CN113651859A - 4-methyl-6-phenyl-8-ferrocenyl pyrone quinoline and preparation method and application thereof - Google Patents
4-methyl-6-phenyl-8-ferrocenyl pyrone quinoline and preparation method and application thereof Download PDFInfo
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- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 title claims abstract description 56
- ZPSJGADGUYYRKE-UHFFFAOYSA-N 2H-pyran-2-one Chemical compound O=C1C=CC=CO1 ZPSJGADGUYYRKE-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 claims abstract description 31
- -1 4-methyl-6-phenyl-8-ferrocenylpyranoquinoline Chemical compound 0.000 claims abstract description 29
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- 239000002131 composite material Substances 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 5
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 42
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 15
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000003480 eluent Substances 0.000 claims description 5
- 238000004440 column chromatography Methods 0.000 claims description 4
- 238000010898 silica gel chromatography Methods 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 239000003208 petroleum Substances 0.000 claims description 3
- 230000002000 scavenging effect Effects 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 2
- HGFMFKSDOFFKRV-UHFFFAOYSA-N 8h-pyrano[2,3-h]quinoline Chemical compound C1=CC=NC2=C(C=CCO3)C3=CC=C21 HGFMFKSDOFFKRV-UHFFFAOYSA-N 0.000 claims 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 26
- OHDRQQURAXLVGJ-HLVWOLMTSA-N azane;(2e)-3-ethyl-2-[(e)-(3-ethyl-6-sulfo-1,3-benzothiazol-2-ylidene)hydrazinylidene]-1,3-benzothiazole-6-sulfonic acid Chemical compound [NH4+].[NH4+].S/1C2=CC(S([O-])(=O)=O)=CC=C2N(CC)C\1=N/N=C1/SC2=CC(S([O-])(=O)=O)=CC=C2N1CC OHDRQQURAXLVGJ-HLVWOLMTSA-N 0.000 abstract description 21
- 150000003254 radicals Chemical class 0.000 abstract description 18
- HHEAADYXPMHMCT-UHFFFAOYSA-N dpph Chemical compound [O-][N+](=O)C1=CC([N+](=O)[O-])=CC([N+]([O-])=O)=C1[N]N(C=1C=CC=CC=1)C1=CC=CC=C1 HHEAADYXPMHMCT-UHFFFAOYSA-N 0.000 abstract description 14
- 230000003078 antioxidant effect Effects 0.000 abstract description 9
- MBVFRSJFKMJRHA-UHFFFAOYSA-N 4-fluoro-1-benzofuran-7-carbaldehyde Chemical compound FC1=CC=C(C=O)C2=C1C=CO2 MBVFRSJFKMJRHA-UHFFFAOYSA-N 0.000 abstract description 8
- GVJHHUAWPYXKBD-UHFFFAOYSA-N (±)-α-Tocopherol Chemical compound OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-UHFFFAOYSA-N 0.000 abstract description 6
- 239000003963 antioxidant agent Substances 0.000 abstract description 5
- 235000006708 antioxidants Nutrition 0.000 abstract description 5
- 238000006555 catalytic reaction Methods 0.000 abstract description 5
- QWONMGLXCDXSCZ-UHFFFAOYSA-N 4-methyl-6,8-diphenylquinoline Chemical compound CC(C1=CC(C2=CC=CC=C2)=C2)=CC=NC1=C2C1=CC=CC=C1 QWONMGLXCDXSCZ-UHFFFAOYSA-N 0.000 abstract description 3
- 229930003427 Vitamin E Natural products 0.000 abstract description 3
- WIGCFUFOHFEKBI-UHFFFAOYSA-N gamma-tocopherol Natural products CC(C)CCCC(C)CCCC(C)CCCC1CCC2C(C)C(O)C(C)C(C)C2O1 WIGCFUFOHFEKBI-UHFFFAOYSA-N 0.000 abstract description 3
- 238000010992 reflux Methods 0.000 abstract description 3
- 238000010490 three component reaction Methods 0.000 abstract description 3
- 235000019165 vitamin E Nutrition 0.000 abstract description 3
- 229940046009 vitamin E Drugs 0.000 abstract description 3
- 239000011709 vitamin E Substances 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 description 22
- 239000000243 solution Substances 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 9
- 238000002835 absorbance Methods 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 5
- 238000011056 performance test Methods 0.000 description 5
- 238000010791 quenching Methods 0.000 description 5
- 230000000171 quenching effect Effects 0.000 description 5
- 230000002292 Radical scavenging effect Effects 0.000 description 4
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 230000007760 free radical scavenging Effects 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- GNZDAXRYGVFYPU-UHFFFAOYSA-N 2,6-ditert-butyl-4-[(3,5-ditert-butyl-4-$l^{1}-oxidanylphenyl)methylidene]cyclohexa-2,5-dien-1-one Chemical compound C1=C(C(C)(C)C)C(=O)C(C(C)(C)C)=CC1=CC1=CC(C(C)(C)C)=C([O])C(C(C)(C)C)=C1 GNZDAXRYGVFYPU-UHFFFAOYSA-N 0.000 description 3
- 235000013405 beer Nutrition 0.000 description 3
- 230000008033 biological extinction Effects 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000011550 stock solution Substances 0.000 description 3
- OCZVHBZNPVABKX-UHFFFAOYSA-N 1,1-diphenyl-2-(2,4,6-trinitrophenyl)hydrazine;ethanol Chemical compound CCO.[O-][N+](=O)C1=CC([N+](=O)[O-])=CC([N+]([O-])=O)=C1NN(C=1C=CC=CC=1)C1=CC=CC=C1 OCZVHBZNPVABKX-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
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- 125000000524 functional group Chemical group 0.000 description 2
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- 230000002195 synergetic effect Effects 0.000 description 2
- 239000012085 test solution Substances 0.000 description 2
- 230000036962 time dependent Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- NAPYSZKXFNWXEM-UHFFFAOYSA-N 2,3,5,6-tetratert-butylcyclohexa-2,5-dien-1-one Chemical compound CC(C)(C)C1=C(C(C)(C)C)C(=O)C(C(C)(C)C)=C(C(C)(C)C)C1 NAPYSZKXFNWXEM-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000013313 FeNO test Methods 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910002567 K2S2O8 Inorganic materials 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- PHSMPGGNMIPKTH-UHFFFAOYSA-K cerium(3+);trifluoromethanesulfonate Chemical compound [Ce+3].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F PHSMPGGNMIPKTH-UHFFFAOYSA-K 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- GLNDAGDHSLMOKX-UHFFFAOYSA-N coumarin 120 Chemical compound C1=C(N)C=CC2=C1OC(=O)C=C2C GLNDAGDHSLMOKX-UHFFFAOYSA-N 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000000132 electrospray ionisation Methods 0.000 description 1
- 230000014509 gene expression Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 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
- 238000006053 organic reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 150000003248 quinolines Chemical class 0.000 description 1
- HZXJVDYQRYYYOR-UHFFFAOYSA-K scandium(iii) trifluoromethanesulfonate Chemical compound [Sc+3].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F HZXJVDYQRYYYOR-UHFFFAOYSA-K 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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Abstract
The invention discloses 4-methyl-6-phenyl-8-ferrocenyl pyrone quinoline and a preparation method and application thereof, wherein the structural formula of the 4-methyl-6-phenyl-8-ferrocenyl pyrone quinoline is as follows:
the present disclosure uses 4-methyl-7-amino pyrone, ferrocene carboxaldehyde and phenylacetylene as raw materials, Ce (OTf)3And Sc (OTf)3As a composite catalyst, Povarov three-component reaction is realized under the condition of heating reflux, and 4-methyl-6-phenyl-8-ferrocenyl pyrone quinoline is efficiently synthesized by catalysis. Adding 4-methyl-6-phenyl-8-ferrocenylpyranoquinoline to ABTS, DPPH and galvinoxyl, respectivelyIn the free radical ethanol solution, ABTS, DPPH and galvinoxyl free radicals can be well eliminated, excellent antioxidant activity is shown, the antioxidant performance of the solution is superior to that of corresponding vitamin E, 4-methyl-6, 8-diphenylquinoline and 4-methyl-6, 8-diphenylpyranone quinoline, and the solution has potential application value.
Description
Technical Field
The invention relates to the field of organic synthesis, and in particular relates to 4-methyl-6-phenyl-8-ferrocenyl pyrone quinoline and a preparation method and application thereof.
Background
Modification of natural framework structures, especially integration of various natural framework structures or functional groups, has become a hotspot in the field of organic synthesis research nowadays.
The pyrone and quinoline compounds respectively have natural structural frameworks of oxygen heterocycle and nitrogen heterocycle, and have various physiological and pharmacological activities of oxidation resistance, tumor resistance, antibiosis and the like. The ferrocenyl is a novel antioxidant functional group, and the derivative thereof has stronger antioxidant activity. Pyrone, quinoline and ferrocene groups are integrated into one molecule, and a novel compound with higher physiological and pharmacological activity performance can be developed.
However, the synthesis and biological performance studies of integrating pyrone, quinoline and ferrocene groups into one molecule have been reported at home and abroad so far. In the process of catalytic reaction, partial catalysts have synergistic effect, the unique interaction can enhance the catalytic effect of each other, and the adoption of the composite catalyst can effectively improve the efficiency of organic reaction and the synthesis yield of a target compound, and the composite catalyst becomes an important research direction of organic catalysis.
Therefore, how to provide a compound integrating pyrone, quinoline and ferrocene groups becomes a technical problem which needs to be solved urgently in the field.
Disclosure of Invention
An object of the present invention is to provide a novel technical scheme of 4-methyl-6-phenyl-8-ferrocenyl pyrone quinoline integrating pyrone, quinoline and ferrocene groups.
According to a first aspect of the present invention there is provided a 4-methyl-6-phenyl-8-ferrocenopyranone quinoline.
The structural formula of the 4-methyl-6-phenyl-8-ferrocenyl pyranoquinoline is as follows:
according to a second aspect of the present invention, there is provided a process for the preparation of the disclosed 4-methyl-6-phenyl-8-ferrocenopyranone quinoline.
The preparation method of the 4-methyl-6-phenyl-8-ferrocenyl pyrone quinoline comprises the following steps:
takes 4-methyl-7-amino pyrone, ferrocene formaldehyde and phenylacetylene as raw materials, and Ce (OTf)3And Sc (OTf)3Mixing 4-methyl-7-aminopyranone, ferrocene formaldehyde, phenylacetylene, Ce (OTf) as composite catalyst3、Sc(OTf)3And toluene, heating in an oil bath for a period of time, cooling to room temperature, concentrating the solvent, and purifying the residue by silica gel column chromatography to obtain 4-methyl-6-phenyl-8-ferrocenyl pyrone quinoline.
Optionally, ferrocene carboxaldehyde, phenylacetylene, 4-methyl-7-aminopyranone, Ce (OTf)3、Sc(OTf)3The molar ratio of toluene to toluene is 100 (90-150): 80-150): 3-8): 4000-5000.
Optionally, ferrocene carboxaldehyde, phenylacetylene, 4-methyl-7-aminopyranone, Ce (OTf)3、Sc(OTf)3And toluene at a molar ratio of 100:120:120:5:5: 4700.
Optionally, the oil bath temperature is 50-120 ℃.
Alternatively, the oil bath temperature is 110 ℃.
Optionally, the reaction time is 1-3 h.
Optionally, the reaction time is 2 h.
Optionally, the eluent for column chromatography is at least one of dichloromethane, petroleum ether and ethyl acetate.
According to a third aspect of the present invention, there is provided a use of the 4-methyl-6-phenyl-8-ferrocenylpyranoquinoline described in the present disclosure in scavenging free radicals.
The present disclosure uses 4-methyl-7-amino pyrone, ferrocene carboxaldehyde and phenylacetylene as raw materials, Ce (OTf)3And Sc (OTf)3As a composite catalyst, Povarov three-component reaction is realized under the condition of heating reflux, and 4-methyl-6-phenyl-8-ferrocenyl pyrone quinoline is efficiently synthesized by catalysis.
The 4-methyl-6-phenyl-8-ferrocenyl pyrone quinoline is added into ABTS, DPPH and galvinoxyl free radical ethanol solutions respectively, ABTS, DPPH and galvinoxyl free radicals can be well eliminated, excellent antioxidant activity is shown, the antioxidant performance of the antioxidant is superior to that of corresponding vitamin E, 4-methyl-6, 8-diphenylquinoline and 4-methyl-6, 8-diphenylpyrone quinoline, and the antioxidant has potential application value.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description, serve to explain the principles of the invention.
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of 4-methyl-6-phenyl-8-ferrocenylpyranoquinoline;
FIG. 2 is a NMR carbon spectrum of 4-methyl-6-phenyl-8-ferrocenylpyranoquinoline;
FIG. 3 is a mass spectrum of 4-methyl-6-phenyl-8-ferrocenylpyranoquinoline.
Detailed Description
Various exemplary embodiments of the present invention will now be described in detail with reference to the accompanying drawings. It should be noted that: the relative arrangement of the components and steps, the numerical expressions and numerical values set forth in these embodiments do not limit the scope of the present invention unless specifically stated otherwise.
The following description of at least one exemplary embodiment is merely illustrative in nature and is in no way intended to limit the invention, its application, or uses.
Techniques, methods, and apparatus known to those of ordinary skill in the relevant art may not be discussed in detail but are intended to be part of the specification where appropriate.
In all examples shown and discussed herein, any particular value should be construed as merely illustrative, and not limiting. Thus, other examples of the exemplary embodiments may have different values.
The structural formula of the 4-methyl-6-phenyl-8-ferrocenyl pyranoquinoline provided by the disclosure is as follows:
the preparation method of the 4-methyl-6-phenyl-8-ferrocenyl pyrone quinoline provided by the disclosure comprises the following steps:
takes 4-methyl-7-amino pyrone, ferrocene formaldehyde and phenylacetylene as raw materials, and Ce (OTf)3And Sc (OTf)3Mixing 4-methyl-7-aminopyranone, ferrocene formaldehyde, phenylacetylene, Ce (OTf) as composite catalyst3、Sc(OTf)3And toluene, heating in an oil bath for a period of time, cooling to room temperature, concentrating the solvent, and purifying the residue by silica gel column chromatography to obtain 4-methyl-6-phenyl-8-ferrocenyl pyrone quinoline.
During the reaction, the reaction was monitored by TLC in real time.
The reaction process is as follows:
ferrocene carboxaldehyde, phenylacetylene, 4-methyl-7-aminopyranone, Ce (OTf)3、Sc(OTf)3The molar ratio of toluene to toluene can be 100 (90-150): 80-150): 3-8): 4000-5000.
Further, ferrocene carboxaldehyde, phenylacetylene, 4-methyl-7-aminopyranone, Ce (OTf)3、Sc(OTf)3And toluene at a molar ratio of 100:120:120:5:5: 4700.
The oil bath temperature can be 50-120 ℃.
Further, the oil bath temperature was 110 ℃.
The reaction time can be 1-3 h.
Further, the reaction time was 2 hours.
The eluent for column chromatography may be at least one of dichloromethane, petroleum ether and ethyl acetate.
In specific implementation, the eluent for column chromatography can be dichloromethane.
The disclosure also provides an application of the 4-methyl-6-phenyl-8-ferrocenyl pyranoquinoline in the field of free radical scavenging.
And carrying out an oxidation resistance test on the 4-methyl-6-phenyl-8-ferrocenyl pyranoquinoline type. The specific process is as follows:
dissolving 4-methyl-6-phenyl-8-ferrocenylpyranoquinoline in ethanol to form an ethanol solution, adding the ethanol solution to a solution of 2, 2' -azo-bis- (3-ethylbenzothiazoline-6-sulfonic acid) diammonium radical (ABTS.), diphenylpicrylhydrazide radical (DPPH.) and 2, 6-di-tert-butyl- (3, 5-di-tert-butyl-4-oxo-2, 5-cyclohexadiene) -p-tolueneoxy radical (galvinoxyl.) in ethanol, then, the time-dependent course of the concentrations of ABTS, DPPH and galvinoxyl radicals was determined at the wavelengths of maximum absorption (734nm, 517nm and 428nm), further, the clearance of the free radical of 4-methyl-6-phenyl-8-ferrocenylpyranoquinoline was determined.
The concentrations of 4-methyl-6-phenyl-8-ferrocenyl pyranoquinoline in ABTS, DPPH and galvinoxyl radical ethanol solutions were 5. mu. mol/L, 10. mu. mol/L and 50. mu. mol/L, respectively, and the reaction time of 4-methyl-6-phenyl-8-ferrocenyl pyranoquinoline with ABTS, DPPH and galvinoxyl radical was 30 min.
The experimental procedures used in the examples below are conventional unless otherwise specified, the materials and reagents used therein are commercially available, and the equipment used in the experiments are well known to those skilled in the art without otherwise specified.
Examples
Main experimental reagents and instruments: 4-methyl-7-aminobenzopyrone, toluene, cerium triflate, scandium triflate, ferrocene carboxaldehyde, phenylacetylene, dichloromethane, an electronic balance, a rotary evaporator, an oil bath, a Bruker Avance III 400MHz NMR spectrometer (Bruker, USA), an ultra performance liquid chromatography-electrospray ionization source-mass spectrometer (Agilent technologies, Inc.).
Ferrocene carboxaldehyde 0.43g (2.0mmol), phenylacetylene 0.24g (2.4mmol), 4-methyl-7-aminopyranone 0.42g (2.4mmol), Ce (OTf)3 0.06g(0.1mmol)、Sc(OTf)30.05g (0.1mmol) and 10mL of toluene were charged into a 25mL round-bottom flask and reacted at reflux (110 ℃ C.) with stirring for 2h (TLC detection). Cooled to room temperature, the solvent was concentrated, and the residue was purified by silica gel column chromatography [ eluent: methylene dichloride]Purifying to obtain 4-methyl-6-phenyl-8-ferrocenyl pyranoquinoline with the yield of 68.7 percent.
The structure of the obtained target compound is detected by a Bruker Avance III 400MHz nuclear magnetic resonance spectrometer (Bruker company in America) and an ultra-high performance liquid chromatography-electrospray ion source-mass spectrometer (Agilent technologies, Inc.),1H NMR、13c NMR and HR-MS are shown in FIGS. 1-3.
Structural characterization data for 4-methyl-6-phenyl-8-ferrocenylpyranoquinoline:
4-methyl-6-ferrocenyl-8-phenylpyranone quinoline: a yellow solid, yield 68.7%, m.p.241-243 ℃;1H NMR(400MHz,CDCl3)δ:8.55(s,1H),8.14(s,2H),7.97(s,1H),7.69(s,1H),7.44(d,J＝6.0Hz,2H),7.40(t,J＝6.8Hz,1H),6.15(s,1H),4.58(s,2H),4.40(s,2H),4.09(s,5H),2.38(s,3H)；13C NMR(100MHz,CDCl3)δ:159.1,157.2,152.4,150.8,129.9,129.0,127.4,126.2,124.7,123.9,117.0,115.6,114.3,88.3,72.2,69.8,68.3,19.4；HR-MS(ESI)m/z:Calcd for C29H21FeNO2{[M+H]+}472.100 0,found 472.103 8。
table 1 shows the effect of reaction conditions on the yield of 4-methyl-6-phenyl-8-ferrocenylpyranoquinoline compound.
TABLE 1 Effect of reaction conditions on the yield of 4-methyl-6-phenyl-8-ferrocenylpyranoquinoline
As can be seen from Table 1, in Ce (OTf)3And Sc (OTf)3The compound is a composite catalyst, the heating reaction is carried out for 2 hours at 110 ℃, the compound is a better method for synthesizing a target compound, and the yield of the compound 4-methyl-6-phenyl-8-ferrocenyl pyranoquinoline is 68.7 percent and is higher than the catalytic yield of other catalysts. The reason is Ce (OTf)3And Sc (OTf)3Both have the function of catalyzing Povarov-3CR, the two have synergistic effect after being compounded, and the unique interaction can enhance the catalysis of each other and generate more than Ce (OTf)3And Sc (OTf)3The catalytic efficiency when the catalyst is used alone enables the reaction to be carried out in the positive direction, reduces the generation of byproducts and greatly improves the reaction efficiency of Povarov-3 CR.
Test for Oxidation resistance
1. ABTS & free radical scavenging Performance test.
Firstly, preparing a solution: weighing 5.0mg ABTS and 1.5mg K2S2O8The mixture was put into a 2mL volumetric flask, distilled water was added to the flask to a constant volume, and the flask was left standing at room temperature in the dark for 24 hours to turn dark blue. Then, the solution was transferred to a 100mL volumetric flask, the absolute ethanol was added to a constant volume, and the solution was left in a 30 ℃ constant temperature water bath for 30min to obtain an ABTS-ethanol solution. The absorbance value of this solution at 734nm was maximal and was 1.671, and the molar extinction coefficient of ABTS at this wavelength was 1.6X 104L/(mol. cm). The procedure for quenching ABTS · free radical by compound is as follows: transferring 1.9mL ABTS free radical ethanol solution and 0.1mL stock solution with concentration of 0.1mmol/L to test solution, adding test solution with final concentration of 5 μmol/L, rapidly mixing, and recording the time-dependent attenuation of absorbance value (A) at maximum absorption wavelength within 30minAnd (4) subtracting the curve, obtaining the concentrations of ABTS & free radical at the initial time and the final time by Lambert beer's law, and obtaining the ABTS & clearance of 4-methyl-6-phenyl-8-ferrocenyl pyrone quinoline by concentration change.
2. DPPH-free radical scavenging performance test.
Firstly, preparing a solution: 4.0mg of DPPH was weighed, added to a 20mL beaker, dissolved in a small amount of absolute ethanol, and then transferred to a 100mL volumetric flask, and the volume was determined with absolute ethanol to obtain a DPPH-ethanol solution having a maximum absorption wavelength of 517nm, an absorbance value of about 1.378, and a molar extinction coefficient at this wavelength of 4.09X 103L/(mol. cm). The procedure for the compound quenching DPPH is consistent with the compound quenching ABTS: transferring 1.9mL of DPPH-ethanol solution and 0.1mL of stock solution of a compound to be detected with the concentration of 0.2mmol/L, adding the solution into a test tube to ensure that the final concentration of the compound to be detected is 10mmol/L, rapidly and uniformly mixing, recording the attenuation curve of the absorbance value (A) along with time at the maximum absorption wavelength within 30min, obtaining the concentrations of DPPH-free radical at the initial time and the final time through the Lambert beer law, and obtaining the DPPH-clearance of 4-methyl-6-phenyl-8-ferrocenyl pyranone quinoline through the change of the concentrations.
3. The galvinoxyl radical scavenging performance was tested.
Firstly, preparing a solution: 1.0mg of galvinoxyl was weighed, added to a 20mL beaker, dissolved in a small amount of absolute ethanol, and transferred to a 100mL volumetric flask, and the volume was fixed with absolute ethanol to obtain a galvinoxyl radical ethanol solution having an absorbance value at 428nm which is the maximum and about 1.108, and a molar extinction coefficient at that wavelength of 1.4X 105L/(mol. cm). The procedure for the compound quenching galvinoxyl radical was consistent with the compound quenching ABTS: transferring 1.9mL of galvinoxyl free radical ethanol solution and 0.1mL of stock solution of a compound to be detected with the concentration of 1mmol/L into a test tube, enabling the final concentration of the compound to be detected to be 50mmol/L, rapidly mixing uniformly, recording the attenuation curve of the absorbance value (A) along with time at the maximum absorption wavelength within 30min, obtaining the concentrations of galvinoxyl free radical at the initial time and the final time through the Lambert beer law, and obtaining the scavenging rate of 4-methyl-6-phenyl-8-ferrocenyl pyrone quinoline on galvinoxyl through the concentration change.
Table 1 shows the compound pair ABTS, DPPH and galvinoxyl radical scavenging rates
Note: the concentration of the 3 compounds in the ABTS & free radical scavenging performance test system is 5 mu mol/L; the concentration of the 3 compounds in a DPPH & free radical scavenging performance test system is 10 mu mol/L; the concentration of 3 compounds in the galvinoxyl radical scavenging performance test system was 50. mu. mol/L.
As can be seen from Table 1, the clearance rates of the 4-methyl-6-phenyl-8-ferrocenyl pyrone quinoline on ABTS, DPPH and galvinoxyl radicals are 85.3%, 81.6% and 75.7%, respectively, the ABTS, DPPH and galvinoxyl radicals can be well cleared, the clearance rates of the radicals are higher than those of vitamin E, 4-methyl-6, 8-diphenylquinoline and 4-methyl-6, 8-diphenylpyrone quinoline, the antioxidant activity is excellent, and the potential application value is realized.
The discovery of the present disclosure employs Ce (OTf)3And Sc (OTf)3The compound catalyst is used for catalyzing 4-methyl-7-aminopyranone, ferrocenecarboxaldehyde and phenylacetylene to generate Povarov three-component reaction, so that the yield of the synthesized 4-methyl-6-phenyl-8-ferrocenylpyranone quinoline with excellent oxidation resistance is obviously single catalyst reaction, the work efficiency is improved, the time is saved, the environment is protected, and the cost is reduced.
Although some specific embodiments of the present invention have been described in detail by way of examples, it should be understood by those skilled in the art that the above examples are for illustrative purposes only and are not intended to limit the scope of the present invention. It will be appreciated by those skilled in the art that modifications may be made to the above embodiments without departing from the scope and spirit of the invention. The scope of the invention is defined by the appended claims.
Claims (10)
1. A4-methyl-6-phenyl-8-ferrocenyl pyranoquinoline characterized by the following structural formula:
2. a method of preparing 4-methyl-6-phenyl-8-ferrocenylpyranoquinoline as claimed in claim 1, comprising the steps of:
takes 4-methyl-7-amino pyrone, ferrocene formaldehyde and phenylacetylene as raw materials, and Ce (OTf)3And Sc (OTf)3Mixing 4-methyl-7-aminopyranone, ferrocene formaldehyde, phenylacetylene, Ce (OTf) as composite catalyst3、Sc(OTf)3And toluene, heating in an oil bath for a period of time, cooling to room temperature, concentrating the solvent, and purifying the residue by silica gel column chromatography to obtain 4-methyl-6-phenyl-8-ferrocenyl pyrone quinoline.
3. The process for preparing 4-methyl-6-phenyl-8-ferrocenylpyranoquinoline as claimed in claim 2, wherein ferrocenecarboxaldehyde, phenylacetylene, 4-methyl-7-aminopyranone, Ce (OTf)3、Sc(OTf)3The molar ratio of toluene to toluene is 100 (90-150): 80-150): 3-8): 4000-5000.
4. The process for preparing 4-methyl-6-phenyl-8-ferrocenylpyranoquinoline as claimed in claim 3, wherein ferrocenecarboxaldehyde, phenylacetylene, 4-methyl-7-aminopyranone, Ce (OTf)3、Sc(OTf)3And toluene at a molar ratio of 100:120:120:5:5: 4700.
5. The method for preparing 4-methyl-6-phenyl-8-ferrocenylpyranoquinoline as claimed in claim 2, wherein the oil bath temperature is 50-120 ℃.
6. The process for the preparation of 4-methyl-6-phenyl-8-ferrocenylpyranoquinoline as claimed in claim 5, wherein the oil bath temperature is 110 ℃.
7. The process for the preparation of 4-methyl-6-phenyl-8-ferrocenylpyranoquinoline as claimed in claim 2, wherein the reaction time is 1 to 3 hours.
8. The process for the preparation of 4-methyl-6-phenyl-8-ferrocenylpyranoquinoline as claimed in claim 7, wherein the reaction time is 2 h.
9. The method for preparing 4-methyl-6-phenyl-8-ferrocenylpyranoquinoline as claimed in claim 2, wherein the eluent for column chromatography is at least one of dichloromethane, petroleum ether and ethyl acetate.
10. Use of 4-methyl-6-phenyl-8-ferrocenylpyranoquinoline as claimed in claim 1 for scavenging free radicals.
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