CN115160228B - Method for synthesizing 3-indazolone compound by photocatalysis - Google Patents

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

A method for photocatalytic synthesis of 3-indazolinone compounds

Technical field

The present invention relates to 3-indazolinone compounds, and in particular to a method for preparing 3-indazolinone compounds by photocatalytically converting anthranilamide compounds.

Background technique

3-Indazolinones are important pharmaceutical intermediates. After further derivatization, they are widely used in drug synthesis, disease treatment, biological research, thermal imaging, antioxidants, etc. At present, it is mainly obtained by reductive amination of amine compounds with o-nitrobenzaldehyde or substitution reaction with o-bromomethylnitrobenzene, and then the intermediate is subjected to David-Beruit reaction under base catalysis in alcohol solution. The 2-substituted indazoles are then hydrolyzed in an acid solution to obtain 3-indazolinone compounds (Chinese patent CN110526898A). This process has many steps, harsh reaction conditions, low yield, and high energy consumption, making it difficult to achieve the synthesis goal of a green, efficient, and economical process.

Therefore, it is imperative to develop green and sustainable synthesis methods or processes for 3-indazolinone compounds to avoid the energy consumption and environmental pollution problems of traditional thermocatalytic synthesis strategies.

Contents of the invention

The object of the present invention is to provide a method for photocatalytically converting anthranilamide compounds to prepare 3-indazolinone compounds, which has the characteristics of high product yield, mild reaction conditions, green and efficient process. The reaction process is as follows:

Among them, etc.; W is hydrogen, halogen, nitro, alkyl, substituted alkyl, etc.

Add the variable-price metal oxide-modified titanium dioxide semiconductor catalyst and anthranilamide compounds to the solvent. After removing the oxygen in the system, turn on the light source to perform a photocatalytic reaction to obtain 3-indazolinone compounds accompanied by with the production of hydrogen gas. The anthranilamide compound, when one or more of X, Y, Z, and W is a halogen, can be F, Cl, Br, I, preferably Cl or Br; when X, Y, When one or more of Z and W are alkyl groups, it can be C _n H _2n+1 (n=1~4); when one or more of X, Y, Z, and W are substituted alkyl groups _{When _ _ _} The position can be on any carbon of the substituted alkyl group. The valence metal in the valence metal oxide modified titanium dioxide catalyst can be Cu, Fe, Ni, Co, Pb, etc., preferably Cu, Fe; the loading of the valence metal oxide is 0.1% to 10.0% (based on mass ratio), preferably It is 0.5~1.0% (based on mass ratio). Titanium dioxide can be a single phase or a mixed phase of anatase phase and rutile phase, and is preferably a mixed phase of anatase phase and rutile phase; the mass ratio of anatase to rutile in the mixed phase of anatase and rutile is 0.1. ~10.0, preferably 1.0~4.0. The light source for the photocatalytic reaction is: 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-price metal oxide-modified titanium dioxide semiconductor catalyst to the solvent is 0.001 to 0.1, preferably 0.005 to 0.01. The photocatalytic reaction time is 1 to 72 hours, preferably 1 hour to 3 hours. Oxygen in the system can be removed by pumping or introducing inert gas.

Combining cuprous oxide and titanium dioxide to create oxygen-rich defect sites on the surface, using the characteristics of oxygen defects to activate N-H bonds, thereby promoting the occurrence of dehydrogenation coupling reactions, can achieve a good combination of photocatalysis and organic synthesis, through transformation Anthranilamide compounds generate 3-indazolinone compounds, which have the characteristics of easy separation of the catalyst from the system, high product yield, mild reaction conditions, and green and efficient process.

Compared with the existing technology, the technical solution of the present invention has the following beneficial effects:

(1) The modified titanium dioxide semiconductor photocatalyst of the present invention uses cuprous oxide. Compared with the method of loading precious metals, the raw materials are cheap and environmentally friendly.

(2) The present invention uses a photocatalytic process to replace the traditional thermocatalytic process, avoiding excessive energy consumption and further reducing production costs.

(3) The photocatalytic reaction of the present invention is a heterogeneous catalytic reaction, and the catalyst can be recovered and recycled. At the same time, the present invention has the advantages of simple process and high product yield.

(4) The process of the present invention can obtain an equal amount of gas product hydrogen while obtaining 3-indazolinone compounds, which is easy to separate from the product and can be used as a clean energy source.

The catalyst of this method has high catalytic activity, is easy to prepare, avoids the use of precious metal supports, and the catalyst after the reaction is easy to separate and recover, can significantly reduce production costs, and has potential application prospects.

Detailed ways

In order to make the technical problems, technical solutions and beneficial effects to be solved by the present invention clearer and clearer, the present invention will be further described in detail below with reference to examples. It should be understood that the specific embodiments described here are only used to explain the present invention and do not limit the present invention.

Example 1

0.1% Cu ₂ O/TiO ₂ catalyst is obtained through the following process: take 1.0g titanium dioxide nanoparticles (mass ratio: rutile phase 20%, anatase phase 80%), add it to 30 mL anhydrous methanol, and add a certain amount of chlorine Copper, where the mass of copper relative to titanium dioxide is 0.1% of the mass of titanium dioxide. Stir evenly and transfer to a quartz kettle. After replacing it with CO three times, irradiate 40W ultraviolet light at 365nm for 2 hours under normal temperature, normal pressure, and CO atmosphere conditions. Photodeposition, followed by water washing three times, placed in a vacuum drying oven at 60°C for 12 hours, and collected under an inert atmosphere (argon) to obtain a 0.1% Cu ₂ O/TiO ₂ catalyst. Take 10 mg of the 0.1% Cu ₂ O/TiO ₂ catalyst prepared above and add it to 1 ml of an anthranilic acid-acetonitrile solution with a mass percentage of anthranilic acid of 20%. After removing oxygen from the system, Turn on the 18W UV LED lamp and conduct the photocatalytic reaction under the condition of UV light source 365nm for 3 hours. After the reaction solution was filtered, gas chromatography analysis showed that the conversion rate of anthranilamide was 90%, the selectivity of 3-indazolinone was 76%, and the yield of 3-indazolinone was 68%.

Example 2

1.0% Cu ₂ O/TiO ₂ catalyst is obtained through the following process: take 1.0g titanium dioxide nanoparticles (mass ratio: rutile phase 20%, anatase phase 80%), add it to 30 mL anhydrous methanol, and add a certain amount of chlorine Copper, where the mass of copper relative to titanium dioxide is 1.0% of the mass of titanium dioxide. Stir evenly and transfer to a quartz kettle. After replacing it with CO three times, irradiate 40W ultraviolet light at 365nm for 2 hours under normal temperature, normal pressure, and CO atmosphere conditions. Photodeposition, followed by water washing three times, placed in a vacuum drying oven at 60°C for 12 hours, and collected under an inert atmosphere (argon) to obtain a 1.0% Cu ₂ O/TiO ₂ catalyst. Take 10 mg of the 1.0% Cu ₂ O/TiO ₂ catalyst prepared above and add it to 1 ml of an anthranilic acid-acetonitrile solution with a mass percentage of anthranilic acid of 20%. After removing oxygen from the system, Turn on the 18W UV LED lamp and conduct the photocatalytic reaction under the condition of UV light source 365nm for 3 hours. After the reaction solution was filtered, gas chromatography analysis showed that the conversion rate of anthranilamide was 94%, the selectivity of 3-indazolinone was 81%, and the yield of 3-indazolinone was 76%.

Example 3

5.0% Cu ₂ O/TiO ₂ catalyst is obtained through the following process: take 1.0g titanium dioxide nanoparticles (mass ratio: rutile phase 20%, anatase phase 80%), add it to 30 mL anhydrous methanol, and add a certain amount of chlorine Copper, where the mass of copper relative to titanium dioxide is 5.0% of the mass of titanium dioxide. Stir evenly and transfer to a quartz kettle. After replacing it with CO three times, irradiate 40W ultraviolet light at 365nm for 2 hours under normal temperature, normal pressure, and CO atmosphere conditions. Photodeposition, followed by water washing three times, placed in a vacuum drying oven at 60°C for 12 hours, and collected under an inert atmosphere (argon) to obtain a 5.0% Cu ₂ O/TiO ₂ catalyst. Take 10 mg of the 1.0% Cu ₂ O/TiO ₂ catalyst prepared above and add it to 1 ml of an anthranilic acid-acetonitrile solution with a mass percentage of anthranilic acid of 20%. After removing oxygen from the system, Turn on the 18W UV LED lamp and conduct the photocatalytic reaction under the condition of UV light source 365nm for 3 hours. After the reaction solution was filtered, gas chromatography analysis showed that the conversion rate of anthranilamide was 92%, the selectivity of 3-indazolinone was 80%, and the yield of 3-indazolinone was 74%.

Example 4

10.0% Cu ₂ O/TiO ₂ catalyst is obtained through the following process: take 10.0g titanium dioxide nanoparticles (mass ratio: rutile phase 20%, anatase phase 80%), add it to 30 mL anhydrous methanol, and add a certain amount of chlorine Copper, where the mass of copper relative to titanium dioxide is 10.0% of the mass of titanium dioxide. Stir evenly and transfer to a quartz kettle. After replacing it with CO three times, irradiate 40W ultraviolet light at 365nm for 2 hours under normal temperature, normal pressure, and CO atmosphere conditions. Photodeposition, followed by water washing three times, placed in a vacuum drying oven at 60°C for 12 hours, and collected under an inert atmosphere (argon) to obtain a 10.0% Cu ₂ O/TiO ₂ catalyst. Take 10 mg of the 10.0% Cu ₂ O/TiO ₂ catalyst prepared above and add it to 1 ml of an anthranilic acid-acetonitrile solution with a mass percentage of anthranilic acid of 20%. After removing oxygen from the system, Turn on the 18W UV LED lamp and conduct the photocatalytic reaction under the condition of UV light source 365nm for 3 hours. After the reaction solution was filtered, gas chromatography analysis showed that the conversion rate of anthranilamide was 87%, the selectivity of 3-indazolinone was 80%, and the yield of 3-indazolinone was 70%.

Example 5

The 0.1% Cu ₂ O/TiO ₂ catalyst is obtained through the following process: take 1.0g titanium dioxide nanoparticles (anatase phase 100%), add it to 30 mL anhydrous methanol, and add a certain amount of copper chloride, in which the mass of copper is relatively When titanium dioxide is 0.1% of the mass of titanium dioxide, stir evenly and transfer to a quartz kettle. After replacing it with CO three times, under normal temperature, normal pressure, and CO atmosphere conditions, irradiate 40W ultraviolet light 365nm for 2 hours for photodeposition, and then wash with water three times. Place it in a vacuum drying oven at 60°C for 12 hours, and collect it under an inert atmosphere (argon) to obtain a 0.1% Cu ₂ O/TiO ₂ catalyst. Take 10 mg of the 0.1% Cu ₂ O/TiO ₂ catalyst prepared above and add it to 1 ml of an anthranilic acid-acetonitrile solution with a mass percentage of anthranilic acid of 20%. After removing oxygen from the system, Turn on the 18W UV LED lamp and conduct the photocatalytic reaction under the condition of UV light source 365nm for 3 hours. After the reaction solution was filtered, gas chromatography analysis showed that the conversion rate of anthranilamide was 94%, the selectivity of 3-indazolinone was 91%, and the yield of 3-indazolinone was 73%.

Example 6

0.1% Cu ₂ O/TiO ₂ catalyst is obtained through the following process: take 1.0g titanium dioxide nanoparticles (100% rutile phase), add it to 30 mL anhydrous methanol, and add a certain amount of copper chloride, where the mass of copper is relative to the mass of titanium dioxide It is 0.1% of the mass of titanium dioxide. After stirring evenly, transfer it to a quartz kettle. After replacing it with CO three times, under normal temperature, normal pressure and CO atmosphere conditions, 40W ultraviolet light 365nm is irradiated for 2 hours for photodeposition, and then washed three times with water, at 60 ℃ vacuum drying oven for 12 hours, collected under an inert atmosphere (argon) to obtain 0.1% Cu ₂ O/TiO ₂ catalyst. Take 10 mg of the 0.1% Cu ₂ O/TiO ₂ catalyst prepared above and add it to 1 ml of an anthranilic acid-acetonitrile solution with a mass percentage of anthranilic acid of 20%. After removing oxygen from the system, Turn on the 18W UV LED lamp and conduct the photocatalytic reaction under the condition of UV light source 365nm for 3 hours. After the reaction solution was filtered, gas chromatography analysis showed that the conversion rate of anthranilamide was 94%, the selectivity of 3-indazolinone was 76%, and the yield of 3-indazolinone was 71%.

Example 7

0.1% Cu ₂ O/TiO ₂ catalyst is obtained through the following process: take 1.0g titanium dioxide nanoparticles (mass ratio: rutile phase 20%, anatase phase 80%), add it to 30 mL anhydrous methanol, and add a certain amount of chlorine Copper, where the mass of copper relative to titanium dioxide is 0.1% of the mass of titanium dioxide. Stir evenly and transfer to a quartz kettle. After replacing it with CO three times, irradiate 40W ultraviolet light at 365nm for 2 hours under normal temperature, normal pressure, and CO atmosphere conditions. Photodeposition, followed by water washing three times, placed in a vacuum drying oven at 60°C for 12 hours, and collected under an inert (argon) atmosphere to obtain a 0.1% Cu ₂ O/TiO ₂ catalyst. Take 10 mg of the 0.1% Cu ₂ O/TiO ₂ catalyst prepared above and add it to 1 ml of an anthranilic acid-acetonitrile solution with a mass percentage of anthranilic acid of 20%. After removing oxygen from the system, The photocatalytic reaction was carried out under sunlight for 3 hours. After the reaction solution was filtered, gas chromatography analysis showed that the conversion rate of anthranilamide was 31%, the selectivity of 3-indazolinone was 79%, and the yield of 3-indazolinone was 24%.

Example 8

0.1% Cu ₂ O/TiO ₂ catalyst is obtained through the following process: take 1.0g titanium dioxide nanoparticles (mass ratio: rutile phase 20%, anatase phase 80%), add it to 30 mL anhydrous methanol, and add a certain amount of chlorine Copper, where the mass of copper relative to titanium dioxide is 0.1% of the mass of titanium dioxide. Stir evenly and transfer to a quartz kettle. After replacing it with CO three times, irradiate 40W ultraviolet light at 365nm for 2 hours under normal temperature, normal pressure, and CO atmosphere conditions. Photodeposition, followed by water washing three times, placed in a vacuum drying oven at 60°C for 12 hours, and collected under an inert atmosphere (argon) to obtain a 0.1% Cu ₂ O/TiO ₂ catalyst. Take 10 mg of the 0.1% Cu ₂ O/TiO ₂ catalyst prepared above and add it to 1 ml of an anthranilic acid-acetonitrile solution with a mass percentage of anthranilic acid of 20%. After removing oxygen from the system, Turn on the 18W UV LED lamp and conduct the photocatalytic reaction under the condition of UV light source 290nm for 3 hours. After the reaction solution was filtered, gas chromatography analysis showed that the conversion rate of anthranilamide was 80%, the selectivity of 3-indazolinone was 80%, and the yield of 3-indazolinone was 64%.

Example 9

0.1% Cu ₂ O/TiO ₂ catalyst is obtained through the following process: take 1.0g titanium dioxide nanoparticles (mass ratio: rutile phase 20%, anatase phase 80%), add it to 30 mL anhydrous methanol, and add a certain amount of chlorine Copper, where the mass of copper relative to titanium dioxide is 0.1% of the mass of titanium dioxide. Stir evenly and transfer to a quartz kettle. After replacing it with CO three times, irradiate 40W ultraviolet light at 365nm for 2 hours under normal temperature, normal pressure, and CO atmosphere conditions. Photodeposition, followed by water washing three times, placed in a vacuum drying oven at 60°C for 12 hours, and collected under an inert (argon) atmosphere to obtain a 0.1% Cu ₂ O/TiO ₂ catalyst. Take 10 mg of the 0.1% Cu ₂ O/TiO ₂ catalyst prepared above and add it to 1 ml of an anthranilic acid-acetonitrile solution with a mass percentage of anthranilic acid of 20%. After removing oxygen from the system, Turn on the 18W UV LED lamp and conduct the photocatalytic reaction under the condition of UV light source 325nm for 3 hours. After the reaction solution was filtered, gas chromatography analysis showed that the conversion rate of anthranilamide was 82%, the selectivity of 3-indazolinone was 79%, and the yield of 3-indazolinone was 65%.

Example 10

0.1% Cu ₂ O/TiO ₂ catalyst is obtained through the following process: take 1.0g titanium dioxide nanoparticles (mass ratio: rutile phase 20%, anatase phase 80%), add it to 30 mL anhydrous methanol, and add a certain amount of chlorine Copper, where the mass of copper relative to titanium dioxide is 0.1% of the mass of titanium dioxide. Stir evenly and transfer to a quartz kettle. After replacing it with CO three times, irradiate 40W ultraviolet light at 365nm for 2 hours under normal temperature, normal pressure, and CO atmosphere conditions. Photodeposition, followed by water washing three times, placed in a vacuum drying oven at 60°C for 12 hours, and collected under an inert (argon) atmosphere to obtain a 0.1% Cu ₂ O/TiO ₂ catalyst. Take 10 mg of the 0.1% Cu ₂ O/TiO ₂ catalyst prepared above and add it to 1 ml of an anthranilic acid-acetonitrile solution with a mass percentage of anthranilic acid of 20%. After removing oxygen from the system, Turn on the 18W UV LED lamp and conduct the photocatalytic reaction under the condition of UV light source 390nm for 3 hours. After the reaction solution was filtered, gas chromatography analysis showed that the conversion rate of anthranilamide was 72%, the selectivity of 3-indazolinone was 80%, and the yield of 3-indazolinone was 58%.

Example 11

0.1% Cu ₂ O/TiO ₂ catalyst is obtained through the following process: take 1.0g titanium dioxide nanoparticles (mass ratio: rutile phase 20%, anatase phase 80%), add it to 30 mL anhydrous methanol, and add a certain amount of chlorine Copper, where the mass of copper relative to titanium dioxide is 0.1% of the mass of titanium dioxide. Stir evenly and transfer to a quartz kettle. After replacing it with CO three times, irradiate 40W ultraviolet light at 365nm for 2 hours under normal temperature, normal pressure, and CO atmosphere conditions. Photodeposition, followed by water washing three times, placed in a vacuum drying oven at 60°C for 12 hours, and collected under an inert (argon) atmosphere to obtain a 0.1% Cu ₂ O/TiO ₂ catalyst. Take 5 mg of the 0.1% Cu ₂ O/TiO ₂ catalyst prepared above and add it to 1 ml of an anthranilic acid-acetonitrile solution with a mass percentage of anthranilic acid of 20%. After removing oxygen from the system, Turn on the 18W UV LED lamp and conduct the photocatalytic reaction under the condition of UV light source 365nm for 3 hours. After the reaction solution was filtered, gas chromatography analysis showed that the conversion rate of anthranilamide was 58%, the selectivity of 3-indazolinone was 79%, and the yield of 3-indazolinone was 46%.

Example 12

0.1% Cu ₂ O/TiO ₂ catalyst is obtained through the following process: take 1.0g titanium dioxide nanoparticles (mass ratio: rutile phase 20%, anatase phase 80%), add it to 30 mL anhydrous methanol, and add a certain amount of chlorine Copper, where the mass of copper relative to titanium dioxide is 0.1% of the mass of titanium dioxide. Stir evenly and transfer to a quartz kettle. After replacing it with CO three times, irradiate 40W ultraviolet light at 365nm for 2 hours under normal temperature, normal pressure, and CO atmosphere conditions. Photodeposition, followed by water washing three times, placed in a vacuum drying oven at 60°C for 12 hours, and collected under an inert (argon) atmosphere to obtain a 0.1% Cu ₂ O/TiO ₂ catalyst. Take 20 mg of the 0.1% Cu ₂ O/TiO ₂ catalyst prepared above and add it to 1 ml of an anthranilic acid-acetonitrile solution with a mass percentage of anthranilic acid of 20%. After removing oxygen from the system, Turn on the 18W UV LED lamp and conduct the photocatalytic reaction under the condition of UV light source 365nm for 3 hours. After the reaction solution was filtered, gas chromatography analysis showed that the conversion rate of anthranilamide was 91%, the selectivity of 3-indazolinone was 82%, and the yield of 3-indazolinone was 75%.

Example 13

0.1% Cu ₂ O/TiO ₂ catalyst is obtained through the following process: take 1.0g titanium dioxide nanoparticles (mass ratio: rutile phase 20%, anatase phase 80%), add it to 30 mL anhydrous methanol, and add a certain amount of chlorine Copper, where the mass of copper relative to titanium dioxide is 0.1% of the mass of titanium dioxide. Stir evenly and transfer to a quartz kettle. After replacing it with CO three times, irradiate 40W ultraviolet light at 365nm for 2 hours under normal temperature, normal pressure, and CO atmosphere conditions. Photodeposition, followed by water washing three times, placed in a vacuum drying oven at 60°C for 12 hours, and collected under an inert (argon) atmosphere to obtain a 0.1% Cu ₂ O/TiO ₂ catalyst. Take 50 mg of the 0.1% Cu ₂ O/TiO ₂ catalyst prepared above and add it to 1 ml of an anthranilic acid-acetonitrile solution with a mass percentage of anthranilic acid of 20%. After removing oxygen from the system, Turn on the 18W UV LED lamp and conduct the photocatalytic reaction under the condition of UV light source 365nm for 3 hours. After the reaction solution was filtered, gas chromatography analysis showed that the conversion rate of anthranilamide was 92%, the selectivity of 3-indazolinone was 81%, and the yield of 3-indazolinone was 75%.

Example 14

0.1% Cu ₂ O/TiO ₂ catalyst is obtained through the following process: take 1.0g titanium dioxide nanoparticles (mass ratio: rutile phase 20%, anatase phase 80%), add it to 30 mL anhydrous methanol, and add a certain amount of chlorine Copper, where the mass of copper relative to titanium dioxide is 0.1% of the mass of titanium dioxide. Stir evenly and transfer to a quartz kettle. After replacing it with CO three times, irradiate 40W ultraviolet light at 365nm for 2 hours under normal temperature, normal pressure, and CO atmosphere conditions. Photodeposition, followed by water washing three times, placed in a vacuum drying oven at 60°C for 12 hours, and collected under an inert atmosphere (argon) to obtain a 0.1% Cu ₂ O/TiO ₂ catalyst. Take 10 mg of the 0.1% Cu ₂ O/TiO ₂ catalyst prepared above and add it to 1 ml of an anthranilic acid-acetonitrile solution with a mass percentage of anthranilic acid of 20%. After removing oxygen from the system, Turn on the 18W UV LED lamp and conduct the photocatalytic reaction under the condition of UV light source 365nm for 1 hour. After the reaction solution was filtered, gas chromatography analysis showed that the conversion rate of anthranilamide was 62%, the selectivity of 3-indazolinone was 80%, and the yield of 3-indazolinone was 49%.

Example 15

0.1% Cu ₂ O/TiO ₂ catalyst is obtained through the following process: take 1.0g titanium dioxide nanoparticles (mass ratio: rutile phase 20%, anatase phase 80%), add it to 30 mL anhydrous methanol, and add a certain amount of chlorine Copper, where the mass of copper relative to titanium dioxide is 0.1% of the mass of titanium dioxide. Stir evenly and transfer to a quartz kettle. After replacing it with CO three times, irradiate 40W ultraviolet light at 365nm for 2 hours under normal temperature, normal pressure, and CO atmosphere conditions. Photodeposition, followed by water washing three times, placed in a vacuum drying oven at 60°C for 12 hours, and collected under an inert (argon) atmosphere to obtain a 0.1% Cu ₂ O/TiO ₂ catalyst. Take 10 mg of the 0.1% Cu ₂ O/TiO ₂ catalyst prepared above and add it to 1 ml of an anthranilic acid-acetonitrile solution with a mass percentage of anthranilic acid of 20%. After removing oxygen from the system, Turn on the 18W UV LED lamp and conduct the photocatalytic reaction under the condition of UV light source 365nm for 10 hours. After the reaction solution was filtered, gas chromatography analysis showed that the conversion rate of anthranilamide was 94%, the selectivity of 3-indazolinone was 80%, and the yield of 3-indazolinone was 75%.

Example 16

0.1% Cu ₂ O/TiO ₂ catalyst is obtained through the following process: take 1.0g titanium dioxide nanoparticles (mass ratio: rutile phase 20%, anatase phase 80%), add it to 30 mL anhydrous methanol, and add a certain amount of chlorine Copper, where the mass of copper relative to titanium dioxide is 0.1% of the mass of titanium dioxide. Stir evenly and transfer to a quartz kettle. After replacing it with CO three times, irradiate 40W ultraviolet light at 365nm for 2 hours under normal temperature, normal pressure, and CO atmosphere conditions. Photodeposition, followed by water washing three times, placed in a vacuum drying oven at 60°C for 12 hours, and collected under an inert (argon) atmosphere to obtain a 0.1% Cu ₂ O/TiO ₂ catalyst. Take 10 mg of the 0.1% Cu ₂ O/TiO ₂ catalyst prepared above and add it to 1 ml of an anthranilic acid-acetonitrile solution with a mass percentage of anthranilic acid of 20%. After removing oxygen from the system, Turn on the 18W UV LED lamp and conduct the photocatalytic reaction under the condition of UV light source 365nm for 24 hours. After the reaction solution was filtered, gas chromatography analysis showed that the conversion rate of anthranilamide was 94%, the selectivity of 3-indazolinone was 82%, and the yield of 3-indazolinone was 77%.

Example 17

0.1% Cu ₂ O/TiO ₂ catalyst is obtained through the following process: take 1.0g titanium dioxide nanoparticles (mass ratio: rutile phase 20%, anatase phase 80%), add it to 30 mL anhydrous methanol, and add a certain amount of chlorine Copper, where the mass of copper relative to titanium dioxide is 0.1% of the mass of titanium dioxide. Stir evenly and transfer to a quartz kettle. After replacing it with CO three times, irradiate 40W ultraviolet light at 365nm for 2 hours under normal temperature, normal pressure, and CO atmosphere conditions. Photodeposition, followed by water washing three times, placed in a vacuum drying oven at 60°C for 12 hours, and collected under an inert (argon) atmosphere to obtain a 0.1% Cu ₂ O/TiO ₂ catalyst. Take 10 mg of the 0.1% Cu ₂ O/TiO ₂ catalyst prepared above and add it to 1 ml of an anthranilic acid-acetonitrile solution with a mass percentage of anthranilic acid of 20%. After removing oxygen from the system, Turn on the 18W UV LED lamp and conduct the photocatalytic reaction under the condition of UV light source 365nm for 72 hours. After the reaction solution was filtered, gas chromatography analysis showed that the conversion rate of anthranilamide was 96%, the selectivity of 3-indazolinone was 83%, and the yield of 3-indazolinone was 80%.

Example 18

The 0.1% FeO/TiO ₂ catalyst is obtained through the following process: take 1.0g titanium dioxide nanoparticles (mass ratio: rutile phase 20%, anatase phase 80%), add it to 30mL anhydrous methanol, and add a certain amount of ferric chloride , the mass of iron is 0.1% of the mass of titanium dioxide relative to titanium dioxide. After stirring evenly, transfer to a quartz kettle. After replacing it with CO three times, under normal temperature, normal pressure, and CO atmosphere, 40W ultraviolet light 365nm is irradiated for 2 hours for photodeposition. , then washed with water three times, placed in a vacuum drying oven at 60°C for 12 hours, and collected under an inert (argon) atmosphere to obtain a 0.1% FeO/TiO ₂ catalyst. Take 10 mg of the 0.1% FeO/TiO ₂ catalyst prepared above and add it to 1 ml of anthranilic acid-acetonitrile solution with a mass percentage of anthranilic acid of 20%. After removing oxygen from the system, turn on 18W UV LED lamp, conduct photocatalytic reaction under the condition of UV light source 365nm for 3 hours. After the reaction solution was filtered, gas chromatography analysis showed that the conversion rate of anthranilamide was 88%, the selectivity of 3-indazolinone was 78%, and the yield of 3-indazolinone was 69%.

Example 19

The 0.1% NiO/TiO ₂ catalyst is obtained through the following process: take 1.0g titanium dioxide nanoparticles (mass ratio: rutile phase 20%, anatase phase 80%), add it to 30mL anhydrous methanol, and add a certain amount of nickel chloride , the mass of nickel relative to titanium dioxide is 0.1% of the mass of titanium dioxide. After stirring evenly, transfer to a quartz kettle. After replacing it with CO three times, under normal temperature, normal pressure, and CO atmosphere, 40W ultraviolet light 365nm is irradiated for 2 hours for photodeposition. , then washed with water three times, placed in a vacuum drying oven at 60°C for 12 hours, and collected under an inert (argon) atmosphere to obtain a 0.1% NiO/TiO ₂ catalyst. Take 10 mg of the 0.1% NiO/TiO ₂ catalyst prepared above and add it to 1 ml of anthranilic acid-acetonitrile solution with a mass percentage of anthranilic acid of 20%. After removing oxygen from the system, turn on 18W UV LED lamp, conduct photocatalytic reaction under the condition of UV light source 365nm for 3 hours. After the reaction solution was filtered, gas chromatography analysis showed that the conversion rate of anthranilamide was 82%, the selectivity of 3-indazolinone was 72%, and the yield of 3-indazolinone was 59%.

Example 20

0.1% Cu ₂ O/TiO ₂ catalyst is obtained through the following process: take 1.0g titanium dioxide nanoparticles (mass ratio: rutile phase 20%, anatase phase 80%), add it to 30 mL anhydrous methanol, and add a certain amount of chlorine Copper, where the mass of copper relative to titanium dioxide is 0.1% of the mass of titanium dioxide. Stir evenly and transfer to a quartz kettle. After replacing it with CO three times, irradiate 40W ultraviolet light at 365nm for 2 hours under normal temperature, normal pressure, and CO atmosphere conditions. Photodeposition, followed by water washing three times, placed in a vacuum drying oven at 60°C for 12 hours, and collected under an inert (argon) atmosphere to obtain a 0.1% Cu ₂ O/TiO ₂ catalyst. Take 10 mg of the 0.1% Cu ₂ O/TiO ₂ catalyst prepared above and add it to 1 ml of an anthranilic acid-acetonitrile solution with a mass percentage of anthranilic acid of 20%. After removing oxygen from the system, Turn on the 6W UV LED lamp and conduct the photocatalytic reaction under the condition of UV light source 365nm for 3 hours. After the reaction solution was filtered, gas chromatography analysis showed that the conversion rate of anthranilamide was 33%, the selectivity of 3-indazolinone was 75%, and the yield of 3-indazolinone was 25%.

Example 21

0.1% Cu ₂ O/TiO ₂ catalyst is obtained through the following process: take 1.0g titanium dioxide nanoparticles (mass ratio: rutile phase 20%, anatase phase 80%), add it to 30 mL anhydrous methanol, and add a certain amount of chlorine Copper, where the mass of copper relative to titanium dioxide is 0.1% of the mass of titanium dioxide. Stir evenly and transfer to a quartz kettle. After replacing it with CO three times, irradiate 40W ultraviolet light at 365nm for 2 hours under normal temperature, normal pressure, and CO atmosphere conditions. Photodeposition, followed by water washing three times, placed in a vacuum drying oven at 60°C for 12 hours, and collected under an inert (argon) atmosphere to obtain a 0.1% Cu ₂ O/TiO ₂ catalyst. Take 10 mg of the 0.1% Cu ₂ O/TiO ₂ catalyst prepared above and add it to 1 ml of a 2-amino-3-methylbenzamide-acetonitrile solution with an anthranilic mass percentage content of 20%. After removing oxygen from the system, turn on the 18W UV LED lamp and conduct the photocatalytic reaction under the condition of UV light source 365nm for 3 hours. After the reaction solution was filtered, gas chromatography analysis showed that the conversion rate of 2-amino-3-methylbenzamide was 88%, the selectivity of 7-methyl-3-indazolinone was 80%, and the selectivity of 7-methyl-3-indazolinone was 80%. The yield of 3-indazolinone was 70%.

Example 22

0.1% Cu ₂ O/TiO ₂ catalyst is obtained through the following process: take 1.0g titanium dioxide nanoparticles (mass ratio: rutile phase 20%, anatase phase 80%), add it to 30 mL anhydrous methanol, and add a certain amount of chlorine Copper, where the mass of copper relative to titanium dioxide is 0.1% of the mass of titanium dioxide. Stir evenly and transfer to a quartz kettle. After replacing it with CO three times, irradiate 40W ultraviolet light at 365nm for 2 hours under normal temperature, normal pressure, and CO atmosphere conditions. Photodeposition, followed by water washing three times, placed in a vacuum drying oven at 60°C for 12 hours, and collected under an inert (argon) atmosphere to obtain a 0.1% Cu ₂ O/TiO ₂ catalyst. Take 10 mg of the 0.1% Cu ₂ O/TiO ₂ catalyst prepared above and add it to 1 ml of 2-amino-4-nitrobenzamide-acetonitrile solution with an anthranilic mass percentage content of 20%. After removing oxygen from the system, turn on the 18W UV LED lamp and conduct the photocatalytic reaction under the condition of UV light source 365nm for 3 hours. After the reaction solution was filtered, gas chromatography analysis showed that the conversion rate of 2-amino-4-nitrobenzamide was 86%, the selectivity of 6-nitro-3-indazolinone was 77%, and the selectivity of 6-nitro- The yield of 3-indazolinone was 66%.

Example 23

0.1% Cu ₂ O/TiO ₂ catalyst is obtained through the following process: take 1.0g titanium dioxide nanoparticles (mass ratio: rutile phase 20%, anatase phase 80%), add it to 30 mL anhydrous methanol, and add a certain amount of chlorine Copper, where the mass of copper relative to titanium dioxide is 0.1% of the mass of titanium dioxide. Stir evenly and transfer to a quartz kettle. After replacing it with CO three times, irradiate 40W ultraviolet light at 365nm for 2 hours under normal temperature, normal pressure, and CO atmosphere conditions. Photodeposition, followed by water washing three times, placed in a vacuum drying oven at 60°C for 12 hours, and collected under an inert (argon) atmosphere to obtain a 0.1% Cu ₂ O/TiO ₂ catalyst. Take 10 mg of the 0.1% Cu ₂ O/TiO ₂ catalyst prepared above and add it to 1 ml of a 2-amino-4-chloro-3-methylbenzamide-acetonitrile solution with an anthranilic mass percentage of 20%. , after removing the oxygen in the system, turn on the 18W UV LED lamp, and conduct the photocatalytic reaction under the condition of UV light source 365nm for 3 hours. After the reaction solution was filtered, gas chromatography analysis showed that the conversion rate of 2-amino-4-chloro-3-methylbenzamide was 86%, and the selectivity of 7-methyl-6-chloro-3-indazolinone was 77%, yield of 7-methyl-6-chloro-3-indazolinone was 66%.

Example 24

0.1% Cu ₂ O/TiO ₂ catalyst is obtained through the following process: take 1.0g titanium dioxide nanoparticles (mass ratio: rutile phase 20%, anatase phase 80%), add it to 30 mL anhydrous methanol, and add a certain amount of chlorine Copper, where the mass of copper relative to titanium dioxide is 0.1% of the mass of titanium dioxide. Stir evenly and transfer to a quartz kettle. After replacing it with CO three times, irradiate 40W ultraviolet light at 365nm for 2 hours under normal temperature, normal pressure, and CO atmosphere conditions. Photodeposition, followed by water washing three times, placed in a vacuum drying oven at 60°C for 12 hours, and collected under an inert (argon) atmosphere to obtain a 0.1% Cu ₂ O/TiO ₂ catalyst. Take 10 mg of the 0.1% Cu ₂ O/TiO ₂ catalyst prepared above and add it to 1 ml of a 2-amino-5-chloromethylbenzamide-acetonitrile solution with an anthranilic mass percentage content of 20%. After removing the oxygen in the system, turn on the 18W UV LED lamp and conduct the photocatalytic reaction under the condition of UV light source 365nm for 3 hours. After the reaction solution was filtered, gas chromatography analysis showed that the conversion rate of 2-amino-5-chloromethylbenzamide was 87%, the selectivity of 5-chloromethyl-3-indazolinone was 69%, and the selectivity of 5-chloromethylbenzamide was 69%. The yield of methyl-3-indazolinone was 60%.

Example 25

0.1% Cu ₂ O/TiO ₂ catalyst is obtained through the following process: take 1.0g titanium dioxide nanoparticles (mass ratio: rutile phase 20%, anatase phase 80%), add it to 30 mL anhydrous methanol, and add a certain amount of chlorine Copper, where the mass of copper relative to titanium dioxide is 0.1% of the mass of titanium dioxide. Stir evenly and transfer to a quartz kettle. After replacing it with CO three times, irradiate 40W ultraviolet light at 365nm for 2 hours under normal temperature, normal pressure, and CO atmosphere conditions. Photodeposition, followed by water washing three times, placed in a vacuum drying oven at 60°C for 12 hours, and collected under an inert (argon) atmosphere to obtain a 0.1% Cu ₂ O/TiO ₂ catalyst. Take 10 mg of the 0.1% Cu ₂ O/TiO ₂ catalyst prepared above and add it to 1 ml of 2-amino-6-propylbenzamide-acetonitrile solution with an anthranilic mass percentage content of 20%. After removing oxygen from the system, turn on the 18W UV LED lamp and conduct the photocatalytic reaction under the condition of UV light source 365nm for 3 hours. After the reaction solution was filtered, gas chromatography analysis showed that the conversion rate of 2-amino-6-propylbenzamide was 78%, the selectivity of 4-propyl-3-indazolinone was 68%, and the selectivity of 4-propyl 3 -The yield of indazolinone is 53%.

Comparative example 1

Take 1.0g of titanium dioxide nanoparticles (mass ratio: rutile phase 20%, anatase phase 80%), add it to 30 mL anhydrous methanol, and add a certain amount of copper chloride, where the mass of copper relative to titanium dioxide is the mass of titanium dioxide. 0.1%, stir for 2 hours until evenly mixed, then place on a heated stirring plate at 80°C until completely dry. After sufficient grinding, place it in a calcining tube and collect it under air conditions at 400°C for 2h (5°C/min) and an inert atmosphere (argon) to obtain a 0.1% CuO/TiO ₂ catalyst. Take 10 mg of the 0.1% CuO/TiO ₂ catalyst prepared above and add it to 1 ml of anthranilic acid-acetonitrile solution with a mass percentage of 20% anthranilic acid. After removing oxygen from the system, turn on 18W UV LED lamp, conduct photocatalytic reaction under the condition of UV light source 365nm for 3 hours. After the reaction solution was filtered, gas chromatography analysis showed that the conversion rate of anthranilamide was 4.6%, the selectivity of 3-indazolinone was 72%, and the yield of 3-indazolinone was 3%.

Comparative example 2

Take 10 mg of titanium dioxide nanoparticles (mass ratio: rutile phase 20%, anatase phase 80%), add it to 1 ml of anthranilic acid-acetonitrile solution with a mass percentage of anthranilic acid of 20%, and remove the After removing oxygen from the system, turn on the 18W UV LED lamp and conduct the photocatalytic reaction under the condition of UV light source 365nm for 3 hours. After the reaction solution was filtered, gas chromatography analysis showed that the conversion rate of anthranilamide was 0.8%, the selectivity of 3-indazolinone was 1.2%, and the yield of 3-indazolinone was 0%.

According to the experimental results of the above Example 1 and Comparative Examples 1 and 2, using the method of the present invention, the conversion rate of anthranilamide and the selectivity and yield of 3-indazolinone are significantly improved, and TiO ₂ that is not loaded with variable valence metal oxides has almost no effect on the reaction to prepare 3-indazolinone 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.