CN113651859B - 4-methyl-6-phenyl-8-ferrocenyl pyranone quinoline and preparation method and application thereof - Google Patents
4-methyl-6-phenyl-8-ferrocenyl pyranone quinoline and preparation method and application thereof Download PDFInfo
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- -1 pyranone quinoline Chemical compound 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims abstract description 49
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 claims abstract description 31
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 17
- 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 14
- 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 5
- 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 21
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-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
- 239000003480 eluent Substances 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 238000004440 column 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
- 238000010898 silica gel chromatography Methods 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 37
- 150000003254 radicals Chemical class 0.000 abstract description 22
- 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 19
- 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
- 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
- 230000003647 oxidation Effects 0.000 abstract description 3
- 238000007254 oxidation reaction Methods 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
- 239000004305 biphenyl Substances 0.000 abstract description 2
- 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 2
- FATAVLOOLIRUNA-UHFFFAOYSA-N formylmethyl Chemical compound [CH2]C=O FATAVLOOLIRUNA-UHFFFAOYSA-N 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 description 24
- 239000000243 solution Substances 0.000 description 17
- WCBPJVKVIMMEQC-UHFFFAOYSA-N 1,1-diphenyl-2-(2,4,6-trinitrophenyl)hydrazine Chemical compound [O-][N+](=O)C1=CC([N+](=O)[O-])=CC([N+]([O-])=O)=C1NN(C=1C=CC=CC=1)C1=CC=CC=C1 WCBPJVKVIMMEQC-UHFFFAOYSA-N 0.000 description 13
- 235000019441 ethanol Nutrition 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 238000005481 NMR spectroscopy Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- ZPSJGADGUYYRKE-UHFFFAOYSA-N 2H-pyran-2-one Chemical compound O=C1C=CC=CO1 ZPSJGADGUYYRKE-UHFFFAOYSA-N 0.000 description 6
- 238000002835 absorbance Methods 0.000 description 6
- 230000003078 antioxidant effect Effects 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 238000010791 quenching Methods 0.000 description 5
- 230000000171 quenching effect Effects 0.000 description 5
- GPWNWKWQOLEVEQ-UHFFFAOYSA-N 2,4-diaminopyrimidine-5-carbaldehyde Chemical compound NC1=NC=C(C=O)C(N)=N1 GPWNWKWQOLEVEQ-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 230000008033 biological extinction Effects 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 230000000694 effects 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
- VOLMSPGWNYJHQQ-UHFFFAOYSA-N Pyranone Natural products CC1=C(O)C(=O)C(O)CO1 VOLMSPGWNYJHQQ-UHFFFAOYSA-N 0.000 description 2
- 230000002292 Radical scavenging effect Effects 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 235000006708 antioxidants Nutrition 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000004896 high resolution mass spectrometry Methods 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000000144 pharmacologic effect Effects 0.000 description 2
- 230000001766 physiological effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 239000012085 test solution Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 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
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000003064 anti-oxidating effect Effects 0.000 description 1
- 230000000259 anti-tumor effect Effects 0.000 description 1
- 235000013405 beer Nutrition 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
- 238000004140 cleaning 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
- MGJZITXUQXWAKY-UHFFFAOYSA-N diphenyl-(2,4,6-trinitrophenyl)iminoazanium Chemical compound [O-][N+](=O)C1=CC([N+](=O)[O-])=CC([N+]([O-])=O)=C1N=[N+](C=1C=CC=CC=1)C1=CC=CC=C1 MGJZITXUQXWAKY-UHFFFAOYSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000007613 environmental effect Effects 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
- 230000006872 improvement Effects 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 239000000463 material 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
- 150000003248 quinolines Chemical class 0.000 description 1
- 230000009467 reduction Effects 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
- 230000002000 scavenging effect Effects 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F17/00—Metallocenes
- C07F17/02—Metallocenes of metals of Groups 8, 9 or 10 of the Periodic System
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P39/00—General protective or antinoxious agents
- A61P39/06—Free radical scavengers or antioxidants
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K15/00—Anti-oxidant compositions; Compositions inhibiting chemical change
- C09K15/04—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds
- C09K15/32—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds containing two or more of boron, silicon, phosphorus, selenium, tellurium or a metal
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention discloses a 4-methyl-6-phenyl-8-ferrocenyl pyranone quinoline, a preparation method and application thereof, wherein the structural formula of the 4-methyl-6-phenyl-8-ferrocenyl pyranone quinoline is as follows:the method takes 4-methyl-7-aminopyrone, ferrocene formaldehyde and phenylacetylene as raw materials, ce (OTf) 3 And Sc (OTf) 3 As a composite catalyst, the Povarov three-component reaction is realized under the condition of heating reflux, and 4-methyl-6-phenyl-8-ferrocenyl pyranone quinoline is efficiently catalyzed and synthesized. 4-methyl-6-phenyl-8-ferrocenylpyrone quinoline was added to ABTS, DPPH and gal, respectivelyIn the vinoxy radical ethanol solution, ABTS, DPPH and galvinoxy radicals can be well removed, the oxidation resistance is superior to that of corresponding vitamin E, 4-methyl-6, 8-diphenyl quinoline and 4-methyl-6, 8-diphenyl pyranone quinoline, and the preparation method has potential application value.
Description
Technical Field
The invention relates to the field of organic synthesis, in particular to 4-methyl-6-phenyl-8-ferrocenyl pyranone quinoline, and a preparation method and application thereof.
Background
Modification of natural framework structures, particularly integration of various natural framework structures or functional groups, has become a hotspot in the field of research on organic synthesis today.
The pyranone and quinoline compounds respectively have natural structure skeletons of oxygen heterocycle and nitrogen heterocycle, and have various physiological and pharmacological activities such as antioxidation, anti-tumor, antibiosis and the like. Ferrocene group is a novel antioxidant functional group, and its derivative has stronger antioxidant activity. The pyranone, quinoline and ferrocene groups are integrated into one molecule, so that a novel compound with higher physiological and pharmacological activity can be developed.
However, synthesis and biological performance studies on the integration of pyrone, quinoline and ferrocene groups into one molecule have been reported recently at home and abroad. In the catalytic reaction process, a synergistic effect exists among partial catalysts, the unique interaction can enhance the catalytic effect of each other, and the adoption of the composite catalyst can effectively improve the efficiency of the organic reaction and the synthesis yield of the target compound, so that the method has become an important research direction of organic catalysis.
Therefore, how to provide a compound integrating pyrone, quinoline and ferrocene groups is a technical problem to be solved in the art.
Disclosure of Invention
It is an object of the present invention to provide a new solution for 4-methyl-6-phenyl-8-ferrocenylpyrone and quinoline integrating pyrone, quinoline and ferrocenyl groups.
According to a first aspect of the present invention there is provided 4-methyl-6-phenyl-8-ferrocenylpyrone quinoline.
The structural formula of the 4-methyl-6-phenyl-8-ferrocenyl pyranone quinoline is as follows:
according to a second aspect of the present invention there is provided a process for the preparation of 4-methyl-6-phenyl-8-ferrocenylpyrone-quinoline of the present disclosure.
The preparation method of the 4-methyl-6-phenyl-8-ferrocenyl pyranone quinoline comprises the following steps:
takes 4-methyl-7-aminopyrone, ferrocene formaldehyde and phenylacetylene as raw materials and Ce (OTf) 3 And Sc (OTf) 3 4-methyl-7-aminopyrone, ferrocene formaldehyde, phenylacetylene, ce (OTf) are mixed as a composite catalyst 3 、Sc(OTf) 3 And 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 the 4-methyl-6-phenyl-8-ferrocenyl pyranone quinoline.
Alternatively, ferrocene carbaldehyde, phenylacetylene, 4-methyl-7-aminopyrone, ce (OTf) 3 、Sc(OTf) 3 The molar ratio of toluene to toluene is 100 (90-150) (80-150) (3-8) (4000-5000).
Alternatively, ferrocene carbaldehyde, phenylacetylene, 4-methyl-7-aminopyrone, ce (OTf) 3 、Sc(OTf) 3 And toluene at a molar ratio of 100:120:120:5:5:4700.
Alternatively, the oil bath temperature is 50-120 ℃.
Alternatively, the oil bath temperature is 110 ℃.
Alternatively, the reaction time is 1-3 hours.
Alternatively, the reaction time was 2h.
Optionally, the column chromatography eluent is at least one of dichloromethane, petroleum ether and ethyl acetate.
According to a third aspect of the present invention there is provided the use of 4-methyl-6-phenyl-8-ferrocenylpyrone-quinoline according to the present disclosure in the field of scavenging free radicals.
The method takes 4-methyl-7-aminopyrone, ferrocene formaldehyde and phenylacetylene as raw materials, ce (OTf) 3 And Sc (OTf) 3 As a composite catalyst, the Povarov three-component reaction is realized under the condition of heating reflux, and 4-methyl-6-phenyl-8-ferrocenyl pyranone quinoline is efficiently catalyzed and synthesized.
The 4-methyl-6-phenyl-8-ferrocenyl pyranone quinoline is respectively added into ABTS, DPPH and galvinoxyl radical ethanol solution, can well remove the ABTS, DPPH and galvinoxyl radical, shows excellent antioxidant activity, has better antioxidant performance than corresponding vitamin E, 4-methyl-6, 8-diphenyl quinoline and 4-methyl-6, 8-diphenyl pyranone quinoline, and 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-ferrocenylpyrone quinoline;
FIG. 2 is a nuclear magnetic resonance carbon spectrum of 4-methyl-6-phenyl-8-ferrocenylpyrone quinoline;
FIG. 3 is a mass spectrum of 4-methyl-6-phenyl-8-ferrocenylpyrone quinoline.
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, numerical expressions and numerical values set forth in these embodiments do not limit the scope of the present invention unless it is specifically stated otherwise.
The following description of at least one exemplary embodiment is merely exemplary in nature and is in no way intended to limit the invention, its application, or uses.
Techniques, methods, and apparatus known to one 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 specific values should be construed as merely illustrative, and not a limitation. Thus, other examples of exemplary embodiments may have different values.
The structural formula of the 4-methyl-6-phenyl-8-ferrocenyl pyranone quinoline provided by the present disclosure is as follows:
the preparation method of the 4-methyl-6-phenyl-8-ferrocenyl pyranone quinoline provided by the disclosure comprises the following steps:
takes 4-methyl-7-aminopyrone, ferrocene formaldehyde and phenylacetylene as raw materials and Ce (OTf) 3 And Sc (OTf) 3 4-methyl-7-aminopyrone, ferrocene formaldehyde, phenylacetylene, ce (OTf) are mixed as a composite catalyst 3 、Sc(OTf) 3 And 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 the 4-methyl-6-phenyl-8-ferrocenyl pyranone quinoline.
During the reaction, TLC was used to detect the reaction in real time.
The reaction process is as follows:
ferrocene carbaldehyde, phenylacetylene, 4-methyl-7-aminopyrone, ce (OTf) 3 、Sc(OTf) 3 The molar ratio of toluene to toluene may be 100 (90-150): (80-150): (3-8): (3-8): (4000-5000).
Further, ferrocene carbaldehyde, phenylacetylene, 4-methyl-7-aminopyrone, ce (OTf) 3 、Sc(OTf) 3 And toluene at a molar ratio of 100:120:120:5:5:4700.
The temperature of the oil bath can be 50-120 ℃.
Further, the oil bath temperature was 110 ℃.
The reaction time may be 1 to 3 hours.
Further, the reaction time was 2h.
The column chromatography eluent can be at least one of dichloromethane, petroleum ether and ethyl acetate.
In particular, the column chromatography eluent may be dichloromethane.
The disclosure also provides an application of the 4-methyl-6-phenyl-8-ferrocenyl pyranone quinoline in the field of free radical removal.
Oxidation resistance testing was performed on 4-methyl-6-phenyl-8-ferrocenylpyrone-quinoline. The specific process is as follows:
dissolving 4-methyl-6-phenyl-8-ferrocenylpyrone quinoline in ethanol to form an ethanol solution, adding the ethanol solution to a 2,2' -azo-bis- (3-ethylbenzothiazoline-6-sulfonic acid) diammonium salt free radical (ABTS), a diphenyl picrylhydrazyl free radical (DPPH) and a 2, 6-di-tert-butyl- (3, 5-di-tert-butyl-4-oxo-2, 5-cyclohexadiene) -p-tolueneoxy free radical (galvinoxyl) ethanol solution respectively, and then measuring the change curves of the concentration of the ABTS, DPPH and galvinoxyl free radicals with time at the maximum absorption wavelengths (734 nm, 517nm and 428 nm) to obtain the clearance rate of the 4-methyl-6-phenyl-8-ferrocenylpyrone quinoline free radical.
The concentrations of 4-methyl-6-phenyl-8-ferrocenylpyrone quinoline in the 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-ferrocenylpyrone quinoline with ABTS, DPPH and galvinoxyl radical was 30min.
The experimental procedures used in the examples below are conventional, and the materials and reagents used, unless otherwise indicated, are commercially available, and the equipment used in the experiments, unless otherwise indicated, are well known to those skilled in the art.
Examples
Main experimental reagents and instruments: 4-methyl-7-aminobenzopyrone, toluene, cerium triflate, scandium triflate, ferrocenecarboxaldehyde, phenylacetylene, dichloromethane, electronic balance, rotary evaporator, oil bath, bruker Avance III MHz nuclear magnetic resonance spectrometer (Bruker Co., U.S.A.), ultra high performance liquid chromatography-electrospray ion source-mass spectrometer (Agilent technologies Co., ltd.).
Ferrocene formaldehyde 0.43g (2.0 mmol), phenylacetylene 0.24g (2.4 mmol), 4-methyl-7-aminopyrone 0.42g (2.4 mmol), ce (OTf) 3 0.06g(0.1mmol)、Sc(OTf) 3 0.05g (0.1 mmol) and 10mL of toluene were added to a 25mL round bottom flask and reacted under stirring at reflux (110 ℃ C.) for 2h (TLC detection). Cooled to room temperature, the solvent concentrated and the residue chromatographed on a silica gel column [ eluent: dichloromethane (dichloromethane)]Purifying to obtain the 4-methyl-6-phenyl-8-ferrocenyl pyranone quinoline with the yield of 68.7%.
The structure of the obtained target compound was detected by Bruker Avance III MHz nuclear magnetic resonance spectrometer (Bruker Co., ltd.) and ultra high performance liquid chromatography-electrospray ion source-mass spectrometer (Agilent technologies Co., ltd.), 1 H NMR、 13 the C NMR and HR-MS are shown in FIGS. 1-3.
Structural characterization data for 4-methyl-6-phenyl-8-ferrocenylpyrone quinoline:
4-methyl-6-ferrocenyl-8-phenylpyranone quinoline: yellow solid, yield 68.7%, m.p. 241-243 ℃; 1 H NMR(400MHz,CDCl 3 )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)； 13 C 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 C 29 H 21 FeNO 2 {[M+H] + }472.100 0,found 472.103 8。
table 1 shows the effect of reaction conditions on the yield of the compound 4-methyl-6-phenyl-8-ferrocenylpyrone quinoline.
TABLE 1 influence of reaction conditions on the yield of 4-methyl-6-phenyl-8-ferrocenylpyrone quinoline
As can be seen from Table 1, with Ce (OTf) 3 And Sc (OTf) 3 As the composite catalyst, the reaction is carried out for 2 hours at 110 ℃, which is a preferred method for synthesizing the target compound, the yield of the compound 4-methyl-6-phenyl-8-ferrocenyl pyranone quinoline is 68.7 percent, which is higher than the catalytic yield of other catalysts. The reason is Ce (OTf) 3 And Sc (OTf) 3 All have the effect of catalyzing Povarov-3CR, and the two have synergistic effect after being compounded, and the unique interaction can enhance the catalysis of each other to generate the catalyst with the activity higher than Ce (OTf) 3 And Sc (OTf) 3 The catalytic efficiency when the catalyst is used alone can lead the reaction to be carried out in the forward direction, reduce the generation of byproducts and greatly improve the reaction efficiency of Povarov-3 CR.
Test of antioxidant Properties
1. And (5) cleaning ABTS and testing free radical performance.
Firstly, preparing a solution: weigh 5.0mg ABTS and 1.5mg K 2 S 2 O 8 Adding into a 2mL volumetric flask, adding distilled water to a certain volume, standing at room temperature in dark place for 24h, and changing the color into dark blue. Then transferring the mixture into a 100mL volumetric flask, fixing the volume by absolute ethyl alcohol, and placing the mixture in a constant-temperature water bath at 30 ℃ for 30min to obtain an ABTS ethanol solution. The absorbance of the solution at 734nm is maximum and is 1.671, and the molar extinction system of ABTS is shown in the wavelengthThe number was 1.6X104L/(mol cm). The procedure for quenching ABTS-radicals by the compounds is as follows: 1.9mL of ABTS radical ethanol solution and 0.1mL of stock solution to be tested compound with the concentration of 0.1mmol/L are removed, the test solution with the final concentration of the compound to be tested of 5 mu mol/L is added into a test tube, the test solution is quickly and evenly mixed, the decay curve of an absorbance value (A) at the maximum absorption wavelength within 30min along with time is recorded, the concentration of the initial moment and the final moment of the ABTS radical is obtained through the lambert beer law, and the concentration change is used for obtaining the ABTS clearance rate of 4-methyl-6-phenyl-8-ferrocenyl pyranone quinoline.
2. DPPH radical scavenging Performance test.
Firstly, preparing a solution: 4.0mg DPPH is weighed, added into a 20mL beaker, dissolved with a small amount of absolute ethyl alcohol, transferred into a 100mL volumetric flask, and subjected to constant volume with absolute ethyl alcohol to obtain DPPH-ethanol solution, wherein the maximum absorption wavelength of the solution is 517nm, the absorbance value is about 1.378, and the molar extinction coefficient at the wavelength is 4.09 multiplied by 103L/(mol cm). Compound quenching DPPH the procedure was consistent with compound quenching ABTS: 1.9mL of DPPH-ethanol solution and 0.1mL of a stock solution of a compound to be tested with the concentration of 0.2mmol/L are removed and added into a test tube, so that the final concentration of the compound to be tested is 10mmol/L, the compound to be tested is quickly and evenly mixed, an attenuation curve of an absorbance value (A) at the maximum absorption wavelength within 30min along with time is recorded, the concentrations of the initial moment and the final moment of DPPH-free radicals are obtained through a lambert law, and the DPPH clearance rate of 4-methyl-6-phenyl-8-ferrocenyl pyranone quinoline is obtained through concentration change.
3. And (3) testing the clearance of galvinoxyl and free radical.
Firstly, preparing a solution: 1.0mg of galvinoxyl was weighed into a 20mL beaker, dissolved with a small amount of absolute ethanol, and transferred to a 100mL volumetric flask, and the volumetric flask was fixed with absolute ethanol to obtain a galvinoxyl radical ethanol solution having an absorbance at 428nm of a maximum value of about 1.108 and a molar extinction coefficient at that wavelength of 1.4X105L/(mol cm). Compound quenching galvinoxyl radical procedure was consistent with compound quenching ABTS: 1.9mL of galvinoxyl radical ethanol solution and 0.1mL of a stock solution of a compound to be tested with the concentration of 1mmol/L are removed and added into a test tube, so that the final concentration of the compound to be tested is 50mmol/L, the compound to be tested is quickly and uniformly mixed, the attenuation curve of an absorbance value (A) at the maximum absorption wavelength within 30min along with time is recorded, the concentrations of the galvinoxyl radical at the initial moment and the final moment are obtained through the lambert law, and the clearance rate of 4-methyl-6-phenyl-8-ferrocenyl pyranone quinoline to the galvinoxyl radical is obtained through the concentration change.
Radical scavenging by the compounds of Table 1 for ABTS, DPPH and galvinoxyl
Note that: the concentration of the 3 compounds in the ABTS-free radical removal performance test system is 5 mu mol/L; the concentration of the 3 compounds in the DPPH free radical removal performance test system is 10 mu mol/L; the concentration of the 3 compounds in the clearance galvinoxyl radical performance test system is 50 mu mol/L.
As shown in Table 1, the clearance rates of the 4-methyl-6-phenyl-8-ferrocenylpyrone quinoline to ABTS, DPPH and galvinoxyl free radicals are 85.3%, 81.6% and 75.7%, respectively, so that the ABTS, DPPH and galvinoxyl free radicals can be well cleared, and the clearance rates of the free radicals are higher than that of vitamin E, 4-methyl-6, 8-diphenylquinoline and 4-methyl-6, 8-diphenylpyrone quinoline, and the preparation method has excellent antioxidant activity and potential application value.
The present disclosure finds use with Ce (OTf) 3 And Sc (OTf) 3 As a composite catalyst, the 4-methyl-7-aminopyrone, ferrocenyl formaldehyde and phenylacetylene are catalyzed to generate Povarov three-component reaction, the yield of the 4-methyl-6-phenyl-8-ferrocenyl pyrone quinoline with excellent oxidation resistance is obviously single catalyst reaction, the improvement of the working efficiency, the time saving, the environmental protection and the cost reduction are facilitated.
While certain specific embodiments of the invention have been described in detail by way of example, it will be appreciated by those skilled in the art that the above examples are for illustration only and are not intended to limit the scope of the 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 (6)
1. The preparation method of the 4-methyl-6-phenyl-8-ferrocenyl pyranone quinoline is characterized in that the structural formula of the 4-methyl-6-phenyl-8-ferrocenyl pyranone quinoline is as follows:
；
the preparation method comprises the following steps:
takes 4-methyl-7-aminopyrone, ferrocene formaldehyde and phenylacetylene as raw materials and Ce (OTf) 3 And Sc (OTf) 3 4-methyl-7-aminopyrone, ferrocene formaldehyde, phenylacetylene, ce (OTf) are mixed as a composite catalyst 3 、Sc(OTf) 3 And toluene, heating in an oil bath at 110 ℃ for a period of time, cooling to room temperature, concentrating the solvent, and purifying the residue by silica gel column chromatography to obtain the 4-methyl-6-phenyl-8-ferrocenyl pyranone quinoline.
2. The process for the preparation of 4-methyl-6-phenyl-8-ferrocenopyrone and quinoline according to claim 1, wherein ferrocenecarboxaldehyde, phenylacetylene, 4-methyl-7-aminopyrone, ce (OTf) 3 、Sc(OTf) 3 The molar ratio of toluene to toluene is 100 (90-150) (80-150) (3-8) (4000-5000).
3. The process for the preparation of 4-methyl-6-phenyl-8-ferrocenopyrone and quinoline according to claim 2, wherein ferrocenecarboxaldehyde, phenylacetylene, 4-methyl-7-aminopyrone, ce (OTf) 3 、Sc(OTf) 3 And toluene at a molar ratio of 100:120:120:5:5:4700.
4. The method for preparing 4-methyl-6-phenyl-8-ferrocenylpyrone quinoline according to claim 1, wherein the reaction time is 1-3h.
5. The method for preparing 4-methyl-6-phenyl-8-ferrocenylpyrone quinoline according to claim 4, wherein the reaction time is 2h.
6. The method for preparing 4-methyl-6-phenyl-8-ferrocenyl pyranone quinoline according to claim 1, wherein the column chromatography eluent is at least one of dichloromethane, petroleum ether and ethyl acetate.
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