CN115160228B - Method for synthesizing 3-indazolone compound by photocatalysis - Google Patents
Method for synthesizing 3-indazolone compound by photocatalysis Download PDFInfo
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- CN115160228B CN115160228B CN202110367384.0A CN202110367384A CN115160228B CN 115160228 B CN115160228 B CN 115160228B CN 202110367384 A CN202110367384 A CN 202110367384A CN 115160228 B CN115160228 B CN 115160228B
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- titanium dioxide
- indazolone
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- anthranilamide
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- -1 3-indazolone compound Chemical class 0.000 title claims abstract description 63
- 238000000034 method Methods 0.000 title claims abstract description 51
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 33
- 238000007146 photocatalysis Methods 0.000 title claims abstract description 31
- 230000002194 synthesizing effect Effects 0.000 title claims description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 206
- PXBFMLJZNCDSMP-UHFFFAOYSA-N ortho-aminobenzoylamine Natural products NC(=O)C1=CC=CC=C1N PXBFMLJZNCDSMP-UHFFFAOYSA-N 0.000 claims abstract description 106
- 238000006243 chemical reaction Methods 0.000 claims abstract description 91
- 239000003054 catalyst Substances 0.000 claims abstract description 89
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 69
- 239000001257 hydrogen Substances 0.000 claims abstract description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 4
- LOCAIGRSOJUCTB-UHFFFAOYSA-N indazol-3-one Chemical class C1=CC=C2C(=O)N=NC2=C1 LOCAIGRSOJUCTB-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052751 metal Inorganic materials 0.000 claims abstract description 4
- 239000002184 metal Substances 0.000 claims abstract description 4
- 229910052802 copper Inorganic materials 0.000 claims description 97
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 32
- 239000001301 oxygen Substances 0.000 claims description 32
- 229910052760 oxygen Inorganic materials 0.000 claims description 32
- 229910044991 metal oxide Inorganic materials 0.000 claims description 14
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 13
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 229910052736 halogen Inorganic materials 0.000 claims description 11
- 150000002367 halogens Chemical group 0.000 claims description 11
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 10
- 238000013032 photocatalytic reaction Methods 0.000 claims description 10
- 150000004706 metal oxides Chemical class 0.000 claims description 9
- 150000002431 hydrogen Chemical group 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 5
- 238000011068 loading method Methods 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 229910052740 iodine Inorganic materials 0.000 claims description 3
- 125000001424 substituent group Chemical group 0.000 claims description 3
- 238000006467 substitution reaction Methods 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 239000004065 semiconductor Substances 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 229910000510 noble metal Inorganic materials 0.000 abstract description 3
- 239000011941 photocatalyst Substances 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 239000000758 substrate Substances 0.000 abstract 1
- 239000010949 copper Substances 0.000 description 96
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 78
- 229910010413 TiO 2 Inorganic materials 0.000 description 72
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 52
- SWEICGMKXPNXNU-UHFFFAOYSA-N 1,2-dihydroindazol-3-one Chemical compound C1=CC=C2C(O)=NNC2=C1 SWEICGMKXPNXNU-UHFFFAOYSA-N 0.000 description 45
- 239000002105 nanoparticle Substances 0.000 description 30
- 229910052786 argon Inorganic materials 0.000 description 26
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 25
- 238000004458 analytical method Methods 0.000 description 25
- 238000004817 gas chromatography Methods 0.000 description 25
- 239000010453 quartz Substances 0.000 description 25
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 25
- 238000001291 vacuum drying Methods 0.000 description 25
- 238000003756 stirring Methods 0.000 description 24
- 238000005406 washing Methods 0.000 description 24
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 23
- 238000000151 deposition Methods 0.000 description 23
- 230000008021 deposition Effects 0.000 description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 23
- 230000001678 irradiating effect Effects 0.000 description 22
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- RBLUNHLISNCJEE-UHFFFAOYSA-N 6-nitroindazol-3-one Chemical compound [O-][N+](=O)C1=CC=C2C(=O)N=NC2=C1 RBLUNHLISNCJEE-UHFFFAOYSA-N 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 2
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 2
- 229940112669 cuprous oxide Drugs 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 2
- 238000002256 photodeposition Methods 0.000 description 2
- HXBMIQJOSHZCFX-UHFFFAOYSA-N 1-(bromomethyl)-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1CBr HXBMIQJOSHZCFX-UHFFFAOYSA-N 0.000 description 1
- FEBQTMQGJXZYKX-UHFFFAOYSA-N 2-amino-3-methylbenzamide Chemical compound CC1=CC=CC(C(N)=O)=C1N FEBQTMQGJXZYKX-UHFFFAOYSA-N 0.000 description 1
- OYWVJWDGBABBIR-UHFFFAOYSA-N 2-amino-4-chloro-3-methylbenzamide Chemical compound CC1=C(Cl)C=CC(C(N)=O)=C1N OYWVJWDGBABBIR-UHFFFAOYSA-N 0.000 description 1
- FHIFCKSBNKKCJM-UHFFFAOYSA-N 2-amino-4-nitrobenzamide Chemical compound NC(=O)C1=CC=C([N+]([O-])=O)C=C1N FHIFCKSBNKKCJM-UHFFFAOYSA-N 0.000 description 1
- CMWKITSNTDAEDT-UHFFFAOYSA-N 2-nitrobenzaldehyde Chemical compound [O-][N+](=O)C1=CC=CC=C1C=O CMWKITSNTDAEDT-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006268 reductive amination reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000001931 thermography Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/54—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings condensed with carbocyclic rings or ring systems
- C07D231/56—Benzopyrazoles; Hydrogenated benzopyrazoles
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a method for preparing 3-indazolone compounds by photocatalysis. According to the method, an anthranilamide compound is used as a substrate, under the action of a titanium dioxide semiconductor photocatalyst loaded by a variable-valence metal, the 3-indazolone compound is prepared under the irradiation of light, the yield of the 3-indazolone compound reaches 76%, and simultaneously hydrogen is generated. The catalyst prepared by the method has high catalytic activity, is easy to prepare, avoids using noble metal to load, is easy to separate and recycle after reaction, can greatly reduce the production cost, and has potential application prospect.
Description
Technical Field
The invention relates to a 3-indazolone compound, in particular to a method for preparing the 3-indazolone compound by photocatalytic conversion of an anthranilamide compound.
Background
The 3-indazolone compound is an important drug intermediate, and is widely applied to aspects of drug synthesis, disease treatment, biological research, thermal imaging, antioxidants and the like after being further derivatized. At present, an intermediate of a product is mainly produced by reductive amination of an amine compound and o-nitrobenzaldehyde or substitution reaction of the amine compound and o-bromomethyl nitrobenzene, then the intermediate is subjected to David-Beruit reaction in an alcohol solution under the catalysis of alkali to obtain 2-substituted indazole, and then the 2-substituted indazole is hydrolyzed in an acid solution to obtain a 3-indazolone compound (Chinese patent CN 110526898A). The method has the advantages of multiple steps, harsh reaction conditions, low yield and high energy consumption, and is difficult to realize the green, efficient and economic synthesis target of the process.
Therefore, it is imperative to develop a green and sustainable synthesis method or process of 3-indazolone compounds, avoiding the problems of energy consumption and environmental pollution of the traditional thermocatalytic synthesis strategy.
Disclosure of Invention
The invention aims to provide a method for preparing a 3-indazolone compound by photocatalytic conversion of an anthranilamide compound, which has the characteristics of high product yield, mild reaction conditions, green and efficient process and the like. The reaction process is as follows:
wherein X is hydrogen, halogen, nitro, alkyl, substituted alkyl, etc.; y is hydrogen, halogen, nitro, alkyl, substituted alkyl, etc.; z is hydrogen, halogen, nitro, alkyl, substituted alkyl, etc.; w is hydrogen, halogen, nitro, alkyl, substituted alkyl, etc.
Adding a titanium dioxide semiconductor catalyst modified by a valence-variable metal oxide and an anthranilamide compound into a solvent, and after removing oxygen in the system, starting a light source to perform a photocatalytic reaction to obtain a 3-indazolone compound accompanied with hydrogen. The anthranilamide compound, when one or more of X, Y, Z, W is halogen, may be F, cl, br, I, preferably Cl or Br; when one or more of X, Y, Z, W are alkyl, they may be C n H 2n+1 (n=1 to 4); when one or more of X, Y, Z, W is a substituted alkyl group, it may be C n H 2n A (n=1 to 4), wherein A is a substituent, and may be halogen, nitro or alkyl (e.g. C n H 2n+1 (n=1 to 4)), the substitution position may be on any carbon of the substituted alkyl group. The valence-changing metal in the titanium dioxide catalyst modified by the valence-changing metal oxide can be Cu, fe, ni, co, pb and the like, and is preferably Cu or Fe; the loading of the variable valence metal oxide is 0.1 to 10.0% (based on mass ratio), preferably 0.5 to 1.0% (based on mass ratio). The titanium dioxide may be in a single phase of the anatase phase, the rutile phase or a mixed phase, preferably a mixed phase of the anatase phase and the rutile phase; the mass ratio of anatase to rutile in the mixed phase of anatase and rutile is 0.1 to 10.0, preferably 1.0 to 4.0. The light source for the photocatalytic reaction is as follows: ultraviolet light or sunlight; the wavelength of the light source is preferably 220-390 nm; the light intensity of the light source is preferably 6-18W. The mass ratio of the variable valence metal oxide modified titanium dioxide semiconductor catalyst to the solvent is 0.001-0.1, preferably 0.005-0.01. The time of the photocatalytic reaction is 1 to 72 hours, preferably 1 to 3 hours. Oxygen in the system can be removed by air extraction or inert gas filling.
The cuprous oxide and titanium dioxide are combined to construct oxygen-enriched defect sites on the surface, the N-H bond is activated by utilizing the characteristic of oxygen defect, further, the combination of photocatalysis and organic synthesis can be well realized by promoting the dehydrogenation coupling reaction, and the 3-indazolone compound is generated by converting the anthranilamide compound.
Compared with the prior art, the technical scheme of the invention has the following beneficial effects:
(1) The modified titanium dioxide semiconductor photocatalyst disclosed by the invention uses cuprous oxide, and compared with a method for loading noble metal, the modified titanium dioxide semiconductor photocatalyst has the advantages of low raw material price and environmental friendliness.
(2) The invention adopts the photocatalysis process to replace the traditional thermocatalysis process, thereby avoiding the excessive energy consumption and further reducing the production cost.
(3) The photocatalysis reaction is a heterogeneous catalysis reaction, and the catalyst can be recovered and recycled.
(4) The process can obtain the 3-indazolone compound and the same amount of hydrogen gas as the gas product, is easy to separate from the product, and can be used as clean energy.
The catalyst prepared by the method has high catalytic activity, is easy to prepare, avoids using noble metal to load, is easy to separate and recycle after reaction, can greatly reduce the production cost, and has potential application prospect.
Detailed Description
In order to make the technical problems, technical schemes and beneficial effects to be solved more clear and obvious, the invention is further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
Example 1
0.1％Cu 2 O/TiO 2 The catalyst is obtained by the following process: adding 1.0g of titanium dioxide nano particles (mass ratio: rutile phase 20% and anatase phase 80%) into 30mL of anhydrous methanol, adding a certain amount of copper chloride, wherein the mass of copper is 0.1% of that of titanium dioxide, stirring uniformly, transferring into a quartz kettle, replacing with CO for 3 times, and standing at normal temperature and normal temperatureUnder the conditions of pressure and CO atmosphere, irradiating 40W ultraviolet light at 365nm for 2h to perform photo-deposition, washing with water for 3 times, placing in a vacuum drying oven at 60 ℃ for 12h, and collecting under inert atmosphere (argon) to obtain 0.1% Cu 2 O/TiO 2 A catalyst. 10mg of the above-prepared 0.1% Cu was taken 2 O/TiO 2 The catalyst is added into 1ml of anthranilamide-acetonitrile solution with the mass percent of the anthranilamide being 20 percent, after oxygen in the system is removed, an 18W ultraviolet LED lamp is started, and photocatalysis reaction is carried out for 3 hours under the 365nm condition of an ultraviolet light source. After the reaction solution was filtered, gas chromatography analysis showed that the conversion of anthranilamide was 90%, the selectivity for 3-indazolone was 76%, and the yield of 3-indazolone was 68%.
Example 2
1.0％Cu 2 O/TiO 2 The catalyst is obtained by the following process: adding 1.0g of titanium dioxide nano particles (mass ratio: 20% of rutile phase and 80% of anatase phase) into 30mL of absolute methanol, adding a certain amount of copper chloride, wherein the mass of copper is 1.0% of that of titanium dioxide, stirring uniformly, transferring into a quartz kettle, replacing with CO for 3 times, performing light deposition by irradiating with 40W ultraviolet light at 365nm for 2 hours under the conditions of normal temperature, normal pressure and CO atmosphere, washing with water for 3 times, placing in a vacuum drying oven at 60 ℃ for 12 hours, and collecting 1.0% Cu under an inert atmosphere (argon) 2 O/TiO 2 A catalyst. 10mg of the above-prepared 1.0% Cu was taken 2 O/TiO 2 The catalyst is added into 1ml of anthranilamide-acetonitrile solution with the mass percent of the anthranilamide being 20 percent, after oxygen in the system is removed, an 18W ultraviolet LED lamp is started, and photocatalysis reaction is carried out for 3 hours under the 365nm condition of an ultraviolet light source. After the reaction solution was filtered, gas chromatography analysis showed that the conversion of anthranilamide was 94%, the selectivity for 3-indazolone was 81%, and the yield of 3-indazolone was 76%.
Example 3
5.0％Cu 2 O/TiO 2 The catalyst is obtained by the following process: 1.0g of titanium dioxide nano particles (mass ratio: rutile phase 20%, anatase phase 80%) are taken and added into 30mL of absolute methanol, and a certain amount of titanium dioxide nano particles are addedCopper chloride, wherein the mass of copper is 5.0% of the mass of titanium dioxide, the titanium dioxide is transferred into a quartz kettle after being stirred uniformly, after being replaced by CO for 3 times, light deposition is carried out by irradiation of 40W ultraviolet light 365nm for 2 hours under the conditions of normal temperature, normal pressure and CO atmosphere, then water washing is carried out for 3 times, the copper is placed in a vacuum drying oven at 60 ℃ for 12 hours, and 5.0% Cu is obtained by collection under inert atmosphere (argon) 2 O/TiO 2 A catalyst. 10mg of the above-prepared 1.0% Cu was taken 2 O/TiO 2 The catalyst is added into 1ml of anthranilamide-acetonitrile solution with the mass percent of the anthranilamide being 20 percent, after oxygen in the system is removed, an 18W ultraviolet LED lamp is started, and photocatalysis reaction is carried out for 3 hours under the 365nm condition of an ultraviolet light source. After the reaction solution was filtered, gas chromatography analysis showed that the conversion of anthranilamide was 92%, the selectivity of 3-indazolone was 80%, and the yield of 3-indazolone was 74%.
Example 4
10.0％Cu 2 O/TiO 2 The catalyst is obtained by the following process: adding 10.0g of titanium dioxide nano particles (mass ratio: 20% of rutile phase and 80% of anatase phase) into 30mL of absolute methanol, adding a certain amount of copper chloride, wherein the mass of copper is 10.0% of that of titanium dioxide, stirring uniformly, transferring into a quartz kettle, replacing with CO for 3 times, performing light deposition by irradiating with 40W ultraviolet light at 365nm for 2 hours under the conditions of normal temperature, normal pressure and CO atmosphere, washing with water for 3 times, placing in a vacuum drying oven at 60 ℃ for 12 hours, and collecting under an inert atmosphere (argon) to obtain 10.0% Cu 2 O/TiO 2 A catalyst. 10mg of the above-prepared Cu of 10.0% was taken 2 O/TiO 2 The catalyst is added into 1ml of anthranilamide-acetonitrile solution with the mass percent of the anthranilamide being 20 percent, after oxygen in the system is removed, an 18W ultraviolet LED lamp is started, and photocatalysis reaction is carried out for 3 hours under the 365nm condition of an ultraviolet light source. After the reaction solution was filtered, gas chromatography analysis showed that the conversion of anthranilamide was 87%, the selectivity of 3-indazolone was 80%, and the yield of 3-indazolone was 70%.
Example 5
0.1％Cu 2 O/TiO 2 CatalystObtained by the following process: adding 1.0g of titanium dioxide nano particles (100% of anatase phase) into 30mL of anhydrous methanol, adding a certain amount of copper chloride, wherein the mass of copper is 0.1% of that of titanium dioxide, stirring uniformly, transferring into a quartz kettle, replacing with CO for 3 times, performing light deposition under the conditions of normal temperature, normal pressure and CO atmosphere, irradiating with 40W ultraviolet light at 365nm for 2h, washing with water for 3 times, placing in a vacuum drying oven at 60 ℃ for 12h, and collecting under an inert atmosphere (argon) to obtain 0.1% Cu 2 O/TiO 2 A catalyst. 10mg of the above-prepared 0.1% Cu was taken 2 O/TiO 2 The catalyst is added into 1ml of anthranilamide-acetonitrile solution with the mass percent of the anthranilamide being 20 percent, after oxygen in the system is removed, an 18W ultraviolet LED lamp is started, and photocatalysis reaction is carried out for 3 hours under the 365nm condition of an ultraviolet light source. After the reaction solution was filtered, gas chromatography analysis showed that the conversion of anthranilamide was 94%, the selectivity for 3-indazolone was 91%, and the yield of 3-indazolone was 73%.
Example 6
0.1％Cu 2 O/TiO 2 The catalyst is obtained by the following process: adding 1.0g of titanium dioxide nano particles (rutile phase 100%) into 30mL of anhydrous methanol, adding a certain amount of copper chloride, wherein the mass of copper is 0.1% of that of titanium dioxide, stirring uniformly, transferring into a quartz kettle, replacing with CO for 3 times, performing light deposition under the conditions of normal temperature, normal pressure and CO atmosphere, irradiating with 40W ultraviolet light at 365nm for 2h, washing with water for 3 times, placing in a vacuum drying oven at 60 ℃ for 12h, and collecting under an inert atmosphere (argon) to obtain 0.1% Cu 2 O/TiO 2 A catalyst. 10mg of the above-prepared 0.1% Cu was taken 2 O/TiO 2 The catalyst is added into 1ml of anthranilamide-acetonitrile solution with the mass percent of the anthranilamide being 20 percent, after oxygen in the system is removed, an 18W ultraviolet LED lamp is started, and photocatalysis reaction is carried out for 3 hours under the 365nm condition of an ultraviolet light source. After the reaction solution was filtered, gas chromatography analysis showed that the conversion of anthranilamide was 94%, the selectivity for 3-indazolone was 76%, and the yield of 3-indazolone was 71%.
Example 7
0.1％Cu 2 O/TiO 2 The catalyst is obtained by the following process: adding 1.0g of titanium dioxide nano particles (mass ratio: 20% of rutile phase and 80% of anatase phase) into 30mL of absolute methanol, adding a certain amount of copper chloride, wherein the mass of copper is 0.1% of that of titanium dioxide, stirring uniformly, transferring into a quartz kettle, replacing with CO for 3 times, performing light deposition by irradiating with 40W ultraviolet light at 365nm for 2 hours under the conditions of normal temperature, normal pressure and CO atmosphere, washing with water for 3 times, placing in a vacuum drying oven at 60 ℃ for 12 hours, and collecting 0.1% Cu in an inert (argon) atmosphere 2 O/TiO 2 A catalyst. 10mg of the above-prepared 0.1% Cu was taken 2 O/TiO 2 The catalyst is added into 1ml of anthranilamide-acetonitrile solution with the mass percent of the anthranilamide being 20 percent, and after oxygen in the system is removed, the photocatalysis reaction is carried out for 3 hours under the irradiation of sun light. After the reaction solution was filtered, gas chromatography analysis showed that the conversion of anthranilamide was 31%, the selectivity for 3-indazolone was 79%, and the yield of 3-indazolone was 24%.
Example 8
0.1％Cu 2 O/TiO 2 The catalyst is obtained by the following process: adding 1.0g of titanium dioxide nano particles (mass ratio: 20% of rutile phase and 80% of anatase phase) into 30mL of absolute methanol, adding a certain amount of copper chloride, wherein the mass of copper is 0.1% of that of titanium dioxide, stirring uniformly, transferring into a quartz kettle, replacing with CO for 3 times, performing light deposition by irradiating with 40W ultraviolet light at 365nm for 2 hours under the conditions of normal temperature, normal pressure and CO atmosphere, washing with water for 3 times, placing in a vacuum drying oven at 60 ℃ for 12 hours, and collecting 0.1% Cu under an inert atmosphere (argon) 2 O/TiO 2 A catalyst. 10mg of the above-prepared 0.1% Cu was taken 2 O/TiO 2 The catalyst is added into 1ml of o-aminobenzamide-acetonitrile solution with the mass percent of the o-aminobenzamide being 20 percent, after oxygen in the system is removed, an 18W ultraviolet LED lamp is started, and photocatalysis reaction is carried out for 3 hours under the condition of an ultraviolet light source of 290 nm. After the reaction solution is filtered, gas chromatographic analysis shows that the o-aminobenzamide is convertedThe conversion was 80%, the selectivity of 3-indazolone was 80%, and the yield of 3-indazolone was 64%.
Example 9
0.1％Cu 2 O/TiO 2 The catalyst is obtained by the following process: adding 1.0g of titanium dioxide nano particles (mass ratio: 20% of rutile phase and 80% of anatase phase) into 30mL of absolute methanol, adding a certain amount of copper chloride, wherein the mass of copper is 0.1% of that of titanium dioxide, stirring uniformly, transferring into a quartz kettle, replacing with CO for 3 times, performing light deposition by irradiating with 40W ultraviolet light at 365nm for 2 hours under the conditions of normal temperature, normal pressure and CO atmosphere, washing with water for 3 times, placing in a vacuum drying oven at 60 ℃ for 12 hours, and collecting 0.1% Cu in an inert (argon) atmosphere 2 O/TiO 2 A catalyst. 10mg of the above-prepared 0.1% Cu was taken 2 O/TiO 2 The catalyst is added into 1ml of anthranilamide-acetonitrile solution with the mass percent of the anthranilamide being 20 percent, after oxygen in the system is removed, an 18W ultraviolet LED lamp is started, and photocatalysis reaction is carried out for 3 hours under the condition of an ultraviolet light source of 325 nm. After the reaction solution was filtered, gas chromatography analysis showed that the conversion of anthranilamide was 82%, the selectivity for 3-indazolone was 79%, and the yield of 3-indazolone was 65%.
Example 10
0.1％Cu 2 O/TiO 2 The catalyst is obtained by the following process: adding 1.0g of titanium dioxide nano particles (mass ratio: 20% of rutile phase and 80% of anatase phase) into 30mL of absolute methanol, adding a certain amount of copper chloride, wherein the mass of copper is 0.1% of that of titanium dioxide, stirring uniformly, transferring into a quartz kettle, replacing with CO for 3 times, performing light deposition by irradiating with 40W ultraviolet light at 365nm for 2 hours under the conditions of normal temperature, normal pressure and CO atmosphere, washing with water for 3 times, placing in a vacuum drying oven at 60 ℃ for 12 hours, and collecting 0.1% Cu in an inert (argon) atmosphere 2 O/TiO 2 A catalyst. 10mg of the above-prepared 0.1% Cu was taken 2 O/TiO 2 Catalyst, added into 1ml of anthranilamide-acetonitrile solution with the mass percentage of anthranilamide being 20%, after removing oxygen in the systemAnd (3) starting an 18W ultraviolet LED lamp, and carrying out photocatalytic reaction for 3 hours under the condition of 390nm of an ultraviolet light source. After the reaction solution was filtered, gas chromatography analysis showed that the conversion of anthranilamide was 72%, the selectivity of 3-indazolone was 80%, and the yield of 3-indazolone was 58%.
Example 11
0.1％Cu 2 O/TiO 2 The catalyst is obtained by the following process: adding 1.0g of titanium dioxide nano particles (mass ratio: 20% of rutile phase and 80% of anatase phase) into 30mL of absolute methanol, adding a certain amount of copper chloride, wherein the mass of copper is 0.1% of that of titanium dioxide, stirring uniformly, transferring into a quartz kettle, replacing with CO for 3 times, performing light deposition by irradiating with 40W ultraviolet light at 365nm for 2 hours under the conditions of normal temperature, normal pressure and CO atmosphere, washing with water for 3 times, placing in a vacuum drying oven at 60 ℃ for 12 hours, and collecting 0.1% Cu in an inert (argon) atmosphere 2 O/TiO 2 A catalyst. 5mg of the above-prepared 0.1% Cu was taken 2 O/TiO 2 The catalyst is added into 1ml of anthranilamide-acetonitrile solution with the mass percent of the anthranilamide being 20 percent, after oxygen in the system is removed, an 18W ultraviolet LED lamp is started, and photocatalysis reaction is carried out for 3 hours under the 365nm condition of an ultraviolet light source. After the reaction solution was filtered, gas chromatography analysis showed that the conversion of anthranilamide was 58%, the selectivity for 3-indazolone was 79%, and the yield of 3-indazolone was 46%.
Example 12
0.1％Cu 2 O/TiO 2 The catalyst is obtained by the following process: adding 1.0g of titanium dioxide nano particles (mass ratio: 20% of rutile phase and 80% of anatase phase) into 30mL of absolute methanol, adding a certain amount of copper chloride, wherein the mass of copper is 0.1% of that of titanium dioxide, stirring uniformly, transferring into a quartz kettle, replacing with CO for 3 times, performing light deposition by irradiating with 40W ultraviolet light at 365nm for 2 hours under the conditions of normal temperature, normal pressure and CO atmosphere, washing with water for 3 times, placing in a vacuum drying oven at 60 ℃ for 12 hours, and collecting 0.1% Cu in an inert (argon) atmosphere 2 O/TiO 2 A catalyst. 20mg of the above-prepared 0.1% Cu was taken 2 O/TiO 2 The catalyst is added into 1ml of anthranilamide-acetonitrile solution with the mass percent of the anthranilamide being 20 percent, after oxygen in the system is removed, an 18W ultraviolet LED lamp is started, and photocatalysis reaction is carried out for 3 hours under the 365nm condition of an ultraviolet light source. After the reaction solution was filtered, gas chromatography analysis showed that the conversion of anthranilamide was 91%, the selectivity for 3-indazolone was 82%, and the yield of 3-indazolone was 75%.
Example 13
0.1％Cu 2 O/TiO 2 The catalyst is obtained by the following process: adding 1.0g of titanium dioxide nano particles (mass ratio: 20% of rutile phase and 80% of anatase phase) into 30mL of absolute methanol, adding a certain amount of copper chloride, wherein the mass of copper is 0.1% of that of titanium dioxide, stirring uniformly, transferring into a quartz kettle, replacing with CO for 3 times, performing light deposition by irradiating with 40W ultraviolet light at 365nm for 2 hours under the conditions of normal temperature, normal pressure and CO atmosphere, washing with water for 3 times, placing in a vacuum drying oven at 60 ℃ for 12 hours, and collecting 0.1% Cu in an inert (argon) atmosphere 2 O/TiO 2 A catalyst. 50mg of the above-prepared 0.1% Cu was taken 2 O/TiO 2 The catalyst is added into 1ml of anthranilamide-acetonitrile solution with the mass percent of the anthranilamide being 20 percent, after oxygen in the system is removed, an 18W ultraviolet LED lamp is started, and photocatalysis reaction is carried out for 3 hours under the 365nm condition of an ultraviolet light source. After the reaction solution was filtered, gas chromatography analysis showed that the conversion of anthranilamide was 92%, the selectivity of 3-indazolone was 81%, and the yield of 3-indazolone was 75%.
Example 14
0.1％Cu 2 O/TiO 2 The catalyst is obtained by the following process: adding 1.0g of titanium dioxide nano particles (mass ratio: rutile phase 20% and anatase phase 80%) into 30mL of absolute methanol, adding a certain amount of copper chloride, wherein the mass of copper is 0.1% of that of titanium dioxide, stirring uniformly, transferring into a quartz kettle, replacing with CO for 3 times, performing light deposition by irradiation of 40W ultraviolet light at 365nm for 2 hours under the conditions of normal temperature, normal pressure and CO atmosphere, washing for 3 times, and heating at 60 DEG CPlacing in a vacuum drying oven for 12h, and collecting under inert atmosphere (argon) to obtain 0.1% Cu 2 O/TiO 2 A catalyst. 10mg of the above-prepared 0.1% Cu was taken 2 O/TiO 2 The catalyst is added into 1ml of anthranilamide-acetonitrile solution with the mass percent of the anthranilamide being 20 percent, after oxygen in the system is removed, an 18W ultraviolet LED lamp is started, and photocatalysis reaction is carried out for 1h under the 365nm condition of an ultraviolet light source. After the reaction solution was filtered, gas chromatography analysis showed that the conversion of anthranilamide was 62%, the selectivity for 3-indazolone was 80%, and the yield of 3-indazolone was 49%.
Example 15
0.1％Cu 2 O/TiO 2 The catalyst is obtained by the following process: adding 1.0g of titanium dioxide nano particles (mass ratio: 20% of rutile phase and 80% of anatase phase) into 30mL of absolute methanol, adding a certain amount of copper chloride, wherein the mass of copper is 0.1% of that of titanium dioxide, stirring uniformly, transferring into a quartz kettle, replacing with CO for 3 times, performing light deposition by irradiating with 40W ultraviolet light at 365nm for 2 hours under the conditions of normal temperature, normal pressure and CO atmosphere, washing with water for 3 times, placing in a vacuum drying oven at 60 ℃ for 12 hours, and collecting 0.1% Cu in an inert (argon) atmosphere 2 O/TiO 2 A catalyst. 10mg of the above-prepared 0.1% Cu was taken 2 O/TiO 2 The catalyst is added into 1ml of anthranilamide-acetonitrile solution with the mass percent of the anthranilamide being 20 percent, after oxygen in the system is removed, an 18W ultraviolet LED lamp is started, and photocatalysis reaction is carried out for 10 hours under the 365nm condition of an ultraviolet light source. After the reaction solution was filtered, gas chromatography analysis showed that the conversion of anthranilamide was 94%, the selectivity of 3-indazolone was 80%, and the yield of 3-indazolone was 75%.
Example 16
0.1％Cu 2 O/TiO 2 The catalyst is obtained by the following process: 1.0g of titanium dioxide nano particles (mass ratio: rutile phase 20% and anatase phase 80%) are taken, added into 30mL of absolute methanol, a certain amount of copper chloride is added, wherein the mass of copper is 0.1% of the mass of titanium dioxide relative to the mass of titanium dioxide, and stirring is carried out uniformlyUniformly transferring into a quartz kettle, replacing with CO for 3 times, irradiating with 40W ultraviolet light at 365nm for 2h under normal temperature, normal pressure and CO atmosphere for photo-deposition, washing with water for 3 times, placing in a vacuum drying oven at 60deg.C for 12h, and collecting under inert (argon) atmosphere to obtain 0.1% Cu 2 O/TiO 2 A catalyst. 10mg of the above-prepared 0.1% Cu was taken 2 O/TiO 2 The catalyst is added into 1ml of anthranilamide-acetonitrile solution with the mass percent of the anthranilamide being 20 percent, after oxygen in the system is removed, an 18W ultraviolet LED lamp is started, and photocatalysis reaction is carried out for 24 hours under the 365nm condition of an ultraviolet light source. After the reaction solution was filtered, gas chromatography analysis showed that the conversion of anthranilamide was 94%, the selectivity for 3-indazolone was 82%, and the yield of 3-indazolone was 77%.
Example 17
0.1％Cu 2 O/TiO 2 The catalyst is obtained by the following process: adding 1.0g of titanium dioxide nano particles (mass ratio: 20% of rutile phase and 80% of anatase phase) into 30mL of absolute methanol, adding a certain amount of copper chloride, wherein the mass of copper is 0.1% of that of titanium dioxide, stirring uniformly, transferring into a quartz kettle, replacing with CO for 3 times, performing light deposition by irradiating with 40W ultraviolet light at 365nm for 2 hours under the conditions of normal temperature, normal pressure and CO atmosphere, washing with water for 3 times, placing in a vacuum drying oven at 60 ℃ for 12 hours, and collecting 0.1% Cu in an inert (argon) atmosphere 2 O/TiO 2 A catalyst. 10mg of the above-prepared 0.1% Cu was taken 2 O/TiO 2 The catalyst is added into 1ml of anthranilamide-acetonitrile solution with the mass percent of the anthranilamide being 20 percent, after oxygen in the system is removed, an 18W ultraviolet LED lamp is started, and photocatalysis reaction is carried out for 72 hours under the 365nm condition of an ultraviolet light source. After the reaction solution was filtered, gas chromatography analysis showed that the conversion of anthranilamide was 96%, the selectivity for 3-indazolone was 83%, and the yield of 3-indazolone was 80%.
Example 18
0.1％FeO/TiO 2 The catalyst is obtained by the following process: 1.0g of titanium dioxide nano particles (mass ratio: rutile phase 20%, anatase phase 8)0 percent) is added into 30mL of anhydrous methanol, a certain amount of ferric chloride is added, wherein the mass of the ferric chloride is 0.1 percent of the mass of the titanium dioxide relative to the titanium dioxide, the mixture is stirred uniformly and then is transferred into a quartz kettle, after 3 times of replacement by CO, the mixture is subjected to light deposition by irradiation for 2 hours under the conditions of normal temperature, normal pressure and CO atmosphere, 40W ultraviolet light is subjected to 365nm, then the mixture is washed for 3 times, the mixture is placed in a vacuum drying oven at 60 ℃ for 12 hours, and 0.1 percent FeO/TiO is obtained by collection under the inert (argon) atmosphere 2 A catalyst. 10mg of the above-prepared 0.1% FeO/TiO is taken 2 The catalyst is added into 1ml of anthranilamide-acetonitrile solution with the mass percent of the anthranilamide being 20 percent, after oxygen in the system is removed, an 18W ultraviolet LED lamp is started, and photocatalysis reaction is carried out for 3 hours under the 365nm condition of an ultraviolet light source. After the reaction solution was filtered, gas chromatography analysis showed that the conversion of anthranilamide was 88%, the selectivity for 3-indazolone was 78%, and the yield of 3-indazolone was 69%.
Example 19
0.1％NiO/TiO 2 The catalyst is obtained by the following process: adding 1.0g of titanium dioxide nano particles (mass ratio: 20% of rutile phase and 80% of anatase phase) into 30mL of absolute methanol, adding a certain amount of nickel chloride, wherein the mass of nickel is 0.1% of that of titanium dioxide, stirring uniformly, transferring into a quartz kettle, replacing with CO for 3 times, performing light deposition by irradiating with 40W ultraviolet light at 365nm for 2 hours under the conditions of normal temperature, normal pressure and CO atmosphere, washing with water for 3 times, placing in a vacuum drying oven at 60 ℃ for 12 hours, and collecting 0.1% NiO/TiO under inert (argon) atmosphere 2 A catalyst. 10mg of the 0.1% NiO/TiO prepared above was taken 2 The catalyst is added into 1ml of anthranilamide-acetonitrile solution with the mass percent of the anthranilamide being 20 percent, after oxygen in the system is removed, an 18W ultraviolet LED lamp is started, and photocatalysis reaction is carried out for 3 hours under the 365nm condition of an ultraviolet light source. After the reaction solution was filtered, gas chromatography analysis showed that the conversion of anthranilamide was 82%, the selectivity for 3-indazolone was 72%, and the yield of 3-indazolone was 59%.
Example 20
0.1％Cu 2 O/TiO 2 Catalyst passageThe method comprises the following steps of: adding 1.0g of titanium dioxide nano particles (mass ratio: 20% of rutile phase and 80% of anatase phase) into 30mL of absolute methanol, adding a certain amount of copper chloride, wherein the mass of copper is 0.1% of that of titanium dioxide, stirring uniformly, transferring into a quartz kettle, replacing with CO for 3 times, performing light deposition by irradiating with 40W ultraviolet light at 365nm for 2 hours under the conditions of normal temperature, normal pressure and CO atmosphere, washing with water for 3 times, placing in a vacuum drying oven at 60 ℃ for 12 hours, and collecting 0.1% Cu in an inert (argon) atmosphere 2 O/TiO 2 A catalyst. 10mg of the above-prepared 0.1% Cu was taken 2 O/TiO 2 The catalyst is added into 1ml of anthranilamide-acetonitrile solution with the mass percent of the anthranilamide being 20 percent, after oxygen in the system is removed, an ultraviolet LED lamp with the power of 6W is started, and photocatalysis reaction is carried out for 3 hours under the condition of 365nm of an ultraviolet light source. After the reaction solution was filtered, gas chromatography analysis showed that the conversion of anthranilamide was 33%, the selectivity of 3-indazolone was 75%, and the yield of 3-indazolone was 25%.
Example 21
0.1％Cu 2 O/TiO 2 The catalyst is obtained by the following process: adding 1.0g of titanium dioxide nano particles (mass ratio: 20% of rutile phase and 80% of anatase phase) into 30mL of absolute methanol, adding a certain amount of copper chloride, wherein the mass of copper is 0.1% of that of titanium dioxide, stirring uniformly, transferring into a quartz kettle, replacing with CO for 3 times, performing light deposition by irradiating with 40W ultraviolet light at 365nm for 2 hours under the conditions of normal temperature, normal pressure and CO atmosphere, washing with water for 3 times, placing in a vacuum drying oven at 60 ℃ for 12 hours, and collecting 0.1% Cu in an inert (argon) atmosphere 2 O/TiO 2 A catalyst. 10mg of the above-prepared 0.1% Cu was taken 2 O/TiO 2 The catalyst is added into 1ml of 2-amino-3-methylbenzamide-acetonitrile solution with the mass percent of anthranilamide being 20 percent, after oxygen in the system is removed, an 18W ultraviolet LED lamp is started, and photocatalysis reaction is carried out for 3 hours under the 365nm condition of an ultraviolet light source. After the reaction solution is filtered, gas chromatographic analysis shows that the conversion rate of 2-amino-3-methylbenzamide is 88 percent, and the selection of 7-methyl-3-indazoloneThe sex was 80%, and the yield of 7-methyl-3-indazolone was 70%.
Example 22
0.1％Cu 2 O/TiO 2 The catalyst is obtained by the following process: adding 1.0g of titanium dioxide nano particles (mass ratio: 20% of rutile phase and 80% of anatase phase) into 30mL of absolute methanol, adding a certain amount of copper chloride, wherein the mass of copper is 0.1% of that of titanium dioxide, stirring uniformly, transferring into a quartz kettle, replacing with CO for 3 times, performing light deposition by irradiating with 40W ultraviolet light at 365nm for 2 hours under the conditions of normal temperature, normal pressure and CO atmosphere, washing with water for 3 times, placing in a vacuum drying oven at 60 ℃ for 12 hours, and collecting 0.1% Cu in an inert (argon) atmosphere 2 O/TiO 2 A catalyst. 10mg of the above-prepared 0.1% Cu was taken 2 O/TiO 2 The catalyst is added into 1ml of 2-amino-4-nitrobenzamide-acetonitrile solution with the mass percent of anthranilamide of 20 percent, after oxygen in the system is removed, an 18W ultraviolet LED lamp is started, and photocatalysis reaction is carried out for 3 hours under the condition of 365nm ultraviolet light source. After the reaction solution was filtered, gas chromatography analysis showed that the conversion of 2-amino-4-nitrobenzamide was 86%, the selectivity of 6-nitro-3-indazolone was 77%, and the yield of 6-nitro-3-indazolone was 66%.
Example 23
0.1％Cu 2 O/TiO 2 The catalyst is obtained by the following process: adding 1.0g of titanium dioxide nano particles (mass ratio: 20% of rutile phase and 80% of anatase phase) into 30mL of absolute methanol, adding a certain amount of copper chloride, wherein the mass of copper is 0.1% of that of titanium dioxide, stirring uniformly, transferring into a quartz kettle, replacing with CO for 3 times, performing light deposition by irradiating with 40W ultraviolet light at 365nm for 2 hours under the conditions of normal temperature, normal pressure and CO atmosphere, washing with water for 3 times, placing in a vacuum drying oven at 60 ℃ for 12 hours, and collecting 0.1% Cu in an inert (argon) atmosphere 2 O/TiO 2 A catalyst. 10mg of the above-prepared 0.1% Cu was taken 2 O/TiO 2 Catalyst, added into 1ml of 2-amino-4-chloro-3-methylbenzamide-acetonitrile solution with the mass percentage of anthranilamide being 20%, removedAfter oxygen is contained, an 18W ultraviolet LED lamp is started, and photocatalytic reaction is carried out for 3 hours under the 365nm ultraviolet light source condition. After the reaction solution was filtered, gas chromatography analysis showed that the conversion of 2-amino-4-chloro-3-methylbenzamide was 86%, the selectivity of 7-methyl-6-chloro-3-indazolone was 77%, and the yield of 7-methyl-6-chloro-3-indazolone was 66%.
Example 24
0.1％Cu 2 O/TiO 2 The catalyst is obtained by the following process: adding 1.0g of titanium dioxide nano particles (mass ratio: 20% of rutile phase and 80% of anatase phase) into 30mL of absolute methanol, adding a certain amount of copper chloride, wherein the mass of copper is 0.1% of that of titanium dioxide, stirring uniformly, transferring into a quartz kettle, replacing with CO for 3 times, performing light deposition by irradiating with 40W ultraviolet light at 365nm for 2 hours under the conditions of normal temperature, normal pressure and CO atmosphere, washing with water for 3 times, placing in a vacuum drying oven at 60 ℃ for 12 hours, and collecting 0.1% Cu in an inert (argon) atmosphere 2 O/TiO 2 A catalyst. 10mg of the above-prepared 0.1% Cu was taken 2 O/TiO 2 The catalyst is added into 1ml of 2-amino-5-chloromethyl benzamide-acetonitrile solution with the mass percent of anthranilamide being 20 percent, after oxygen in the system is removed, an 18W ultraviolet LED lamp is started, and photocatalysis reaction is carried out for 3 hours under the 365nm condition of an ultraviolet light source. After the reaction solution was filtered, gas chromatography analysis showed that the conversion of 2-amino-5-chloromethylbenzamide was 87%, the selectivity of 5-chloromethyl-3-indazolone was 69%, and the yield of 5-chloromethyl-3-indazolone was 60%.
Example 25
0.1％Cu 2 O/TiO 2 The catalyst is obtained by the following process: adding 1.0g of titanium dioxide nano particles (mass ratio: 20% of rutile phase and 80% of anatase phase) into 30mL of absolute methanol, adding a certain amount of copper chloride, wherein the mass of copper is 0.1% of that of titanium dioxide, stirring uniformly, transferring into a quartz kettle, replacing with CO for 3 times, performing light deposition by irradiating with 40W ultraviolet light at 365nm for 2 hours under the conditions of normal temperature, normal pressure and CO atmosphere, washing with water for 3 times, placing in a vacuum drying oven at 60 ℃ for 12 hours, and performing inert (argon) atmosphereCollecting the mixture under the condition of 0.1% Cu 2 O/TiO 2 A catalyst. 10mg of the above-prepared 0.1% Cu was taken 2 O/TiO 2 The catalyst is added into 1ml of 2-amino-6-propyl benzamide-acetonitrile solution with the mass percent of anthranilamide being 20 percent, after oxygen in the system is removed, an 18W ultraviolet LED lamp is started, and photocatalysis reaction is carried out for 3 hours under the 365nm condition of an ultraviolet light source. After the reaction solution was filtered, gas chromatography analysis showed that the conversion of 2-amino-6-propylbenzamide was 78%, the selectivity of 4-propyl-3-indazolone was 68%, and the yield of 4-propyl-3-indazolone was 53%.
Comparative example 1
1.0g of titanium dioxide nano particles (mass ratio: 20% of rutile phase and 80% of anatase phase) are taken, added into 30mL of absolute methanol, a certain amount of copper chloride is added, wherein the mass of copper is 0.1% of the mass of titanium dioxide relative to the mass of titanium dioxide, stirred for 2 hours until the titanium dioxide nano particles are uniformly stirred, and then placed on a heating stirring disc at 80 ℃ until the titanium dioxide nano particles are completely dried. Fully grinding, then placing into a roasting tube, and collecting under the air condition at 400 ℃ for 2 hours (5 ℃/min) and inert atmosphere (argon) to obtain 0.1 percent of CuO/TiO 2 A catalyst. 10mg of the above-prepared 0.1% CuO/TiO was taken 2 The catalyst is added into 1ml of anthranilamide-acetonitrile solution with the mass percent of the anthranilamide being 20 percent, after oxygen in the system is removed, an 18W ultraviolet LED lamp is started, and photocatalysis reaction is carried out for 3 hours under the 365nm condition of an ultraviolet light source. After the reaction solution was filtered, gas chromatography analysis showed that the conversion of anthranilamide was 4.6%, the selectivity of 3-indazolone was 72%, and the yield of 3-indazolone was 3%.
Comparative example 2
10mg of titanium dioxide nano particles (mass ratio: 20% of rutile phase and 80% of anatase phase) are added into 1ml of anthranilamide-acetonitrile solution with the mass percentage of anthranilamide being 20%, after oxygen in a system is removed, an 18W ultraviolet LED lamp is started, and photocatalytic reaction is carried out for 3 hours under the condition of 365nm of ultraviolet light source. After the reaction solution was filtered, gas chromatography analysis showed that the conversion of anthranilamide was 0.8%, the selectivity of 3-indazolone was 1.2%, and the yield of 3-indazolone was 0%.
By the experimental results of the above example 1 and comparative examples 1 and 2, the conversion of anthranilamide and the selectivity and yield of 3-indazolone were significantly improved by the method of the present invention, while TiO without supporting the variable valence metal oxide 2 There is little effect on the reaction for preparing 3-indazolone compounds under ultraviolet light.
Claims (9)
1. A method for synthesizing 3-indazolone compounds by photocatalysis is characterized in that:
adding a titanium dioxide catalyst modified by a valence-variable metal oxide and an anthranilamide compound into a solvent, and starting a light source to perform a photocatalytic reaction after removing oxygen in a system to obtain a 3-indazolone compound accompanied with hydrogen generation;
the valence-changing metal in the valence-changing metal oxide modified titanium dioxide catalyst is one or more than two of Cu, fe and Ni; the loading capacity of the variable valence metal oxide is 0.1% -10.0% of the carrier mass;
the reaction process is as follows:
wherein X is hydrogen, halogen, nitro, alkyl or substituted alkyl; y is hydrogen, halogen, nitro, alkyl or substituted alkyl; z is hydrogen, halogen, nitro, alkyl or substituted alkyl; w is hydrogen, halogen, nitro, alkyl or substituted alkyl;
the anthranilamide compounds, when one or more of X, Y, Z, W are halogen, are F, cl, br or I, respectively; when one or more of X, Y, Z, W are alkyl groups, the alkyl groups are C respectively n H 2n+1 N=1 to 4; when one or more of X, Y, Z, W are substituted alkyl groups, the substituted alkyl groups are each C n H 2n A, n=1 to 4, A is a substituent, F, cl, br or I, nitro or C 1 -C 4 Alkyl, the substitution position of substituent A is on any carbon of the substituted alkyl.
2. The method of claim 1, wherein: the valence-changing metal in the valence-changing metal oxide modified titanium dioxide catalyst is one or two of Cu and Fe; the loading of the variable valence metal oxide is 0.5-1.0% of the mass of the carrier.
3. The method of claim 1, wherein: the titanium dioxide catalyst modified by the variable valence metal oxide is characterized in that titanium dioxide is in a single phase or a mixed phase of anatase phase and rutile phase.
4. A method as claimed in claim 3, wherein: the titanium dioxide catalyst modified by the variable valence metal oxide is a mixed phase of an anatase phase and a rutile phase; the mass ratio of anatase to rutile in the mixed phase of anatase and rutile is 0.1-10.0.
5. A method according to claim 1 or 2, characterized in that: the light source for the photocatalytic reaction is as follows: ultraviolet light or sunlight; the wavelength of the light source is 220-390 nm; the light intensity of the light source is 6-18W.
6. The method according to claim 1 or 2, wherein the mass ratio of the variable valence metal oxide modified titanium dioxide catalyst to the solvent is 0.001 to 0.1.
7. The method of claim 6, wherein the mass ratio of the variable valence metal oxide modified titanium dioxide catalyst to the solvent is 0.005-0.01.
8. The method according to claim 1 or 2, wherein the photocatalytic reaction takes 1 to 72 hours.
9. The method of claim 8, wherein the photocatalytic reaction is performed for a period of 1h to 3h.
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| CS163533B1 (en) * | 1973-01-12 | 1975-09-15 | ||
| CN102939283A (en) * | 2010-04-22 | 2013-02-20 | 詹森药业有限公司 | Indazole compounds useful as ketohexokinase inhibitors |
| CN109734666A (en) * | 2018-05-03 | 2019-05-10 | 湖南大学 | A kind of carbon dioxide promotes and synthesizes indazole quinoline ketone compounds preparation method without photochemical catalyst photoinduction |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CS163533B1 (en) * | 1973-01-12 | 1975-09-15 | ||
| CN102939283A (en) * | 2010-04-22 | 2013-02-20 | 詹森药业有限公司 | Indazole compounds useful as ketohexokinase inhibitors |
| CN109734666A (en) * | 2018-05-03 | 2019-05-10 | 湖南大学 | A kind of carbon dioxide promotes and synthesizes indazole quinoline ketone compounds preparation method without photochemical catalyst photoinduction |
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