Photo-assisted oxidation method for compounds containing saturated carbon-hydrogen bonds

Abstract

The present invention belongs to the field of organic intermediate synthesis technology and provides a method for the photo-promoted oxidation of a saturated carbon-hydrogen bond-containing compound, which comprises mixing the saturated carbon-hydrogen bond-containing compound with a catalyst, and oxidizing the saturated carbon-hydrogen bond-containing compound under an oxygen gas or air atmosphere, irradiating light and at a temperature of 20° C. to 100° C. to produce an oxidation product. This method is a direct oxidation method for a saturated carbon-hydrogen bond-containing compound promoted by light, which can be carried out at a relatively low temperature, has good compatibility of functional groups, a short reaction time, high reaction efficiency, low reaction cost, high added value, simple operation, good safety, and is a mild and environmentally friendly oxidation method.

Description

[Technical field]

[0001] The present invention claims priority to a Chinese patent application filed with the State Intellectual Property Office of China on June 9, 2021, bearing application number 202110642049.7 and entitled "Method for photo-promoted oxidation of saturated carbon-hydrogen bond-containing compounds", and a Chinese patent application filed with the State Intellectual Property Office of China on February 15, 2022, bearing application number 202210137499.5 and entitled "Method for photo-promoted oxidation of saturated carbon-hydrogen bond-containing compounds", both of which are incorporated by reference in their entireties into the present invention.

[0002] The present invention belongs to the field of synthetic techniques for organic intermediates, and specifically relates to a method for the photo-promoted oxidation of compounds containing saturated carbon-hydrogen bonds. [Background technology]

[0003] Oxygen-containing organic compounds such as alcohols, alcohol peroxides, aldehydes, ketones, carboxylic acids and peroxy acids have important application value in daily life and basic chemical industry. Among them, terephthalic acid is the raw material for polyester, with an annual production of hundreds of millions of tons; salicylic acid is widely used in personal health and food freshness preservation; and peroxyacetic acid is an eco-bactericide and a bleaching agent for wood pulp, etc. Oxidation is a very important reaction in the chemical industry, and most oxygen-containing compounds are produced by oxidation. As shown in Figure 1, homogeneous oxidation or heterogeneous catalytic oxidation is generally used in conventional oxidation methods. For example, the oxidizing agent for homogeneous oxidation is a metal oxidizing agent (potassium permanganate (KMnO 4 )), transition metals, diiodine pentoxide (iodine V), peroxides (t-butanol peroxide (t-BuOOH), m-chloroperoxybenzoic acid (m-CPBA), hydrogen peroxide (H 2 O 2 ) and N-hydroxyphthalimide (NHPI). The above catalysts are used in large quantities and are expensive, which limits the development and application of oxidation reactions.

[0004] Under the guidance of the idea of ​​sustainable development, it is necessary to develop new energy-saving and environmentally friendly synthetic methods. How to efficiently oxidize alkane compounds using inexpensive catalysts under mild and environmentally friendly conditions is a goal that is sought in the field of chemical synthesis. Organic oxidation reactions using oxygen gas as an oxidant have the characteristics of relatively high atomic economy, low cost and relatively small environmental damage, and therefore meet the ever-increasing demand for environmental protection, and have become a research direction of interest. In recent years, chemical reactions promoted by photosensitive organometallic catalysts or organic dyes have been developing rapidly. The currently developed photo-promoted oxidation reactions require the use of expensive metal catalysts such as ruthenium, platinum, iridium, etc., or organic photosensitizers with complex structures such as methylacridine and anthraquinone derivatives, and the use of these two types of catalysts has certain deficiencies in terms of economy and environmental protection, and leads to increased reaction costs and environmental pollution. Summary of the Invention

[0005] The present invention has been made to solve the above problems, and aims to provide a method for oxidizing compounds containing saturated carbon-hydrogen bonds, which is accelerated by light, does not involve metals, and is environmentally friendly. The specific technical proposal is as follows:

[0006] The present invention provides a method for the photo-promoted oxidation of a saturated carbon-hydrogen bond-containing compound, which is characterized in that the method for the photo-promoted oxidation of a saturated carbon-hydrogen bond-containing compound includes mixing the saturated carbon-hydrogen bond-containing compound with a catalyst, and oxidizing the saturated carbon-hydrogen bond-containing compound under an oxygen gas or air atmosphere, under light irradiation and at a temperature of 20°C to 100°C to generate an oxidation product.

[0007] In the present invention, the process for oxidizing a saturated carbon-hydrogen bond-containing compound refers to a process for oxidizing a carbon-hydrogen bond on a carbon atom that does not contain an unsaturated bond.

[0008] The photo-promoted oxidation method for a saturated carbon-hydrogen bond-containing compound provided by the present invention is further characterized in that the catalyst is any one selected from the group consisting of t-butyl hypochlorite, hydrochloric acid and hydrobromic acid, or the catalyst is a mixture capable of generating hydrochloric acid and hydrobromic acid in situ, and the mixture is a mixture of a chloride and acetic acid or a mixture of a bromide and acetic acid.

[0009] The method for photo-promoted oxidation of a saturated carbon-hydrogen bond-containing compound provided by the present invention is further characterized in that the saturated carbon-hydrogen bond-containing compound is selected from C1 to C8 alkanes.

[0010] The present invention provides a method for the photo-promoted oxidation of a saturated carbon-hydrogen bond-containing compound, further comprising the steps of: the saturated carbon-hydrogen bond-containing compound is selected from a C1-C8 alkane substituted with phenyl, biphenyl, or substituted phenyl; and the substituent of the substituted phenyl is selected from halogen, nitro, cyano, hydroxy, amino, carboxyl, a C2-C8 carboxylate group, and [ka] The compound is characterized in that it is any one selected from the group: The photo-promoted oxidation method for a saturated carbon-hydrogen bond-containing compound provided by the present invention is further characterized in that the catalyst is an oxygen-containing acid, and the oxygen-containing acid is any one selected from p-toluenesulfonic acid, sulfuric acid, and nitric acid.

[0011] The method for photo-promoted oxidation of a saturated carbon-hydrogen bond-containing compound provided by the present invention is further characterized in that the wavelength of the light is 300 nm to 800 nm.

[0012] The photo-promoted oxidation method for a saturated carbon-hydrogen bond-containing compound provided by the present invention is further characterized in that the oxidation product is at least one selected from the group consisting of alcohols, alcohol peroxides, aldehydes, ketones, carboxylic acids, and acid peroxides.

[0013] The method for photo-promoted oxidation of a saturated carbon-hydrogen bond-containing compound provided by the present invention is further characterized in that the pressure of the oxygen gas or air in the reaction system is 1 to 100 atmospheres.

[0014] The method for photo-promoted oxidation of a saturated carbon-hydrogen bond-containing compound provided by the present invention is further characterized in that the molar ratio of the saturated carbon-hydrogen bond-containing compound to the catalyst is 1:0.0001 to 1:1.

[0015] The method for photo-promoted oxidation of a saturated carbon-hydrogen bond-containing compound provided by the present invention is further characterized in that a solvent for the oxidation reaction is any one selected from acetonitrile, tetrahydrofuran, dichloromethane, dichloroethane, trichloromethane, dimethylsulfoxide, dibromoethane, and N,N-dimethylformamide.

[0016] The present invention provides a method for the photo-promoted oxidation of a saturated carbon-hydrogen bond-containing compound, which comprises oxidizing a saturated carbon-hydrogen bond-containing compound with oxygen gas under the condition of light irradiation under the action of a catalyst to synthesize a corresponding oxidation product, for example, at least one selected from alcohols, alcohol peroxides, aldehydes, ketones, carboxylic acids, and acid peroxides. This method is a direct oxidation method for a saturated carbon-hydrogen bond-containing compound promoted by light, and has the advantages of being able to be carried out at a relatively low temperature (20°C to 100°C), having good compatibility of functional groups, a short reaction time, high reaction efficiency, low reaction cost, high added value, simple operation, and good safety, and is a mild and environmentally friendly oxidation method.

[0017] Of course, it is not necessary for all of the above advantages to be achieved simultaneously in order to practice any product or method herein. [Brief description of the drawings]

[0018] [Figure 1] FIG. 1 is a diagram of a conventional oxidation method. [Diagram 2]FIG. 2 is a hydrogen nuclear magnetic spectrum of the product in Example 15 of the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0019] Hereinafter, the present invention will be described in detail based on examples and drawings in order to clarify the technical means, features, objectives and effects of the present invention. However, the scope of protection of the present invention is not limited to the specific examples, and other examples obtained by those skilled in the art based on the examples of the present invention are also included in the scope of protection of the present invention.

[0020] The present invention provides a light-promoted oxidation method for a saturated carbon-hydrogen bond-containing compound, which comprises mixing a saturated carbon-hydrogen bond-containing compound with a catalyst, and subjecting the saturated carbon-hydrogen bond-containing compound to an oxidation reaction under an oxygen gas or air atmosphere, light irradiation and a temperature of 20°C to 100°C to generate an oxidation product.

[0021] In the present invention, the process for oxidizing a saturated carbon-hydrogen bond-containing compound refers to a process for oxidizing a carbon-hydrogen bond on a carbon atom that does not contain an unsaturated bond.

[0022] In some embodiments of the present invention, the catalyst is any one selected from t-butyl hypochlorite, hydrochloric acid and hydrobromic acid, or the catalyst is a mixture of various compounds capable of generating hydrochloric acid and hydrobromic acid in situ, the mixture being a mixture of chloride and acetic acid or a mixture of bromide and acetic acid. Here, the molar ratio of chloride and acetic acid or the molar ratio of bromide and acetic acid is 1:1 to 1:10. Exemplarily, a mixture of ammonium chloride and acetic acid in a molar ratio of 1:1 may be used as the catalyst.

[0023] In some embodiments of the present invention, the saturated carbon-hydrogen bond-containing compound is selected from C1-C8 alkanes. In the present invention, the C1-C8 alkanes may be linear alkanes, branched alkanes and cycloalkanes, and the C1-C8 alkanes may include, but are not limited to, methane, ethane, propane, butane, isobutane, pentane, isopentane, hexane, isohexane, heptane, isoheptane, octane, isooctane, cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, and cyclooctane.

[0024] In some embodiments of the present invention, the saturated carbon-hydrogen bond-containing compound is selected from C1-C8 alkanes substituted with phenyl, biphenyl, or substituted phenyl, the substituents of the substituted phenyl being halogen, nitro, cyano, hydroxy, amino, carboxyl, C2-C8 carboxylic acid ester, and [ka] The substituent of the halogen is selected from fluorine, chlorine, bromine, and iodine, and the substitution position of the substituent of the substituted phenyl may be ortho, meta, or para.

[0025] In some embodiments of the present invention, the catalyst is an oxygen-containing acid, and the oxygen-containing acid is any one selected from p-toluenesulfonic acid, sulfuric acid, and nitric acid.

[0026] In some embodiments of the present invention, the wavelength of the light is from 300 nm to 800 nm.

[0027] In some embodiments of the present invention, the oxidation product is at least one selected from an alcohol, a peroxy alcohol, an aldehyde, a ketone, a carboxylic acid, and a peroxy acid.

[0028] In some embodiments of the present invention, the pressure of oxygen gas or air in the reaction system is 1 to 100 atmospheres (atm).

[0029] In some embodiments of the present invention, the molar ratio of the saturated carbon-hydrogen bond-containing compound to the catalyst is from 1:0.0001 to 1:1.

[0030] In some embodiments of the present invention, the solvent for the oxidation reaction is any one selected from acetonitrile, tetrahydrofuran, dichloromethane, dichloroethane, trichloromethane, dimethyl sulfoxide, dibromoethane, and N,N-dimethylformamide. In the present invention, the reaction vessel used needs to cause an oxidation reaction by photo-promotion under a certain atmosphere. The reaction vessel used includes, but is not limited to, a photoreactor or a quartz tube.

[0031] In the present invention, the type of the light source used is not particularly limited as long as the object of the present invention can be achieved. In the present invention, the power range of the light source used is from 1 W to 100 W. Exemplarily, a 40 W light-emitting diode (LED) lamp is used as the light source.

[0032] In the present invention, the method for separating the target product after the photo-promoted reaction stops is a separation method commonly used in this field such as filtration, vacuum distillation, extraction, etc. The present invention does not limit the separation method as long as the object of the present invention can be achieved.

[0033] In the present invention, the term "yield" means the molar percentage of the actual yield to the theoretical yield of a certain product. In the present invention, the calculation formula for the yield is: yield of the target product = actual number of moles of the target product produced / theoretical number of moles of the target product produced × 100%.

[0034] Hereinafter, the embodiments of the present invention will be described more specifically by way of examples and comparative examples. Various tests and evaluations are carried out by the following methods. Unless otherwise specified, "parts" and "%" are based on mass.

[0035] Measurement methods and equipment The hydrogen nuclear magnetic spectrum of the target product was measured by a nuclear magnetic resonance spectrometer to quantitatively measure the yield of the target product and confirm the molecular structure of the target product. Example 1 Preparation of benzoic acid: [ka]

[0036] In a 25 mL quartz tube, add toluene (92 mg, 1 mmol), hydrochloric acid (200 μL, 1 M), acetonitrile (CH 3 CN, 2 mL) were added in this order and mixed to obtain a mixed solution. The resulting mixed solution was irradiated with a blue LED lamp (40 W) with a wavelength of 380 nm to 550 nm under an oxygen gas atmosphere (1 atm) and reacted at room temperature for 12 hours. After the reaction was stopped, the solvent was removed under reduced pressure to obtain 103 mg of the corresponding benzoic acid, with a yield of 84%.

[0037] The hydrogen nuclear magnetic spectrum of this product was as follows: 1 H NMR (400 MHz, DMSO) δ 12.98 (s, 1H), 7.95 (d, J = 8.0 Hz, 2H), 7.63 (t, J = 7.2 Hz, 1H), 7.50 (t, J = 7.6 Hz, 2H). 13 C NMR (100 MHz, DMSO) δ 167.4, 132.9, 130.8, 129.3, 128.6. The product of the reaction is indicative of the desired benzoic acid. Example 2 Preparation of benzoic acid: [ka]

[0038] Compared with Example 1, the difference was that the conversion reaction temperature was 60° C. Specifically, the following was performed. Toluene (92 mg, 1 mmol), hydrochloric acid (200 μL, 1 M), and acetonitrile (2 mL) were added in this order to a 25 mL quartz tube and mixed to obtain a mixed solution. The resulting mixed solution was irradiated with a blue LED lamp (40 W) with a wavelength of 380 nm to 550 nm under an oxygen gas atmosphere (1 atm) and reacted at 60 °C for 12 hours. After the reaction was stopped, the solvent was removed under reduced pressure to obtain 109 mg of the corresponding benzoic acid, with a yield of 89%. Example 3 Preparation of benzoic acid: [ka]

[0039] The difference from Example 1 was that a light source of 390 nm was used. Toluene (92 mg, 1 mmol), hydrochloric acid (200 μL, 1 M), and acetonitrile (2 mL) were added in this order to a 25 mL quartz tube and mixed to obtain a mixed solution. The resulting mixed solution was irradiated with an LED lamp (40 W) with a wavelength of 390 nm under an oxygen gas atmosphere (1 atm) and reacted at room temperature for 12 hours. After the reaction was stopped, the solvent was removed under reduced pressure to obtain 112 mg of the corresponding benzoic acid, with a yield of 92%. Example 4 Preparation of benzoic acid: [ka]

[0040] The difference from Example 1 was that hydrobromic acid was used as a catalyst. Toluene (92 mg, 1 mmol), hydrobromic acid (200 μL, 1 M), and acetonitrile (2 mL) were added in this order to a 25 mL quartz tube and mixed to obtain a mixed solution. The resulting mixed solution was irradiated with a blue LED lamp (40 W) with a wavelength of 380 nm to 550 nm under an oxygen gas atmosphere (1 atm) and reacted at room temperature for 12 hours. The solvent was removed under reduced pressure to obtain 76 mg of the corresponding benzoic acid, with a yield of 62%. Example 5 Preparation of benzoic acid: [ka]

[0041] The difference from Example 1 was that p-toluenesulfonic acid was used as a catalyst. Toluene (92 mg, 1 mmol), p-toluenesulfonic acid (TsOH, 200 μL, 1 M), and acetonitrile (2 mL) were added in this order to a 25 mL quartz tube and mixed to obtain a mixed solution. The resulting mixed solution was irradiated with a blue LED lamp (40 W) with a wavelength of 380 nm to 550 nm under an oxygen gas atmosphere (1 atm) and reacted at room temperature for 12 hours. The solvent was removed under reduced pressure to obtain 70 mg of the corresponding benzoic acid, with a yield of 57%. Example 6 Preparation of benzoic acid: [ka]

[0042] The difference from Example 1 was that a mixture of lithium chloride and acetic acid was used as a catalyst. Toluene (92 mg, 1 mmol), a mixture of lithium chloride and acetic acid (molar ratio of LiCl to AcOH = 1:1, 200 μL, 1 M), and acetonitrile (2 mL) were added in this order to a 25 mL quartz tube, mixed, and then irradiated with a blue LED lamp (40 W) with a wavelength of 380 nm to 550 nm under an oxygen gas atmosphere (1 atm) and reacted at room temperature for 12 hours. The solvent was removed under reduced pressure to obtain 92 mg of the corresponding benzoic acid, with a yield of 75%. Example 7 Preparation of benzoic acid: [ka]

[0043] The difference from Example 1 was that a mixture of ammonium chloride and acetic acid was used as a catalyst. In a 25 mL quartz tube, toluene (92 mg, 1 mmol) and a mixture of ammonium chloride and acetic acid (NH 4 The mixture was mixed with Cl:AcOH (molar ratio = 1:1, 200μL, 1M) and acetonitrile (2mL) in that order, and then irradiated with a blue LED lamp (40W) with a wavelength of 380nm-550nm under an oxygen gas atmosphere (1atm) and reacted at room temperature for 12 hours. The solvent was removed under reduced pressure to obtain 98mg of the corresponding benzoic acid, with a yield of 80%. Example 8 Preparation of benzoic acid: [ka]

[0044] The difference from Example 1 was that sulfuric acid was used as a catalyst. Specifically, the process was as follows. Toluene (92 mg, 1 mmol), sulfuric acid (200 μL, 1 M), and acetonitrile (2 mL) were added in this order to a 25 mL quartz tube and mixed to obtain a mixed solution. The resulting mixed solution was irradiated with a blue LED lamp (40 W) with a wavelength of 380 nm to 550 nm under an oxygen gas atmosphere (1 atm) and reacted at room temperature for 12 hours. The solvent was removed under reduced pressure to obtain 105 mg of the corresponding benzoic acid, with a yield of 86%. Example 9 Preparation of benzoic acid: [ka]

[0045] The difference from Example 1 was that nitric acid was used as a catalyst. Toluene (92 mg, 1 mmol), nitric acid (200 μL, 1 M), and acetonitrile (2 mL) were added in this order to a 25 mL quartz tube and mixed to obtain a mixed solution. The resulting mixed solution was irradiated with a blue LED lamp (40 W) with a wavelength of 380 nm to 550 nm under an oxygen gas atmosphere (1 atm) and reacted at room temperature for 12 hours. The solvent was removed under reduced pressure to obtain 102 mg of the corresponding benzoic acid, with a yield of 84%. Example 10 Preparation of benzoic acid: [ka]

[0046] The difference from Example 1 was that t-butyl hypochlorite was used as a catalyst. Toluene (92 mg, 1 mmol), t-butyl hypochlorite (t-BuOCl, 200 μL, 1 M), and acetonitrile (2 mL) were added in this order to a 25 mL quartz tube and mixed to obtain a mixed solution. The resulting mixed solution was irradiated with a blue LED lamp (40 W) with a wavelength of 380 nm to 550 nm under an oxygen gas atmosphere (1 atm) and reacted at room temperature for 12 hours. The solvent was removed under reduced pressure to obtain 0.112 g of the corresponding benzoic acid, with a yield of 92%. Example 11

[0047] Preparation of 4-phenylbenzoic acid: [ka] In a 25 mL quartz tube, 4-phenyltoluene (168 mg, 1 mmol), hydrochloric acid (200 μL, 1 M), and acetonitrile (2 mL) were added in this order and mixed to obtain a mixed solution. The resulting mixed solution was irradiated with a blue LED lamp (40 W) with a wavelength of 380 nm to 550 nm under an oxygen gas atmosphere (1 atm) and reacted at room temperature for 12 hours. After the reaction was stopped, the solvent was removed under reduced pressure to obtain 170 mg of the corresponding 4-phenylbenzoic acid, with a yield of 86%. The hydrogen nuclear magnetic spectrum of this product was as follows: 1H NMR (400 MHz, DMSO) δ 13.04 (s, 1H), 8.05 (d, J = 8.4 Hz, 2H), 7.81 (d, J = 8.4 Hz, 2H), 7.74 (d, J = 7.2 Hz, 2H), 7.51 (t, J = 7.6 Hz, 2H), 7.44 (t, J = 7.2 Hz, 1H). 13 C NMR (100 MHz, DMSO) δ 167.3, 144.4, 139.2, 130.1, 129.7, 129.2, 128.4, 127.1, 126.9, indicating that the product of the reaction is the desired product, 4-phenylbenzoic acid. Example 12

[0048] Preparation of 1-indanone: [ka] In a 25 mL quartz tube, indane (168 mg, 1 mmol), hydrochloric acid (200 μL, 1 M), and acetonitrile (2 mL) were added in this order and mixed to obtain a mixed solution. The resulting mixed solution was irradiated with a blue LED lamp (40 W) with a wavelength of 380 nm to 550 nm under an oxygen gas atmosphere (1 atm) and reacted at room temperature for 12 hours. After the reaction was stopped, the solvent was removed under reduced pressure to obtain 103 mg of the corresponding 1-indanone, with a yield of 78%. The hydrogen nuclear magnetic spectrum of this product was as follows: 1 H NMR (400 MHz, CDCl 3 ) δ 7.77 (d, J = 7.6 Hz, 1H), 7.59 (t, J = 7.6 Hz, 1H), 7.49 (d, J = 7.6 Hz, 1H), 7.38 (t, J = 7.2 Hz, 1H), 3.17 - 3.14 (m, 2H), 2.72 - 2.69 (m, 2H). 13 C NMR (100 MHz, CDCl 3) δ 207.1, 155.1, 137.1, 134.6, 127.3, 126.7, 123.7, 36.2, 25.8, indicating that the product of the reaction is the desired product, 1-indanone. Example 13

[0049] Preparation of benzophenone: [ka] Diphenylmethane (168 mg, 1 mmol), hydrochloric acid (200 μL, 1 M), and acetonitrile (2 mL) were added in this order to a 25 mL quartz tube and mixed to obtain a mixed solution. The resulting mixed solution was irradiated with a blue LED lamp (40 W) with a wavelength of 380 nm to 550 nm under an oxygen gas atmosphere (1 atm) and reacted at room temperature for 24 hours. After the reaction was stopped, the solvent was removed under reduced pressure to obtain 162 mg of the corresponding benzophenone, with a yield of 89%. The hydrogen nuclear magnetic spectrum of this product was as follows: 1 H NMR (400 MHz, CDCl 3 ) δ 7.81 (dd, J = 8.4, 1.3 Hz, 4H), 7.62-7.57 (m, 2H), 7.49 (t, J = 7.6 Hz, 4H). 13 C NMR (100 MHz, CDCl 3 ) δ 132.4, 130.1, 128.3, indicating that the product of the reaction is the desired product, benzophenone. Example 14

[0050] Celecoxib Oxidation: [ka] Celecoxib (381 mg, 1 mmol), hydrochloric acid (200 μL, 1 M), and acetonitrile (2 mL) were added in this order to a 25 mL quartz tube and mixed to obtain a mixed solution. The resulting mixed solution was irradiated with a blue LED lamp (40 W) with a wavelength of 380 nm to 550 nm under an oxygen gas atmosphere (1 atm) and reacted at room temperature for 24 hours. After the reaction stopped, it was rapidly separated and 262 mg of the corresponding oxidation product was obtained, with a yield of 64%. The hydrogen nuclear magnetic spectrum of this product was as follows: 1 H NMR (400 MHz, DMSO-d6) δ 12.11 (brs, 1H), 7.94 (d, J = 8.4 Hz, 2H), 7.88 (d, J = 8.8 Hz, 2H), 7.55 (d, J = 8.8 Hz, 2H), 7.52 (s, 2H), 7.44 (d, J = 8.4 Hz, 2H), 7.35 (s, 1H). 13 C NMR (100 MHz, DMSO-d6) δ 167.0, 144.6, 144.5, 142.5 (q, J = 10.0 Hz), 141.2, 132.6, 131.7, 130.0, 129.5, 127.3, 126.4, 120.3 (q, J = 247.0 Hz), 107.4. 19 F NMR (377 MHz, DMSO-d6) δ -60.87. The product of the reaction is shown to be the desired product. Example 15

[0051] Methane Oxidation: [ka] In the photoreactor, add hydrochloric acid (200 μL, 1 M), deuterated acetonitrile (CD 3CN, 2 mL) were added in this order, the reaction vessel was closed, and then 20 atm oxygen gas and 40 atm methane were passed through. The reaction was carried out at room temperature for 24 hours, with irradiation using a blue LED lamp (40 W) with a wavelength of 380 nm to 550 nm. After the reaction was stopped, detection was performed using nuclear magnetic resonance spectroscopy, and the yield of methanol was 3.3% and the yield of formic acid was 16.5%. The hydrogen nuclear magnetic spectrum of the reaction product is shown in Figure 2. The hydrogen nuclear magnetic spectrum of formic acid was as follows: 1 H NMR (400 MHz, CD 3 CN) δ 8.08 (s, 1H). The hydrogen nuclear magnetic spectrum of methanol was as follows: 1 H NMR (400 MHz, CD 3 CN) δ 3.31 (s, 0.6 H). Example 16

[0052] Methane Oxidation: [ka] A stirrer was placed in a 25 mL sealed tube, and hydrochloric acid (5.0 μL, 12.0 M) and deuterium acetonitrile (750.0 μL) were added in that order. Then, the tube was evacuated under refrigeration conditions (-20°C) and a mixture of methane and oxygen gas (the total pressure of the mixed gas was 1 atm, and the gas pressure ratio was CH 4 :O 2 =1:1) was aerated. The sealed tube was then placed in front of a 390 nm LED lamp (40 W) and reacted at room temperature for 24 hours. After the reaction was stopped, the corresponding oxidation products and their yields were obtained by detection using nuclear magnetic resonance spectroscopy, as shown in Table 1. [Table 1] Example 17

[0053] Ethane Oxidation: [ka] A stirrer was placed in a 25 mL sealed tube, and hydrochloric acid (5.0 μL, 0.1 M) and deuterium acetonitrile (750.0 μL) were added in that order. The tube was then evacuated under refrigeration conditions (-20°C) and mixed with ethane and oxygen gas (the total pressure of the mixed gas was 1 atm, and the gas pressure ratio was ethane:O 2 The reaction was then stopped and detected by nuclear magnetic resonance spectroscopy to obtain the corresponding oxidation products and their yields, which are shown in Table 2. [Table 2] Example 18

[0054] Propane Oxidation: [ka] A stirrer was placed in a 25 mL sealed tube, and hydrochloric acid (5.0 μL, 0.1 M) and deuterium acetonitrile (750.0 μL) were added in that order. The tube was then evacuated under refrigeration conditions (-20°C) and mixed with propane and oxygen gas (the total pressure of the mixed gas was 1 atm, and the gas pressure ratio was propane:O 2 =1:1) was aerated. The sealed tube was then placed in front of a 390 nm LED lamp (40 W) and reacted at room temperature for 24 hours. After the reaction was stopped, the corresponding oxidation products and their yields were obtained by detection using nuclear magnetic resonance spectroscopy, as shown in Table 3. [Table 3] Example 19

[0055] Butane Oxidation: [ka] A stirrer was placed in a 25 mL sealed tube, and hydrochloric acid (5.0 μL, 0.1 M) and deuterium acetonitrile (750.0 μL) were added in that order. The tube was then evacuated under refrigeration conditions (-20°C) and mixed with butane and oxygen gas (the total pressure of the mixed gas was 1 atm, and the gas pressure ratio was butane:O2 =1:1) was aerated. The sealed tube was then placed in front of a 390 nm LED lamp (40 W) and reacted at room temperature for 24 hours. After the reaction was stopped, the corresponding oxidation products and their yields were obtained by detection using nuclear magnetic resonance spectroscopy, as shown in Table 4. [Table 4] Example 20

[0056] Mixed gas oxidation: [ka] A stirrer was placed in a 25 mL sealed tube, and hydrochloric acid (5.0 μL, 0.1 M) and deuterium acetonitrile (750.0 μL) were added in that order. The tube was then evacuated under refrigeration conditions (-20°C) to obtain a mixed gas of alkane gas and oxygen gas (the total pressure of the mixed gas was 1 atm, and the gas pressure ratio was methane:ethane:propane:butane:O). 2 The mixture of alkane gas (ratio of alkane to alkane) was aerated, and the ratio of the mixed alkane gas was simulated the ratio of each alkane in natural gas. The sealed tube was then placed in front of a 390 nm LED lamp (40 W) and reacted at room temperature for 24 hours. After the reaction was stopped, the corresponding oxidation products and their yields were obtained by detection using nuclear magnetic resonance spectroscopy, and are shown in Table 5. [Table 5] Example 21

[0057] Petroleum Ether Oxidation: [ka] A stirrer was placed in a 25 mL sealed tube, and hydrochloric acid (5.0 μL, 0.1 M), petroleum ether (22.6 mg), and deuterium acetonitrile (750.0 μL) were added in that order. The tube was then evacuated under refrigeration conditions (-20°C) and oxygen gas (1 atm) was passed through. The sealed tube was then placed in front of a 390 nm LED lamp (40 W) and reacted at room temperature for 24 hours. After the reaction was stopped, the corresponding oxidation products and their yields were obtained by detection using nuclear magnetic resonance spectroscopy, and are shown in Table 6. [Table 6] Example 22

[0058] n-Hexane Oxidation: [ka] A stirrer was placed in a 25 mL sealed tube, and hydrochloric acid (5.0 μL, 0.1 M), n-hexane (17.2 mg), and deuterium acetonitrile (750.0 μL) were added in that order. The tube was then evacuated under refrigeration conditions (-20°C) and oxygen gas (1 atm) was passed through. The sealed tube was then placed in front of a 390 nm LED lamp (40 W) and reacted at room temperature for 24 hours. After the reaction was stopped, the corresponding oxidation products and their yields were obtained by detection using nuclear magnetic resonance spectroscopy, and are shown in Table 7. [Table 7] Example 23

[0059] Cyclohexane Oxidation: [ka] A stirrer was placed in a 25 mL sealed tube, and hydrochloric acid (5.0 μL, 0.1 M), cyclohexane (16.8 mg), and deuterium acetonitrile (750.0 μL) were added in that order. The tube was then evacuated under refrigeration conditions (-20°C) and oxygen gas (1 atm) was passed through. The sealed tube was then placed in front of a 390 nm LED lamp (40 W) and reacted at room temperature for 24 hours. After the reaction was stopped, the corresponding oxidation products and their yields were obtained by detection using nuclear magnetic resonance spectroscopy, and are shown in Table 8. [Table 8] Example 24

[0060] Isooctane Oxidation: [ka] A stirrer was placed in a 25 mL sealed tube, and hydrochloric acid (5.0 μL, 0.1 M), isooctane (22.8 mg), and deuterium acetonitrile (750.0 μL) were added in that order. The tube was then evacuated under refrigeration conditions (-20°C) and oxygen gas (1 atm) was passed through. The sealed tube was then placed in front of a 390 nm LED lamp (40 W) and reacted at room temperature for 24 hours. After the reaction was stopped, the corresponding oxidation products and their yields were obtained by detection using nuclear magnetic resonance spectroscopy, and are shown in Table 9. [Table 9] Example 25

[0061] n-Heptane oxidation: [ka] A stirrer was placed in a 25 mL sealed tube, and hydrochloric acid (5.0 μL, 0.1 M), n-heptane (20.0 mg), and deuterium acetonitrile (750.0 μL) were added in that order. The tube was then evacuated under refrigeration conditions (-20°C) and oxygen gas (1 atm) was passed through. The sealed tube was then placed in front of a 390 nm LED lamp (40 W) and reacted at room temperature for 24 hours. After the reaction was stopped, the corresponding oxidation products and their yields were obtained by detection using nuclear magnetic resonance spectroscopy, and are shown in Table 10. [Table 10] Example 26

[0062] n-Octane Oxidation: [ka] A stirrer was placed in a 25 mL sealed tube, and hydrochloric acid (5.0 μL, 0.1 M), n-octane (22.8 mg), and deuterium acetonitrile (750.0 μL) were added in that order. The tube was then evacuated under refrigeration conditions (-20°C) and oxygen gas (1 atm) was passed through. The sealed tube was then placed in front of a 390 nm LED lamp (40 W) and reacted at room temperature for 24 hours. After the reaction was stopped, the corresponding oxidation products and their yields were obtained by detection using nuclear magnetic resonance spectroscopy, and are shown in Table 11. [Table 11] Example 27

[0063] Cyclohexane Oxidation: [ka] A stirrer was placed in a 25 mL sealed tube, and hydrochloric acid (5.0 μL, 0.1 M), cyclohexane (16.8 mg), and deuterium acetonitrile (750.0 μL) were added in that order. The tube was then evacuated under refrigeration conditions (-20°C) and air (1 atm) was passed through. The sealed tube was then placed in front of a 390 nm LED lamp (40 W) and reacted at room temperature for 24 hours. After the reaction was stopped, the corresponding oxidation products and their yields were obtained by detection using nuclear magnetic resonance spectroscopy, and are shown in Table 12. [Table 12]

[0064] According to an embodiment of the present invention, there is provided a method for the photo-promoted oxidation of a saturated carbon-hydrogen bond-containing compound, which comprises oxidizing a saturated carbon-hydrogen bond-containing compound with oxygen gas under the condition of light irradiation by the action of a catalyst to synthesize a corresponding oxidation product, for example, at least one selected from alcohols, alcohol peroxides, aldehydes, ketones, carboxylic acids, and acid peroxides. This method is a direct oxidation method for a saturated carbon-hydrogen bond-containing compound promoted by light, and has the advantages of being able to be carried out at a relatively low temperature (20°C to 100°C), having good compatibility of functional groups, a short reaction time, high reaction efficiency, low reaction cost, high added value, simple operation, and good safety. Moreover, this method is a milder and more environmentally friendly oxidation method because it requires only light to promote the reaction.

[0065] The above embodiment is a preferred example of the present invention, and is not intended to limit the scope of protection of the present invention. Of course, any amendments, equivalent replacements, improvements, etc. are included in the scope of the claims of the present invention within the scope of the spirit and principle of the present invention.

Claims

1. mixing a saturated carbon-hydrogen bond-containing compound with a catalyst, and oxidizing the saturated carbon-hydrogen bond-containing compound under an oxygen gas or air atmosphere, at a temperature of 20°C to 100°C, with light irradiation to generate an oxidation product; the saturated carbon-hydrogen bond-containing compound is toluene, 4-phenyltoluene, indane, diphenylmethane, celecoxib, methane, ethane, propane, butane, petroleum ether, n-hexane, n-heptane, n-octane, or isooctane; The catalyst is t-butyl hypochlorite, hydrochloric acid, a mixture of chlorides capable of producing hydrochloric acid and acetic acid, sulfuric acid, or nitric acid; A method for the light-promoted oxidation of a saturated carbon-hydrogen bond-containing compound, characterized in that a solvent for the oxidation reaction is any one selected from the group consisting of acetonitrile, tetrahydrofuran, dichloromethane, dichloroethane, trichloromethane, dimethylsulfoxide, dibromoethane, and N,N-dimethylformamide.

2. 2. The method for photo-promoted oxidation of a saturated carbon-hydrogen bond-containing compound according to claim 1, wherein the wavelength of the light is 300 nm to 800 nm.

3. The method for photo-accelerated oxidation of a saturated carbon-hydrogen bond-containing compound according to claim 1, wherein the oxidation product is at least one selected from the group consisting of alcohols, alcohol peroxides, aldehydes, ketones, carboxylic acids, and acid peroxides.

4. 2. The method for photo-promoted oxidation of a compound containing a saturated carbon-hydrogen bond according to claim 1, wherein the pressure of the oxygen gas or air in the reaction system is 1 to 100 atmospheres.

5. 2. The method for photo-promoted oxidation of a saturated carbon-hydrogen bond-containing compound according to claim 1, wherein a molar ratio of the saturated carbon-hydrogen bond-containing compound to the catalyst is 1:0.0001 to 1:1.

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