CN115124478A - Iron-nitrogen co-doped carbon material catalyst and application thereof in synthesis of quinazoline and derivatives thereof - Google Patents
Iron-nitrogen co-doped carbon material catalyst and application thereof in synthesis of quinazoline and derivatives thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 78
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 74
- YYXHRUSBEPGBCD-UHFFFAOYSA-N azanylidyneiron Chemical compound [N].[Fe] YYXHRUSBEPGBCD-UHFFFAOYSA-N 0.000 title claims abstract description 55
- JWVCLYRUEFBMGU-UHFFFAOYSA-N quinazoline Chemical compound N1=CN=CC2=CC=CC=C21 JWVCLYRUEFBMGU-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 20
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 20
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 73
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 46
- 238000006243 chemical reaction Methods 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 26
- 230000003197 catalytic effect Effects 0.000 claims description 24
- 229910052742 iron Inorganic materials 0.000 claims description 24
- 238000007254 oxidation reaction Methods 0.000 claims description 23
- 238000001354 calcination Methods 0.000 claims description 22
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- 239000002245 particle Substances 0.000 claims description 19
- 239000002904 solvent Substances 0.000 claims description 18
- 238000002360 preparation method Methods 0.000 claims description 16
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 15
- 230000003647 oxidation Effects 0.000 claims description 15
- 239000007787 solid Substances 0.000 claims description 15
- 229920001661 Chitosan Polymers 0.000 claims description 14
- 125000003118 aryl group Chemical group 0.000 claims description 13
- 150000003278 haem Chemical class 0.000 claims description 13
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 11
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 11
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims description 11
- 229910052801 chlorine Inorganic materials 0.000 claims description 9
- -1 alcohol compound Chemical class 0.000 claims description 8
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 8
- 239000007800 oxidant agent Substances 0.000 claims description 8
- 125000004191 (C1-C6) alkoxy group Chemical group 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 7
- 229910021529 ammonia Inorganic materials 0.000 claims description 7
- 229910052794 bromium Inorganic materials 0.000 claims description 7
- 229910052731 fluorine Inorganic materials 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 238000002156 mixing Methods 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
- 230000001681 protective effect Effects 0.000 claims description 6
- 125000001424 substituent group Chemical group 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 4
- 125000001624 naphthyl group Chemical group 0.000 claims description 3
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 3
- 125000004076 pyridyl group Chemical group 0.000 claims description 3
- 238000006467 substitution reaction Methods 0.000 claims description 3
- 125000001544 thienyl group Chemical group 0.000 claims description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 2
- 125000003158 alcohol group Chemical group 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 238000002604 ultrasonography Methods 0.000 claims description 2
- 235000019441 ethanol Nutrition 0.000 description 11
- 239000000843 powder Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- 238000002390 rotary evaporation Methods 0.000 description 9
- 238000004817 gas chromatography Methods 0.000 description 8
- 238000001035 drying Methods 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 239000012043 crude product Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000010898 silica gel chromatography Methods 0.000 description 4
- 238000009210 therapy by ultrasound Methods 0.000 description 4
- 229920000877 Melamine resin Polymers 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 3
- 150000003246 quinazolines Chemical class 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000001093 anti-cancer Effects 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 2
- UZFMOKQJFYMBGY-UHFFFAOYSA-N 4-hydroxy-TEMPO Chemical compound CC1(C)CC(O)CC(C)(C)N1[O] UZFMOKQJFYMBGY-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 206010061218 Inflammation Diseases 0.000 description 1
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001409 amidines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000002155 anti-virotic effect Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000003935 benzaldehydes Chemical class 0.000 description 1
- 150000003939 benzylamines Chemical class 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000001225 therapeutic effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
- C07D239/70—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings condensed with carbocyclic rings or ring systems
- C07D239/72—Quinazolines; Hydrogenated quinazolines
- C07D239/74—Quinazolines; Hydrogenated quinazolines with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, attached to ring carbon atoms of the hetero ring
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
- C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
- C07D405/04—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
- C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
- C07D409/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
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Abstract
The invention discloses an iron-nitrogen co-doped carbon material catalyst and application thereof in synthesis of quinazoline and derivatives thereof.
Description
Technical Field
The invention relates to the technical field of synthesis of quinazoline and derivatives thereof, in particular to an iron-nitrogen co-doped carbon material catalyst and application thereof in synthesis of quinazoline and derivatives thereof.
Background
Quinazoline and its derivatives have important biological activity and medicinal value, are important compounds, and have therapeutic properties of anticancer, antivirus, anti-inflammation and anticancer, etc. In recent years, methods and routes for producing quinazolines have been varied, for example, halogenated benzaldehydes, halogenated benzonitrileThe quinazoline obtained by oxidation catalysis has moderate to excellent yield as the raw material reacts with amidine or guanidine; however, quinazoline-like compounds contain two nitrogen atoms and these two-component strategies may suffer from the unavailability of starting materials and limited substrate range. In addition, the reaction of ortho-aminoarylketones with benzylamines is also an important tool for the synthesis of quinazolines, but requires I 2 And CuO nanoparticles, 4-hydroxy TEMPO, tert-butyl hydroperoxide and other excessive oxidants, and the catalysts and the oxidants have more or less obvious problems, such as low catalytic efficiency, poor reaction selectivity, harsh reaction conditions, high reaction cost, poor substrate tolerance and the like.
Disclosure of Invention
The invention aims to overcome one or more defects in the prior art, and provides an application of a novel iron-nitrogen co-doped carbon material catalyst in the synthesis of quinazoline and derivatives thereof.
The invention also provides the novel iron-nitrogen co-doped carbon material catalyst.
In order to achieve the purpose, the invention adopts a technical scheme that:
the application of the iron-nitrogen co-doped carbon material catalyst in catalytic oxidation synthesis of quinazoline and derivatives thereof is characterized in that the iron-nitrogen co-doped carbon material catalyst takes a nitrogen-doped carbon material as a carrier, iron element particles are loaded on the carrier, and the iron element particles at least comprise iron atoms (Fe) 0 ) And iron oxide (FeO) x ) The forms coexist.
According to some preferred aspects of the invention, the elemental iron particles are present as both iron atoms and iron oxide.
According to some preferred and specific aspects of the present invention, the iron oxide is ferric oxide.
According to some preferred aspects of the present invention, the iron atom and the iron oxide are each nano-sized.
According to the inventionIn some preferred and specific aspects, the method for preparing the iron-nitrogen co-doped carbon material catalyst comprises: by making graphite-like phase carbon nitride (g-C) 3 N 4 ) Dispersing chitosan and heme iron in a first solvent, uniformly mixing, removing the first solvent to obtain a solid intermediate, and calcining under a protective atmosphere.
According to some preferred aspects of the present invention, in the preparation process of the iron-nitrogen co-doped carbon material catalyst, the feeding mass ratio of the graphite-like phase carbon nitride, the chitosan and the heme iron is 5-15: 0.5-2.5: 1. Further, the feeding mass ratio of the graphite-like phase carbon nitride to the chitosan to the heme iron is 8-12: 1-1.5: 1.
According to some preferred aspects of the invention, in the preparation process of the iron-nitrogen co-doped carbon material catalyst, the first solvent is an alcohol solvent, and the alcohol solvent is a C1-C6 alcohol compound. In some embodiments of the present invention, the first solvent may be ethanol, propanol, or the like.
According to some preferred aspects of the present invention, during the preparation of the iron-nitrogen co-doped carbon material catalyst, the blending is performed at room temperature, and is performed by stirring and/or ultrasound.
According to some preferred aspects of the present invention, the iron-nitrogen co-doped carbon material catalyst is prepared by allowing the solid intermediate to be in a dry state before being calcined.
According to some preferred aspects of the invention, during the preparation of the iron-nitrogen co-doped carbon material catalyst, the calcination is carried out at the calcination temperature of 750-850 ℃, which is more favorable for obtaining a catalyst with a desired structure, and the catalytic oxidation effect on quinazoline and derivatives thereof is better.
According to some preferred aspects of the present invention, during the preparation of the iron-nitrogen co-doped carbon material catalyst, the temperature rising rate from room temperature to the calcination temperature during the calcination is controlled to be 4-6 ℃/min.
According to some preferred aspects of the present invention, in the preparation of the iron-nitrogen co-doped carbon material catalyst, the calcination time of the calcination is controlled to be 1 to 3 hours.
In some embodiments of the present invention, during the preparation process of the iron-nitrogen co-doped carbon material catalyst, the protective gas used in the protective atmosphere is nitrogen, argon, or the like.
In some embodiments of the present invention, the preparation of the iron-nitrogen co-doped carbon material catalyst is performed by:
(1) dispersing graphite-like phase carbon nitride, chitosan and heme iron in ethanol to form a mixed solution;
(2) ultrasonically treating the mixed solution and stirring overnight;
(3) carrying out rotary evaporation on the intermediate obtained in the step (2), and drying to obtain solid powder;
(4) further drying the solid powder obtained in the step (3);
(5) calcining the dry powder obtained in the step (4) in a protective atmosphere to prepare the iron-nitrogen co-doped carbon material catalyst, Fe-FeO for short x @ NC (where Fe and FeO x Indicating the presence of iron particles and NC indicating nitrogen-doped carbon material).
In some embodiments of the invention, in step (4), drying is carried out at 55-65 ℃ for 10-14 hours.
In some embodiments of the invention, in step (5), the calcining is performed in a tube furnace.
According to some preferred aspects of the invention, in the application of synthesizing quinazoline and derivatives thereof, aromatic o-aminocarbonyl compounds, alcohol compounds and ammonia water are subjected to catalytic oxidation reaction in a second solvent in the presence of an oxidant and an iron-nitrogen co-doped carbon material catalyst to generate quinazoline and derivatives thereof.
According to some preferred aspects of the present invention, the oxidizing agent is oxygen, and the oxidizing agent is provided by introducing pure oxygen gas having a purity of more than 99% into the reaction system or introducing air.
According to some preferred aspects of the invention, the second solvent comprises water. In some embodiments of the present invention, the second solvent may be selected from water.
According to some preferred aspects of the present invention, the aromatic ortho-aminocarbonyl compound, the alcohol compound, and the ammonia in the ammonia water are fed in a molar ratio of 1: 2 to 4: 6 to 10. Furthermore, the feeding molar ratio of the aromatic o-aminocarbonyl compound, the alcohol compound and the ammonia in the ammonia water is 1: 2.5-3.5: 7-9.
In some embodiments of the invention, the aqueous ammonia is commercially available and commercially available industrial aqueous ammonia is used at a concentration of about 25% to about 28%.
According to some preferred aspects of the present invention, the amount of the iron-nitrogen co-doped carbon material catalyst is 5 to 65% of the amount of the aromatic ortho-aminocarbonyl compound added, in terms of mass percentage.
According to some preferred aspects of the invention, the catalytic oxidation reaction is carried out under heated conditions. Further, the catalytic oxidation reaction is carried out at 100-150 ℃, and further at 120-140 ℃. According to a particular aspect of the invention, the catalytic oxidation reaction is carried out at 130 ℃.
According to a particular aspect of the invention, the catalytic oxidation reaction can be carried out in a sealed reactor with air.
According to some preferred aspects of the present invention, the aromatic ortho-aminocarbonyl compound has the structure shown in formula (I):
in the formula (I), n is 0, 1, 2, 3 or 4, R 1 Is H, F, Br, Cl, nitro, cyano, unsubstituted or substituted C1-C6 alkyl, R 2 Is H, unsubstituted or substituted C1-C6 alkyl, unsubstituted or substituted C6-C12 aryl, -NH-R 4 ，R 4 Is unsubstituted or substituted C1-C6 alkyl; wherein, the substituent in the substituted C1-C6 alkyl is one or more of F, Br, Cl, nitro, cyano and C1-C6 alkoxy, and the substituent in the substituted C6-C12 aryl is one or more of F, Br, Cl, nitro, cyano, C1-C6 alkoxy and halogenated C1-C6 alkyl.
In some embodiments of the invention, n is 0 or 1, and when n is 1, R is 1 Substituted at the para position of the amino group.
Further, R 2 Is methyl, ethyl, H, phenyl or halogenated phenyl.
According to some preferred aspects of the invention, the alcohol compound has a structure represented by formula (ii):
in the formula (II), R 3 Is the following unsubstituted or substituted group: phenyl, naphthyl, thienyl,
Pyridyl, wherein the substituent adopted by the substitution is one or more of the following groups: F. br, Cl, nitro, cyano, C1-C6 alkyl, phenyl, C1-C6 alkoxy, halogenated C1-C6 alkyl.
Further, R 3 In the optional groups in (2), the substitution positions of naphthyl, thienyl and pyridyl are as follows:
in the present invention, the C1-C6 alkyl group may be methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, hexyl, etc.; the halogen used for the halogenation can be fluorine, chlorine or bromine; the C1-C6 alkoxy group may be methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, etc.
According to the invention, in the application of the iron-nitrogen co-doped carbon material catalyst in catalytic oxidation synthesis of quinazoline and derivatives thereof, the catalyst is recycled after the reaction is finished, and can be repeatedly utilized for many times, and the catalytic activity is not obviously attenuated.
In some embodiments of the invention, ethyl acetate is added to the reaction mixture after the catalytic oxidation reaction is completed, and the organic phase and ethyl acetate are removed by rotary evaporation to obtain a crude product. Finally, the pure product was obtained by silica gel column chromatography.
In some embodiments of the invention, the quinazoline and derivatives thereof have a structure as shown in formula (iii):
In the invention, the quinazoline and the derivative thereof are synthesized by adopting the catalyst one-pot method, so that the quinazoline and the derivative thereof are more green and efficient, have good reusability and are beneficial to large-scale production.
The invention provides another technical scheme that: the iron-nitrogen co-doped carbon material catalyst takes a nitrogen-doped carbon material as a carrier, iron element particles are loaded on the carrier, and the iron element particles exist in the form of iron atoms and iron oxide at least at the same time.
In the invention, the iron-nitrogen co-doped carbon material catalyst is in the form of an iron-nitrogen co-doped porous carbon material.
The invention provides another technical scheme that: a preparation method of an iron-nitrogen co-doped carbon material catalyst comprises the following steps: rendering graphite-like phase carbon nitride (g-C) 3 N 4 ) Dispersing chitosan and heme iron in a first solvent, uniformly mixing, removing the first solvent to obtain a solid intermediate, and calcining under a protective atmosphere.
In the present invention, the graphite-like phase carbon nitride (g-C) 3 N 4 ) The chitosan can respectively play a role in supporting and stabilizing the catalyst in the catalyst, so that the catalyst with uniformly dispersed iron element particles can be obtained, and the formed nitrogen-doped carbon material can fix or coat iron atoms and FeO x And (3) granules.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:
based on the defects of catalytic oxidation synthesis of quinazoline and derivatives thereof in the prior art, a large number of experimental researches show that when an iron-nitrogen co-doped carbon material is adopted, a nitrogen-doped carbon material is taken as a carrier, iron element particles are loaded on the carrier, and the iron element particles exist at least in the form of iron atoms and iron oxide at the same time, and are applied to the catalytic oxidation synthesis of quinazoline and derivatives thereof, quinazoline and derivatives thereof can be obtained efficiently and selectively, and the quinazoline and derivatives thereof have good stability, good reusability, simple process, low requirements on raw materials, expanded selectable range of raw materials and good substrate tolerance.
Drawings
Fig. 1 is an SEM image of an iron-nitrogen co-doped carbon material catalyst prepared in example 1 of the present invention;
FIG. 2 is a TEM image of an iron-nitrogen co-doped carbon material catalyst prepared in example 1 of the present invention;
fig. 3 is an XRD pattern of the iron-nitrogen co-doped carbon material catalyst prepared in example 1 of the present invention;
fig. 4 is an XPS chart of the iron-nitrogen co-doped carbon material catalyst prepared in example 1 of the present invention.
Detailed Description
The above-described scheme is further illustrated below with reference to specific examples; it is to be understood that these embodiments are provided to illustrate the general principles, essential features and advantages of the present invention, and the present invention is not limited in scope by the following embodiments; the implementation conditions used in the examples can be further adjusted according to specific requirements, and the implementation conditions not indicated are generally the conditions in routine experiments.
The following examples are not specifically illustrated and all starting materials are either commercially available or prepared by conventional methods known in the art.
g-C 3 N 4 The melamine is prepared by continuously calcining melamine for 2h after the melamine is raised to 550 ℃ at the speed of 5 ℃/min under the nitrogen atmosphere; the chitosan is purchased from Aladdin, the specification is 100g, and the product number is C105802-100 g; the heme iron was purchased from Mecanne, 100g specification, H885986.
EXAMPLE 1 catalyst Fe-FeO x Preparation of @ NC
The embodiment provides a preparation method of an iron-nitrogen co-doped carbon material catalyst, which comprises the following steps:
(1) feeding materials in a mass ratio of 10: 1.2: 1 g-C 3 N 4 Dissolving chitosan and heme iron in absolute ethyl alcohol to prepare a mixed solution, and performing ultrasonic treatment at room temperature for 3 hours; then stirring overnight for 24 hours, and then removing the absolute ethyl alcohol by rotary evaporation; then, the drying was continued at 60 ℃ for 12 hours to obtain a solid powder.
(2) Calcining the solid powder obtained in the step (1) in a tubular furnace at 800 ℃ for 2h (the heating rate is 5 ℃/min) in a nitrogen atmosphere to obtain the final granular carbon material catalyst in the form of the iron-nitrogen co-doped porous carbon material, namely the iron-nitrogen co-doped carbon material catalyst, which is recorded as Fe-FeO x @ NC (where Fe and FeO x Indicating the presence of iron particles and NC indicating nitrogen-doped carbon material). The obtained iron-nitrogen co-doped carbon material catalyst was tested as follows, and SEM, TEM, XRD and XPS graphs thereof are shown in fig. 1, 2, 3 and 4, respectively. SEM figure illustrates that the carbon material is present in a randomly aggregated state; the TEM diagram illustrates the presence of a nitrogen-doped carbon layer in the carbon material surrounding the nano-iron particles, which is uniformly distributed on the carbon material; TEM and XRD patterns confirm the possible presence of Fe in the iron particles 0 And Fe 2 O 3 A plurality of valence states are equal; the XPS chart shows the states (valence state, combination state, etc.) of iron and nitrogen elements which may exist respectively.
Example 2
The embodiment provides a preparation method of an iron-nitrogen co-doped carbon material catalyst, which comprises the following steps:
(1) feeding materials in a mass ratio of 10: 1.5: 1 g-C 3 N 4 Dissolving chitosan and heme iron in absolute ethyl alcohol to prepare a mixed solution, and performing ultrasonic treatment at room temperature for 3 hours; then stirring overnight for 24 hours, and then removing the absolute ethyl alcohol by rotary evaporation; then, the drying was continued at 60 ℃ for 12 hours to obtain a solid powder.
(2) And (2) calcining the solid powder obtained in the step (1) in a tubular furnace at 800 ℃ for 2h (the heating rate is 5 ℃/min) in a nitrogen atmosphere to obtain the final iron-nitrogen co-doped porous carbon material type granular carbon material catalyst, namely the iron-nitrogen co-doped carbon material catalyst.
Example 3
The embodiment provides a preparation method of an iron-nitrogen co-doped carbon material catalyst, which comprises the following steps:
(1) feeding materials according to the mass ratio of 12: 1.2: 1 g-C 3 N 4 Dissolving chitosan and heme iron in absolute ethyl alcohol to prepare a mixed solution, and performing ultrasonic treatment at room temperature for 3 hours; then stirring overnight for 24 hours, and then removing the absolute ethyl alcohol by rotary evaporation; then, the drying was continued at 60 ℃ for 12 hours to obtain a solid powder.
(2) And (2) calcining the solid powder obtained in the step (1) in a tubular furnace at 820 ℃ for 2h (the heating rate is 5 ℃/min) in a nitrogen atmosphere to obtain the final iron-nitrogen co-doped porous carbon material type granular carbon material catalyst, namely the iron-nitrogen co-doped carbon material catalyst.
Comparative example 1
Basically, the method is the same as the method of the embodiment 1, and the method only differs from the method in that: the step (1) is different and comprises the following specific steps:
(1) mixing the raw materials in a mass ratio of 10:1.2 to obtain the product 3 N 4 Dispersing chitosan and the chitosan into absolute ethyl alcohol to prepare a mixed solution, and performing ultrasonic treatment at room temperature for 3 hours; then stirring overnight for 24 hours, and then removing the absolute ethyl alcohol by rotary evaporation; then, the drying was continued at 60 ℃ for 12 hours to obtain a solid powder.
(2) And (2) calcining the solid powder obtained in the step (1) in a tubular furnace at 800 ℃ for 2h under the nitrogen atmosphere (the heating rate is 5 ℃/min), and obtaining the final granular carbon material catalyst in the form of the iron-nitrogen co-doped porous carbon material, which is recorded as NC (wherein NC represents a nitrogen-doped carbon material).
Comparative example 2
Basically, the method is the same as the method of the embodiment 1, and the method only differs from the method in that: in the presence of Fe-FeO x After the preparation of @ NC is finished, Fe-FeO without iron particles is prepared by 1mol/L hydrochloric acid pickling x @ NC-A (where Fe and FeO x Indicating the presence of iron particles, NC indicates nitrogen-doped carbon material, a indicates an acid washing process).
Comparative example 3
Basically, the method is the same as the method of the embodiment 1, and the method only differs from the method in that: the step (1) is different, and the heme iron is replaced by ferric nitrate nonahydrate (the charging mass of the ferric nitrate is controlled to be the same as that of the heme iron).
Examples 4-28 preparation of quinazolines and derivatives thereof
0.25mmol of an aromatic o-aminocarbonyl compound having a structure shown in Table 1 below, 0.75mmol of an alcohol compound, 2mmol of aqueous ammonia (commercially available industrial aqueous ammonia having a concentration of about 26.5. + -. 1.5%), and 20mg of Fe-FeO prepared in example 1 x @ NC, 1mL of water is added into a reaction vessel, the reaction vessel is heated to about 130 ℃ under the air condition and sealed for 24 hours, after the reaction is finished and the temperature is reduced, the catalyst and the reaction liquid are centrifugally separated, the reaction yield and the selectivity are determined by Gas Chromatography (GC) and gas chromatography mass spectrometry (GC-MS), and Fe-FeO is centrifugally separated x @ NC, rotary evaporation to remove the organic phase to give the crude product. Finally, the pure product was obtained by simple silica gel column chromatography. The specific results are shown in table 1.
Application comparative example 1
Basically, the method is the same as the method in example 4, and only differs from the method in that: the "Fe-FeO prepared in example 1 x @ NC "was replaced with catalyst NC prepared in comparative example 1. Specific results are shown in table 1.
Comparative application example 2
Basically, the method is the same as the method in example 4, and only differs from the method in that: the "Fe-FeO prepared in example 1 x Replacement of @ NC "with the catalyst Fe-FeO made in comparative example 2 x @ NC-A. Specific results are shown in table 1.
Comparative application example 3
Basically, the method is the same as the method in example 4, and only differs from the method in that: the "Fe-FeO prepared in example 1 x @ NC "was replaced with the catalyst prepared in comparative example 3. The specific results are shown in table 1.
TABLE 1
Example 29:
aromatic o-aminocarbonyl compound
0.25mmol, alcohol Compound
0.75mmol, 2mmol of ammonia (commercial industrial ammonia, concentration of about 26.5 + -1.5%), 20mg of the catalyst prepared in example 2, 1mL of water in a reaction vessel, heating to about 130 ℃ under air, sealing for reaction for 24 hours, cooling after the reaction is finished, centrifuging the catalyst and the reaction solution, determining the reaction yield and selectivity by Gas Chromatography (GC) and gas chromatography mass spectrometry (GC-MS), centrifuging the catalyst, and removing the organic phase by rotary evaporation to obtain a crude product. Finally, the pure product was obtained by simple silica gel column chromatography. The yield was 92%.
Example 30:
aromatic o-aminocarbonyl compound
0.25mmol, alcohol Compound
0.75mmol of ammonia water (commercial)Commercial industrial ammonia, concentration about 26.5 ± 1.5%), 2mmol, 20mg of the catalyst prepared in example 3, 1mL of water were put into a reaction vessel, heated to about 130 ℃ under air conditions, sealed and reacted for 24 hours, after the reaction was completed and cooled, the catalyst and the reaction solution were separated by centrifugation, the reaction yield and selectivity were determined by Gas Chromatography (GC) and gas chromatography-mass spectrometry (GC-MS), the catalyst was separated by centrifugation, and the organic phase was removed by rotary evaporation to obtain a crude product. Finally, the pure product was obtained by simple silica gel column chromatography. The yield was 90%.
Example 31: catalyst reuse Activity test
Aromatic o-aminocarbonyl compound
0.25mmol, alcohol Compound
0.75mmol, 2mmol of aqueous ammonia (commercial industrial ammonia, concentration: 26.5. + -. 1.5%), 20mg of Fe-FeO prepared in example 1 x @ NC, 1mL of water was added to the reaction vessel, heated to about 130 ℃ under air conditions, and sealed for 12 hours (indicating that the reaction time for the recovery experiment was short, so the yield was low, the recovery effect was seen under the low yield condition, and the recoverability of the catalyst was more pronounced), after the reaction was completed and the temperature was lowered, the catalyst and the reaction solution were centrifugally separated, the reaction yield and selectivity were determined by Gas Chromatography (GC) and gas chromatography mass spectrometry (GC-MS), and centrifugally separated Fe-FeO x @ NC as catalyst for the same reaction in the next batch. The yields in the 1 to 5 reactions used newly and mechanically are as follows: 67%, 64%, 67%, 64%, 55%, 51%, no significant decay in catalyst activity.
The above embodiments are only for illustrating the technical idea and features of the present invention, and the purpose of the present invention is to enable those skilled in the art to understand the content of the present invention and implement the present invention, and not to limit the protection scope of the present invention by this means. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
Claims (10)
1. The application of the iron-nitrogen co-doped carbon material catalyst in catalytic oxidation synthesis of quinazoline and derivatives thereof is characterized in that the iron-nitrogen co-doped carbon material catalyst takes a nitrogen-doped carbon material as a carrier, iron element particles are loaded on the carrier, and the iron element particles exist in the form of iron atoms and ferric oxide at least at the same time.
2. The application of the iron-nitrogen co-doped carbon material catalyst in catalytic oxidation synthesis of quinazoline and derivatives thereof according to claim 1, wherein the iron oxide is ferric oxide; and/or, the iron element particles exist in the form of iron atoms and iron oxide at the same time; and/or the iron atoms and the iron oxide are respectively in a nanometer size.
3. The application of the iron-nitrogen co-doped carbon material catalyst in catalytic oxidation synthesis of quinazoline and derivatives thereof according to claim 1, wherein the preparation method of the iron-nitrogen co-doped carbon material catalyst comprises the following steps: dispersing graphite-like phase carbon nitride, chitosan and heme iron in a first solvent, uniformly mixing, removing the first solvent to obtain a solid intermediate, and calcining under a protective atmosphere.
4. The application of the iron-nitrogen co-doped carbon material catalyst in catalytic oxidation synthesis of quinazoline and derivatives thereof according to claim 3, wherein the feeding mass ratio of the graphite-like phase carbon nitride, the chitosan and the heme iron is 5-15: 0.5-2.5: 1.
5. The application of the iron-nitrogen co-doped carbon material catalyst in catalytic oxidation synthesis of quinazoline and derivatives thereof according to claim 3, wherein the first solvent is an alcohol solvent, and the alcohol solvent is a C1-C6 alcohol compound; and/or, the blending is carried out at room temperature by adopting stirring and/or ultrasound.
6. The application of the iron-nitrogen co-doped carbon material catalyst in catalytic oxidation synthesis of quinazoline and derivatives thereof according to claim 3, characterized in that the solid intermediate is in a dry state before being calcined; and/or the calcination is carried out at a calcination temperature of 750-850 ℃; and/or controlling the heating rate of heating from room temperature to the calcining temperature to be 4-6 ℃/min in the calcining process; and/or controlling the calcination time of the calcination to be 1-3 h.
7. The application of the iron and nitrogen co-doped carbon material catalyst in catalytic oxidation synthesis of quinazoline and derivatives thereof according to claim 1 is characterized in that an aromatic o-aminocarbonyl compound, an alcohol compound and ammonia water are subjected to catalytic oxidation reaction in a second solvent in the presence of an oxidant and the iron and nitrogen co-doped carbon material catalyst to generate quinazoline and derivatives thereof.
8. The application of the iron-nitrogen co-doped carbon material catalyst in catalytic oxidation synthesis of quinazoline and derivatives thereof according to claim 7, wherein the oxidant is oxygen, and the oxidant is provided by introducing pure oxygen with a purity of more than 99% into a reaction system or introducing air; and/or, the second solvent comprises water; and/or the feeding molar ratio of the aromatic ortho-aminocarbonyl compound, the alcohol compound and the ammonia in the ammonia water is 1: 2-4: 6-10; and/or the dosage of the iron-nitrogen co-doped carbon material catalyst is 5-65% of the addition amount of the aromatic o-aminocarbonyl compound in percentage by mass; and/or, allowing the catalytic oxidation reaction to proceed under heating conditions.
9. The application of the iron-nitrogen co-doped carbon material catalyst in catalytic oxidation synthesis of quinazoline and derivatives thereof according to claim 7, wherein the aromatic o-aminocarbonyl compound has a structure shown in formula (I):
in formula (I), n is 0, 1, 2, 3 or 4, R 1 Is H, F, Br, Cl, nitro, cyano, unsubstituted or substituted C1-C6 alkyl, R 2 Is H, unsubstituted or substituted C1-C6 alkyl, unsubstituted or substituted C6-C12 aryl, -NH-R 4 ，R 4 Is unsubstituted or substituted C1-C6 alkyl; wherein, the substituent in the substituted C1-C6 alkyl is one or more selected from F, Br, Cl, nitro, cyano and C1-C6 alkoxy, and the substituent in the substituted C6-C12 aryl is one or more selected from F, Br, Cl, nitro, cyano, C1-C6 alkoxy and halogenated C1-C6 alkyl;
the alcohol compound has a structure shown in a formula (II):
in the formula (II), R 3 Is the following unsubstituted or substituted group: phenyl, naphthyl, thienyl,
Pyridyl, wherein the substituent adopted by the substitution is one or more of the following groups: F. br, Cl, nitro, cyano, C1-C6 alkyl, phenyl, C1-C6 alkoxy and halogenated C1-C6 alkyl.
10. The iron-nitrogen co-doped carbon material catalyst is characterized in that: the iron-nitrogen co-doped carbon material catalyst takes a nitrogen-doped carbon material as a carrier, iron element particles are loaded on the carrier, and the iron element particles exist in the form of iron atoms and iron oxide at least at the same time.
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