroxide, dicumyl peroxide and tert-butyl hydroperoxide; the photosensitizer is terpyridine ruthenium chloride hexahydrate or one of iridium bis (2-phenylpyridine) acetylacetonate, 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 purpose, the invention adopts the following technical scheme for synthesizing the compound:
adding N-aryl glycine ester compound 1, butynedioic acid ester compound 2, oxidant, photosensitizer and reaction solvent into a reaction tube in sequence, and placing the reaction tube under the irradiation of blue light (blue LED) to react for 24 hours at room temperature after the addition. And after the reaction is finished, performing flash column chromatography separation to obtain the quinoline derivative 3.
The reaction light source in the method is a 24W blue LED lamp.
Dicumyl peroxide is selected as the reaction oxidant in the method.
The reaction photosensitizer is selected from rose bengal in the photosensitizers in the method.
Dimethyl sulfoxide is selected as the reaction solvent in the organic solvent in the method.
The mass ratio of the N-methylbiphenyl-2-amine compound 1, the butynedicarboxylate compound 2, the oxidant and the photosensitizer in the above method is 1.
Compared with the route of the prior art, 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 extension range.
(2) The method is simple, green, efficient and superior to the synthesis method reported in the existing literature, and the quinoline derivative is prepared by the addition cyclization reaction of the N-aryl glycine ester compound and the butynedioic acid ester compound under the irradiation of blue light without using transition metal catalysis.
Detailed Description
The invention is described in further detail with reference to specific examples, but the scope of the invention as claimed is not limited thereto.
Example 1 was carried out: 0.018g (0.1 mmol) of ethyl N-phenylglycine 1a,0.028g (0.2 mmol) of methyl butynedicarboxylate 2a, 0.006g (0.01 mmol) of ruthenium terpyridine chloride hexahydrate, 0.054g (0.2 mmol) of dicumyl peroxide and 2mL of DMSO were added in this order to a 10mL reaction tube, the reaction was magnetically stirred 24h under irradiation of a 24W blue LED and the progress of the reaction was monitored by TLC. After the reaction, column chromatography was performed to obtain 2-ethoxycarbonyl-3,4-dimethoxycarbonylquinoline 3a as a yellow oily substance 22mg with a yield of 68%. 1 H NMR(400Hz,CDCl 3 )(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). 13 C NMR(100MHz,CDCl 3 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 the reaction principle for example 1 is implemented as follows:
example 2 was carried out: 0.018g (0.1 mmol) of ethyl N-phenylglycine 1a,0.028g (0.2 mmol) of methyl butynedicarboxylate 2a, 0.006g (0.01 mmol) of ruthenium terpyridine chloride hexahydrate, 0.048g (0.2 mmol) of benzoyl peroxide and 2mL of DMSO were sequentially added to a 10mL reaction tube, the reaction was magnetically stirred under irradiation of a 24W blue LED for 24h, and the progress of the reaction was monitored by TLC. After the reaction, column chromatography was performed to obtain 2-ethoxycarbonyl-3,4-dimethoxycarbonylquinoline 3a as a yellow oily substance 20mg in 62% yield. Example 2 the reaction principle is as follows:
example 3 of implementation: 0.018g (0.1 mmol) of ethyl N-phenylglycine 1a,0.028g (0.2 mmol) of methyl butynedicarboxylate 2a, 0.006g (0.01 mmol) of ruthenium terpyridine chloride hexahydrate, 0.054g (0.2 mmol) of potassium persulfate and 2mL of DMSO were sequentially added to a 10mL reaction tube, the reaction was magnetically stirred under irradiation of a 24W blue LED for 24h, and the progress of the reaction was monitored by TLC. After the reaction, column chromatography was performed to obtain 2-ethoxycarbonyl-3,4-dimethoxycarbonylquinoline 3a as a yellow oily substance 21mg in a yield of 65%. Example 3 the reaction principle is as follows:
example 4 of implementation: 0.018g (0.1 mmol) of ethyl N-phenylglycine 1a,0.028g (0.2 mmol) of methyl butynedicarboxylate 2a, 0.008g (0.01 mmol) of erythrosin B, 0.054g (0.2 mmol) of dicumyl peroxide and 2mL of DMSO were sequentially added to a 10mL reaction tube, the reaction was magnetically stirred under irradiation of a 24W blue LED for 24h, and the progress of the reaction was monitored by TLC. After the reaction, column chromatography was performed to give 2-ethoxycarbonyl-3,4-dimethoxycarbonylquinoline 3a as a yellow oil, 23mg, yield 72%. Example 4 the reaction principle is as follows:
example 5 was carried out: 0.018g (0.1 mmol) of ethyl N-phenylglycine 1a,0.028g (0.2 mmol) of methyl butynedicarboxylate 2a, 0.007g (0.01 mmol) of eosin Y, 0.054g (0.2 mmol) of dicumyl peroxide and 2mL of DMSO are added in succession to a 10mL reaction tube, the reaction is stirred magnetically under the irradiation of a 24W blue LED 24h and the progress of the reaction is monitored by TLC. After the reaction, column chromatography was performed to give 2-ethoxycarbonyl-3,4-dimethoxycarbonylquinoline 3a as a yellow oil 22mg in 70% yield. Example 5 the reaction principle is as follows:
example 6 was carried out: 0.018g (0.1 mmol) of ethyl N-phenylglycine 1a,0.028g (0.2 mmol) of methyl butynedicarboxylate 2a, 0.010g (0.01 mmol) of Rose bengal (Rose B), 0.054g (0.2 mmol) of dicumyl peroxide and 2mL of DMSO were added in succession to a 10mL reaction tube, the reaction was stirred magnetically under the irradiation of a 24W blue LED 24h and the progress of the reaction was monitored by TLC. After the reaction, column chromatography was performed to obtain 2-ethoxycarbonyl-3,4-dimethoxycarbonylquinoline 3a as a yellow oily substance in a yield of 25mg (78%). Example 6 the reaction principle is as follows:
example 7 was carried out: 0.018g (0.1 mmol) of ethyl N-phenylglycine 1a,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 tetrahydrofuran were sequentially added to a 10mL reaction tube, the reaction was magnetically stirred under irradiation of a 24W blue LED for 24h, and the progress of the reaction was monitored by TLC. After the reaction, column chromatography was performed to give 2-ethoxycarbonyl-3,4-dimethoxycarbonylquinoline 3a as a yellow oil (7 mg) in 23% yield. Example 7 the reaction principle is as follows:
example 8 was carried out: 0.018g (0.1 mmol) of ethyl N-phenylglycine 1a,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 acetonitrile were successively charged into a 10mL reaction tube, the reaction was magnetically stirred under irradiation of a 24W blue LED for 24h, and the progress of the reaction was monitored by TLC. After the reaction, column chromatography was performed to give 2-ethoxycarbonyl-3,4-dimethoxycarbonylquinoline 3a as a yellow oil 13mg in 42% yield. Example 8 the reaction principle is as follows:
example 9 was carried out: 0.019g (0.1 mmol) of ethyl N- (4-methyl-) phenylglycine 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 were added in this order to a 10mL reaction tube, the reaction was magnetically stirred 24h under the irradiation of a 24W blue LED, and the progress of the reaction was monitored by TLC. After the reaction, 6-methyl-2-ethoxycarbonyl-3,4-dimethoxycarbonylquinoline 3b was obtained as a yellow oily substance (29.5 mg) with a yield of 89% by column chromatography. 1 H NMR(400MHz,CDCl 3 ,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). 13 C NMR(100MHz,CDCl 3 Ppm) delta 166.20,165.51,147.33,146.40,140.76,139.30,134.58,130.27,124.29,123.80,122.89,119.82,77.37,77.05,76.73,62.69,53.33,53.18,22.12,14.17 the reaction principle for example 9 is implemented as follows:
example 10 of implementation: 0.021g (0.1 mmol) of ethyl N- (3,5-dimethyl-) phenylglycine 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 were sequentially added to a 10mL reaction tube, the reaction was magnetically stirred under irradiation of a 24W blue LED for 24h, and the progress of the reaction was monitored by TLC. After the reaction, column chromatography was performed to give 5,7-dimethyl-2-ethoxycarbonyl-3,4-dimethoxycarbonylquinoline 3c as a yellow oil 29.7mg, yield 86%. 1 H NMR(400MHz,CDCl 3 ,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). 13 C NMR(100MHz,CDCl 3 ,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 the reaction principle for example 10 is implemented as follows:
example 11 of implementation: 0.026g (0.1 mmol) of ethyl N- (4-bromo-) phenylglycine 1d,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 were added in succession to a 10mL reaction tube, the reaction was stirred magnetically 24h under irradiation of a 24W blue LED, and the progress of the reaction was monitored by TLC. After the reaction, column chromatography separation was performed to obtain 2-ethoxycarbonyl-3,4-dimethoxycarbonyl-6-bromoquinoline 3d as a white solid (24.1 mg) with a yield of 61%. 1 H NMR(400MHz,CDCl 3 ,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). 13 C NMR(100MHz,CDCl 3 Ppm) delta 165.75,165.41,165.03,148.37,146.26,138.68,135.78,132.09,127.88,124.94,124.84,124.22,77.37,77.05,76.74,62.93,53.60,53.35,14.15 the reaction principle for example 11 is implemented as follows:
example 12 of implementation: 0.020g (0.1 mmol) of ethyl N- (4-fluoro-) phenylglycine 1e,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 added in succession to a 10mL reaction tube, the reaction is stirred magnetically 24h under the irradiation of a 24W blue LED and the progress of the reaction is monitored by TLC. After the reaction, column chromatography was performed to obtain 2-ethoxycarbonyl-3,4-dimethoxycarbonyl-6-fluoroquinoline 3e as a pale yellow solid, 24.8mg, and 74% yield. 1 H NMR(400MHz,CDCl 3 ,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). 13 C NMR(100MHz,CDCl 3 Ppm) delta 166.00,165.48,163.84,161.32,147.27,144.84,138.70,133.46,125.12,124.61,122.78,109.65,77.36,77.05,76.73,62.88,53.52,53.32,14.16 the reaction principle for example 12 is implemented as follows:
example 13: 0.022g (0.1 mmol) of N- (4-chloro-) phenylglycine ethyl ester 1f,0.028g (0.2 mmol) of but-idenedicarboxylic acid methyl ester 2a, 0.010g (0.01 mmol) of Rose B, 0.054g (0.2 mmol) of dicumyl peroxide and 2mL of DMSO are added in succession to a 10mL reaction tube, the reaction is stirred magnetically for 24h under the irradiation of a 24W blue LED, and the progress of the reaction is monitored by TLC. After the reaction, column chromatography separation was performed to obtain 2-ethoxycarbonyl-3,4-dimethoxycarbonyl-6-chloroquinoline 3f as a pale yellow solid (26.4 mg) in a yield of 75%. 1 H NMR(400Hz,CDCl 3 )(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)； 13 C NMR(100MHz,CDCl 3 ) δ 165.76,165.39,164.99,148.25,146.06,138.74,136.51,133.17,132.09,129.31,124.56,121.04,77.36,77.04,76.72,62.89,53.55,53.31,14.14 the reaction principle for example 13 was implemented as follows:
example 14 was carried out: 0.017g (0.1 mmol) of methyl N-phenylglycine 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 successively introduced into a 10mL reaction tube, the reaction is magnetically stirred under the irradiation of a 24W blue LED for 24h, and the progress of the reaction is monitored by TLC. After the reaction, column chromatography was performed to obtain 3g of 2-methoxycarbonyl-3,4-dimethoxycarbonylquinoline as a yellow solid (16.7 mg) with a yield of 55%. 1 H NMR(500Hz,CDCl 3 )(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)； 13 C NMR(100MHz,CDCl 3 ) δ 165.95,165.89,165.71,147.76,147.63,140.04,132.21,130.58,130.15,125.67,123.83,123.18,77.37,77.05,76.73,53.51,53.38,53.31 the reaction principle for example 14 was implemented as follows:
example 15 of implementation: 0.018g (0.1 mmol) of ethyl N-phenylglycine 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 were successively introduced into a 10mL reaction tube, the reaction was magnetically stirred under the irradiation of a 24W blue LED for 24h, and the progress of the reaction was monitored by TLC. After the reaction, column chromatography separation was performed to obtain 2-ethoxycarbonyl-3,4-di-tert-butoxycarbonylquinoline in 20.9mg of a yellow solid in 52% yield for 3 h. 1 H NMR(400Hz,CDCl 3 )(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)； 13 C NMR(100MHz,CDCl 3 ) δ 165.89,165.00,164.23,149.16,147.34,141.93,131.58,130.37,129.43,125.36,123.88,122.92,84.53,83.72,77.36,77.04,76.73,62.49,28.15,27.92,14.17 the reaction principle for example 15 was implemented as follows:
Claims (6)
1. a method for preparing quinoline derivatives by photocatalysis of N-aryl glycine ester is characterized by comprising the following steps: dissolving an N-aryl glycine ester compound 1 and a butynedioic acid ester compound 2 in a reaction solvent, adding an oxidant and a photosensitizer, reacting at room temperature for 24 hours under the irradiation of a blue light LED, and after the reaction is finished, performing column chromatography separation to obtain a target product quinoline derivative 3, wherein the reaction formula is as follows:
wherein R is 1 Represented by H, or by fluorine, chlorine, bromine, methyl, ethyl, propyl, butyl, isopropyl, tert-butyl, methoxy, ethoxy, trifluoromethyl, substituted phenyl, these substituents being substitutable in the ortho, meta, para and multi-positions of the phenyl ring; r 2 Expressed as methyl, ethyl, propyl, butyl, isopropyl, tert-butyl, benzyl; r is 3 Expressed as methyl, ethyl, propyl, butyl, isopropyl, tert-butyl, phenyl, benzyl; using a blue LED lamp as a light source; the oxidant is di-tert-butyl peroxide, or one of benzoyl peroxide, dicumyl peroxide and tert-butyl hydroperoxide; the photosensitizer is terpyridine ruthenium chloride hexahydrate or one of iridium bis (2-phenylpyridine) acetylacetonate, 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.
2. The method for preparing quinoline derivative 3 through photocatalysis of N-aryl glycine ester according to claim 1, wherein a 24W blue LED lamp is selected as the reaction light source.
3. The method for preparing quinoline derivative 3 by photocatalysis of N-aryl glycine ester of claim 1, wherein dicumyl peroxide is selected as the reaction oxidant.
4. The method for preparing quinoline derivative 3 through N-arylglycine ester photocatalysis according to claim 1, wherein rose bengal is selected as the reaction photosensitizer.
5. The method for preparing quinoline derivative 3 by photocatalysis of N-aryl glycine ester of claim 1, wherein dimethyl sulfoxide is used as the reaction solvent.
6. The method for preparing quinoline derivatives 3 by photocatalysis of N-aryl glycine ester according to claim 1, wherein the mass ratio of the N-aryl glycine ester compound 1, the butyndicarboxylate compound 2, the oxidant and the photosensitizer is 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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| Title |
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| HUI XU，GUAN-WU WANG: "Solvent-Free Mechanosynthesis of Polysubstituted 1, 2- Dihydroquinolines from Anilines and Alkyne Esters", J. ORG. CHEM., vol. 87, 22 June 2022 (2022-06-22), pages 8480 * |
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| RENATE ROHLMANN等: "Iron-Catalyzed Oxidative Tandem Reactions with TEMPO Oxoammonium Salts: Synthesis of Dihydroquinazolines and Quinolines", J. ORG. CHEM., vol. 78, 24 May 2013 (2013-05-24), pages 6050 * |
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