Method for synthesizing alcohol, aldehyde, ketone or acid compound from compound containing saturated carbon-hydrogen bond

Abstract

The invention provides a method for synthesizing an alcohol, aldehyde, ketone or acid compound from a compound containing a saturated carbon-hydrogen bond, which comprises the following steps: under the condition of visible light, carrying out oxidation reaction on the compound containing the saturated carbon-hydrogen bond and an oxidant under the action of a catalyst to obtain the alcohol, aldehyde, ketone or acid compound, wherein the catalyst is a compound capable of generating chlorine or bromine free radicals in situ; the oxidant is selected from oxygen or air; the compound containing the saturated carbon-hydrogen bond is selected from at least one of C1-C20 alkanes, C4-C20 cycloalkanes or aryl alkane compounds; the aryl alkane compound is selected from at least one of compounds as shown in a formula I in the specification. The method provided by the invention has the advantages of abundant and easily available reaction raw material sources, mild reaction conditions, good compatibility of raw material functional groups, simple operation, high reaction safety, environmental protection, low production cost and the like. # imgabs0 #

Description

Technical Field

[0001] The present application relates to the technical field of organic intermediate synthesis, and in particular to a method for synthesizing alcohol, aldehyde, ketone or acid compounds from compounds containing saturated carbon-hydrogen bonds. Background Art

[0002] Oxygen-containing organic compounds such as alcohols, aldehydes, ketones and acids have important application value in daily life and basic chemical industry. Oxidation reaction is a very important reaction in the chemical industry, and most oxygen-containing compounds are prepared by oxidation reaction. In traditional oxidation methods, a large amount of metal oxidants, or expensive transition metals, peroxides and complex catalysts are required, which restricts the development and application of oxidation reactions.

[0003] Under the guidance of the concept of sustainable development, it is imperative to develop new energy-saving and environmentally friendly synthesis methods. How to efficiently oxidize alkane compounds using cheap catalysts under mild and green conditions has always been a goal pursued in the field of chemical synthesis. Organic oxidation reactions using oxygen as an oxidant meet the growing environmental protection requirements due to their high atomic economy, low cost and relatively small environmental damage, and have become a widely concerned research direction. In recent years, chemical reactions promoted by organic metal catalysts or organic dyes with photosensitivity have developed rapidly. Most of the currently developed light-promoted oxidation reactions require the use of expensive metal catalysts such as ruthenium, platinum, and iridium, or complex organic photosensitizers such as methyl acridine and anthraquinone derivatives. The use of these catalysts has certain defects in terms of economy and environmental protection, which will increase the reaction cost and pollute the environment. Summary of the invention

[0004] The purpose of the present application is to provide a method for synthesizing alcohols, aldehydes, ketones or acid compounds from compounds containing saturated carbon-hydrogen bonds, which has the advantages of abundant and readily available reaction raw materials, mild reaction conditions, simple operation, high reaction safety, green environmental protection and low production cost.

[0005] The present application provides a method for synthesizing alcohol, aldehyde, ketone or acid compound from a compound containing saturated carbon-hydrogen bonds, comprising: under visible light conditions, the compound containing saturated carbon-hydrogen bonds and an oxidant undergo an oxidation reaction under the action of a catalyst to obtain an alcohol, aldehyde, ketone or acid compound;

[0006] Wherein, the catalyst is a compound that can generate chlorine or bromine free radicals in situ; the oxidant is selected from oxygen or air; the compound containing saturated carbon-hydrogen bonds is selected from C 1 -C 20 Alkanes, C 4 -C 20At least one of cycloalkane or arylalkane compounds; the arylalkane compound is selected from at least one of the compounds represented by formula I;

[0007]

[0008] R 1 -R 7 Each independently selected from H, C 1 -C 10 Hydrocarbon, C 1 -C 10 Hydrocarbyloxy, C 6 -C 20 Aryl, C 5 -C 20 Heteroaryl, C 5 -C 20 Unsaturated cyclic group, C 2 -C 10 ester group, hydroxyl group, mercapto group, trifluoromethylthio group, trifluoromethoxy group, cyano group, nitro group, trifluoromethyl group, halogen group, benzoyl group, alcohol methyl group or aldehyde group; R 1 -R 7 Two adjacent groups in the heteroaryl group can be connected to form a five- to ten-membered ring; the heteroatoms on the heteroaryl group are each independently selected from O, S or N.

[0009] In some embodiments of the present application, the compound containing a saturated carbon-hydrogen bond is selected from C 1 -C 8 Alkanes, C 5 -C 10 At least one of cycloalkane or arylalkane compounds; the arylalkane compound is selected from at least one of the compounds represented by formula IIa or the compounds represented by formula IIb;

[0010]

[0011] In the formula IIa, n is 1, 2 or 3, R 1 -R 5 Each independently selected from H, C 1 -C 10 Hydrocarbon, C 1 -C 10 Hydrocarbyloxy, C 6 -C 20 Aryl, C 5 -C 20 Heteroaryl, C 5 -C 20 Unsaturated cyclic group, C 2 -C 10ester group, hydroxyl group, mercapto group, trifluoromethylthio group, trifluoromethoxy group, cyano group, nitro group, trifluoromethyl group, halogen group, benzoyl group, alcohol methyl group or aldehyde group; R 1 -R 5 Two adjacent groups in the heteroaryl group can be connected to form a five- to ten-membered ring; the heteroatoms on the heteroaryl group are each independently selected from O, S or N;

[0012] In the formula IIb, R 1 -R 4 Each independently selected from H, C 1 -C 10 Hydrocarbon, C 1 -C 10 Hydrocarbyloxy, C 6 -C 20 Aryl, C 5 -C 20 Heteroaryl, C 5 -C 20 Unsaturated cyclic group, C 2 -C 10 ester group, hydroxyl group, mercapto group, trifluoromethylthio group, trifluoromethoxy group, cyano group, nitro group, trifluoromethyl group, halogen group, benzoyl group, alcohol methyl group or aldehyde group; R 1 -R 4 Two adjacent groups in the heteroaryl group can be connected to form a five- to ten-membered ring; the heteroatoms on the heteroaryl group are each independently selected from O, S or N.

[0013] In some embodiments of the present application, in the formula IIa, R 1 -R 5 Each independently selected from H, C 1 -C 10 Hydrocarbon, C 1 -C 10 Hydrocarbyloxy, C 2 -C 10 Ester, cyano, nitro, trifluoromethyl, halogen or benzoyl; R 1 -R 5 Two adjacent groups can be linked to form a five- to eight-membered ring.

[0014] In some embodiments of the present application, in the formula IIa, R 1 -R 5 Each independently selected from H, C 1 -C 5 Hydrocarbon, C 1 -C 3 Hydrocarbyloxy, C 2 -C 3 ester, cyano, nitro, trifluoromethyl, F, Cl, Br, I or benzoyl; R 1 -R 5Two adjacent groups can be linked to form a five- to eight-membered ring.

[0015] In some embodiments of the present application, in the formula IIa, R 1 -R 5 R is independently selected from H, F, Cl, Br, I, cyano, acetoxy, nitro, trifluoromethyl, benzoyl, methoxy or tert-butyl; 1 -R 5 Two adjacent groups can be connected to form a five- to seven-membered ring.

[0016] In some embodiments of the present application, in the formula IIa, R 1 -R 5 One of them is selected from F, Cl, Br, I, cyano, acetoxy, nitro, trifluoromethyl, benzoyl, methoxy or tert-butyl, and the others are selected from H.

[0017] In some embodiments of the present application, in the formula IIb, R 1 -R 4 Each is independently selected from H, F, Cl, Br, I, cyano, acetoxy, nitro, trifluoromethyl, benzoyl, methoxy or tert-butyl.

[0018] In some embodiments of the present application, the compound containing a saturated carbon-hydrogen bond is selected from methane, ethane, propane, butane, cyclopentane, cyclohexane, n-octane, toluene, 4-chlorotoluene, 4-cyanotoluene, 3-cyanotoluene, 4-acetoxytoluene, 2-bromotoluene, 2-fluorotoluene, 4-fluorotoluene, 4-nitrotoluene, 4-trifluoromethyltoluene, 3-trifluoromethyltoluene, 4-benzoyltoluene, 4-methoxytoluene, 4-tert-butyltoluene, tetralin or ethyl benzene.

[0019] In some embodiments of the present application, the compound containing a saturated carbon-hydrogen bond is selected from methane, ethane, propane, butane, cyclopentane, cyclohexane, n-octane, toluene, 4-chlorotoluene, 4-cyanotoluene, 3-cyanotoluene, 4-acetoxytoluene, 2-bromotoluene, 2-fluorotoluene, 4-fluorotoluene, 4-trifluoromethyltoluene, 3-trifluoromethyltoluene, 4-benzoyltoluene, tetralin or ethylbenzene.

[0020] In some embodiments of the present application, the compound containing a saturated carbon-hydrogen bond is selected from methane, ethane, propane, butane, cyclopentane, cyclohexane, n-octane, toluene, 4-chlorotoluene, 4-cyanotoluene, 3-cyanotoluene, 2-fluorotoluene, 4-fluorotoluene, 4-trifluoromethyltoluene, 3-trifluoromethyltoluene, 4-benzoyltoluene, tetralin or ethyl benzene.

[0021] In some embodiments of the present application, the catalyst is selected from a halogen-containing organic solvent, and the halogen-containing organic solvent is selected from at least one of dichloromethane, deuterated dichloromethane, 1,1-dichloroethane, 1,2-dichloroethane, trichloroethane, tetrachloroethane, dibromomethane, 1,1-dibromoethane, 1,2-dibromoethane, trichloromethane, tribromomethane, tetrachloromethane, tetrabromomethane, chlorobenzene, bromobenzene, dichlorobenzene, dibromobenzene, trichlorobenzene and tribromobenzene.

[0022] In some embodiments of the present application, the reaction temperature of the oxidation reaction is 0°C-100°C, preferably 20°C-40°C; the reaction time of the oxidation reaction is 8h-48h.

[0023] In some embodiments of the present application, the pressure of the oxidant is 0.5 atm-100 atm, preferably 0.5 atm-5 atm.

[0024] In some embodiments of the present application, the wavelength of the visible light is 330nm-550nm.

[0025] In some embodiments of the present application, the solvent used in the oxidation reaction is selected from at least one of acetonitrile, deuterated acetonitrile, dichloromethane, deuterated dichloromethane, 1,1-dichloroethane, 1,2-dichloroethane, trichloroethane, tetrachloroethane, dibromomethane, 1,1-dibromoethane, 1,2-dibromoethane, trichloromethane, tribromomethane, tetrachloromethane, tetrabromomethane, chlorobenzene, bromobenzene, dichlorobenzene, dibromobenzene, trichlorobenzene and tribromobenzene.

[0026] Beneficial effects of this application:

[0027] The present application uses compounds containing saturated carbon-hydrogen bonds as starting materials, and uses cheap, green and easily available oxygen or air as an oxidant. Since the solvent itself, such as dichloromethane, can generate chlorine or bromine free radicals in situ, the chlorine or bromine free radicals generated in situ in the solvent can be directly used as a catalyst. The present application has the advantages of abundant and readily available sources of reaction raw materials, mild reaction conditions, good compatibility of raw material functional groups, simple operation, high reaction safety, green environmental protection and low production cost.

[0028] Of course, implementing any product or method of the present application does not necessarily require achieving all of the advantages described above at the same time. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present application, and for ordinary technicians in this field, other embodiments can also be obtained based on these drawings.

[0030] Figure 1 This is the hydrogen nuclear magnetic resonance spectrum of the target product benzoic acid prepared in Example 1;

[0031] Figure 2 This is the carbon NMR spectrum of the target product benzoic acid prepared in Example 1. DETAILED DESCRIPTION

[0032] The following will be combined with the drawings in the embodiments of the present application to clearly and completely describe the technical solutions in the embodiments of the present application. Obviously, the described embodiments are only part of the embodiments of the present application, rather than all the embodiments. All other embodiments obtained by those skilled in the art based on the present application belong to the scope of protection of the present application.

[0033] The present application provides a method for synthesizing alcohol, aldehyde, ketone or acid compounds from a compound containing a saturated carbon-hydrogen bond, comprising:

[0034] Under visible light conditions, compounds containing saturated carbon-hydrogen bonds and oxidants undergo oxidation reactions under the action of catalysts to obtain alcohols, aldehydes, ketones or acid compounds;

[0035] Wherein, the catalyst is a compound that can generate chlorine or bromine free radicals in situ;

[0036] The oxidant is selected from oxygen or air;

[0037] The compound containing saturated carbon-hydrogen bonds is selected from C 1 -C 20 Alkanes, C 4 -C 20 At least one of cycloalkane or arylalkane compounds; the arylalkane compound is selected from at least one of the compounds represented by formula I;

[0038]

[0039] R 1 -R 7 Each independently selected from H, C 1 -C 10 Hydrocarbon, C 1 -C 10 Hydrocarbyloxy, C 6 -C 20 Aryl, C 5 -C 20 Heteroaryl, C 5 -C 20 Unsaturated cyclic group, C 2 -C 10 ester group, hydroxyl group, mercapto group, trifluoromethylthio group, trifluoromethoxy group, cyano group, nitro group, trifluoromethyl group, halogen group, benzoyl group, alcohol methyl group or aldehyde group; R 1-R 7 Two adjacent groups in the heteroaryl group can be connected to form a five- to ten-membered ring; the heteroatoms on the heteroaryl group are each independently selected from O, S or N.

[0040] The C 5 -C 20 Unsaturated cyclic group refers to C 5 -C 20 A partially or fully unsaturated cyclic group.

[0041] The benzoyl group mentioned in this application refers to C 6 H 5 -C(O)-.

[0042] The present application has no particular limitation on the method for separating and purifying the target product, as long as the purpose of the present application can be achieved. For example, column chromatography can be used for separation, which may specifically include the following steps: after the oxidation reaction is completed, the catalyst is removed under reduced pressure, and then the target product is obtained by column chromatography.

[0043] In some embodiments of the present application, the compound containing a saturated carbon-hydrogen bond is selected from C 1 -C 8 Alkanes, C 5 -C 10 At least one of cycloalkane or arylalkane compounds; the arylalkane compound is selected from at least one of the compounds represented by formula IIa or the compounds represented by formula IIb;

[0044]

[0045] In the formula IIa, n is 1, 2 or 3, R 1 -R 5 Each independently selected from H, C 1 -C 10 Hydrocarbon, C 1 -C 10 Hydrocarbyloxy, C 6 -C 20 Aryl, C 5 -C 20 Heteroaryl, C 5 -C 20 Unsaturated cyclic group, C 2 -C 10 ester group, hydroxyl group, mercapto group, trifluoromethylthio group, trifluoromethoxy group, cyano group, nitro group, trifluoromethyl group, halogen group, benzoyl group, alcohol methyl group or aldehyde group; R 1 -R 5 Two adjacent groups in the heteroaryl group can be connected to form a five- to ten-membered ring; the heteroatoms on the heteroaryl group are each independently selected from O, S or N;

[0046] In the formula IIb, R 1 -R 4 Each independently selected from H, C 1 -C 10 Hydrocarbon, C 1 -C 10 Hydrocarbyloxy, C 6 -C 20 Aryl, C 5 -C 20 Heteroaryl, C 5 -C 20 Unsaturated cyclic group, C 2 -C 10 ester group, hydroxyl group, mercapto group, trifluoromethylthio group, trifluoromethoxy group, cyano group, nitro group, trifluoromethyl group, halogen group, benzoyl group, alcohol methyl group or aldehyde group; R 1 -R 4 Two adjacent groups in the heteroaryl group can be connected to form a five- to ten-membered ring; the heteroatoms on the heteroaryl group are each independently selected from O, S or N.

[0047] In some embodiments of the present application, in the formula IIa, R 1 -R 5 Each independently selected from H, C 1 -C 10 Hydrocarbon, C 1 -C 10 Hydrocarbyloxy, C 2 -C 10 Ester, cyano, nitro, trifluoromethyl, halogen or benzoyl; R 1 -R 5 Two adjacent groups can be linked to form a five- to eight-membered ring.

[0048] In some embodiments of the present application, in the formula IIa, R 1 -R 5 Each independently selected from H, C 1 -C 5 Hydrocarbon, C 1 -C 3 Hydrocarbyloxy, C 2 -C 3 ester, cyano, nitro, trifluoromethyl, F, Cl, Br, I or benzoyl; R 1 -R 5 Two adjacent groups can be linked to form a five- to eight-membered ring.

[0049] In some embodiments of the present application, in the formula IIa, R 1 -R 5 R is independently selected from H, F, Cl, Br, I, cyano, acetoxy, nitro, trifluoromethyl, benzoyl, methoxy or tert-butyl;1 -R 5 Two adjacent groups can be connected to form a five- to seven-membered ring.

[0050] The acetoxy group mentioned in this application refers to CH 3 -C(O)-O-; the tert-butyl group mentioned in this application refers to -C(CH 3 ) 3 .

[0051] In some embodiments of the present application, in the formula IIa, R 1 -R 5 One of them is selected from F, Cl, Br, I, cyano, acetoxy, nitro, trifluoromethyl, benzoyl, methoxy or tert-butyl, and the others are selected from H.

[0052] In some embodiments of the present application, in the formula IIb, R 1 -R 4 Each is independently selected from H, F, Cl, Br, I, cyano, acetoxy, nitro, trifluoromethyl, benzoyl, methoxy or tert-butyl.

[0053] In some embodiments of the present application, the compound containing a saturated carbon-hydrogen bond is selected from methane, ethane, propane, butane, cyclopentane, cyclohexane, n-octane, toluene, 4-chlorotoluene, 4-cyanotoluene, 3-cyanotoluene, 4-acetoxytoluene, 2-bromotoluene, 2-fluorotoluene, 4-fluorotoluene, 4-nitrotoluene, 4-trifluoromethyltoluene, 3-trifluoromethyltoluene, 4-benzoyltoluene, 4-methoxytoluene, 4-tert-butyltoluene, tetralin or ethyl benzene.

[0054] In some embodiments of the present application, the compound containing a saturated carbon-hydrogen bond is selected from methane, ethane, propane, butane, cyclopentane, cyclohexane, n-octane, toluene, 4-chlorotoluene, 4-cyanotoluene, 3-cyanotoluene, 4-acetoxytoluene, 2-bromotoluene, 2-fluorotoluene, 4-fluorotoluene, 4-trifluoromethyltoluene, 3-trifluoromethyltoluene, 4-benzoyltoluene, tetralin or ethylbenzene.

[0055] In some embodiments of the present application, the compound containing a saturated carbon-hydrogen bond is selected from methane, ethane, propane, butane, cyclopentane, cyclohexane, n-octane, toluene, 4-chlorotoluene, 4-cyanotoluene, 3-cyanotoluene, 2-fluorotoluene, 4-fluorotoluene, 4-trifluoromethyltoluene, 3-trifluoromethyltoluene, 4-benzoyltoluene, tetralin or ethyl benzene.

[0056] In some embodiments of the present application, the catalyst is selected from a halogen-containing organic solvent, and the halogen-containing organic solvent is selected from at least one of dichloromethane, deuterated dichloromethane, 1,1-dichloroethane, 1,2-dichloroethane, trichloroethane, tetrachloroethane, dibromomethane, 1,1-dibromoethane, 1,2-dibromoethane, trichloromethane, tribromomethane, tetrachloromethane, tetrabromomethane, chlorobenzene, bromobenzene, dichlorobenzene, dibromobenzene, trichlorobenzene and tribromobenzene.

[0057] The present application has no particular limitation on the amount of the catalyst, as long as the purpose of the present application can be achieved. For example, when the compound containing a saturated carbon-hydrogen bond described in the present application is liquid at room temperature, the ratio of the number of moles of the compound containing a saturated carbon-hydrogen bond to the volume of the catalyst is (0.1-0.5) mol: (0.1-0.7) mL, which can be 0.1 mol: 0.7 mL, 0.3 mol: 0.7 mL, 0.5 mol: 0.7 mL, 0.1 mol: 0.4 mL, 0.3 mol: 0.4 mL, 0.5 mol: 0.4 mL, 0.1 mol: 0.1 mL, 0.3 mol: 0.1 mL, 0.5 mol: 0.1 mL, or any two of the above ratios. is a ratio within the range formed by the endpoint; when the compound containing saturated carbon-hydrogen bonds described in the present application is in a gaseous state at room temperature, such as methane, ethane, propane and butane, the ratio of the amount of the compound containing saturated carbon-hydrogen bonds and the volume of the catalyst is (0.3-0.7) atm: (0.1-0.7) mL, which can be 0.3atm: 0.7mL, 0.5atm: 0.7mL, 0.7atm: 0.7mL, 0.3atm: 0.4mL, 0.5atm: 0.4mL, 0.7atm: 0.4mL, 0.3atm: 0.1mL, 0.5atm: 0.1mL, 0.7atm: 0.1mL or any two of the above ratios as the ratio within the range formed by the endpoint.

[0058] In some embodiments of the present application, the reaction temperature of the oxidation reaction is 0°C-100°C, preferably 20°C-40°C; the reaction time of the oxidation reaction is 8h-48h. In some embodiments of the present application, the reaction temperature of the oxidation reaction described in the present application can be 0°C, 10°C, 20°C, 30°C, 40°C, 50°C, 60°C, 70°C, 80°C, 90°C, 100°C or a value within the range formed by any two of the above values ​​as endpoints. The reaction temperature of the oxidation reaction of the present application is set within the above range, with good reaction speed and reaction efficiency; when the reaction temperature is too low, the reaction speed and efficiency will be reduced; and when the reaction temperature is too high, the solvent and / or catalyst are easy to volatilize, affecting the reaction efficiency.

[0059] In some embodiments of the present application, the pressure of the oxidant is 0.5atm-100atm, preferably 0.5atm-5atm. In some embodiments of the present application, the pressure of the oxidant described in the present application can be 0.5atm, 1atm, 2atm, 3atm, 4atm, 5atm, 10atm, 20atm, 30atm, 40atm, 50atm, 60atm, 70atm, 90atm, 100atm or any two of the above values ​​as endpoints. The pressure of the oxidant of the present application is set within the above range, with a good reaction yield, and a low reaction cost and a small safety hazard; when the pressure of the oxidant is too low, the reaction yield will decrease; and when the pressure of the oxidant is too high, the cost of the reaction and the safety hazard will increase.

[0060] In some embodiments of the present application, the wavelength of the visible light is 330nm-550nm. In some embodiments of the present application, the wavelength of the visible light described in the present application can be 330nm, 340nm, 350nm, 360nm, 370nm, 380nm, 390nm, 400nm, 410nm, 420nm, 430nm, 440nm, 450nm, 460nm, 470nm, 480nm, 490nm, 500nm, 510nm, 520nm, 530nm, 540nm, 550nm or any two of the above numerical values ​​as the numerical value in the range formed by endpoints. The visible light wavelength of the present application is arranged in the above range, with good reaction yield. The visible light described in the present application can be derived from a monochromatic light source with a wavelength of 330nm-550nm.

[0061] In some embodiments of the present application, the solvent used in the oxidation reaction is selected from at least one of acetonitrile, deuterated acetonitrile, dichloromethane, deuterated dichloromethane, 1,1-dichloroethane, 1,2-dichloroethane, trichloroethane, tetrachloroethane, dibromomethane, 1,1-dibromoethane, 1,2-dibromoethane, trichloromethane, tribromomethane, tetrachloromethane, tetrabromomethane, chlorobenzene, bromobenzene, dichlorobenzene, dibromobenzene, trichlorobenzene and tribromobenzene. The present application has no particular limitation on the amount of solvent used, as long as the purpose of the present application can be achieved. For example, when the compound containing a saturated carbon-hydrogen bond described in the present application is liquid at room temperature, the ratio of the number of moles of the compound containing a saturated carbon-hydrogen bond to the volume of the solvent is (0.1-0.5) mol: (1.3-2.0) mL, which can be 0.1 mol: 1.3 mL, 0.3 mol: 1.3 mL, 0.5 mol: 1.3 mL, 0.1 mol: 1.6 mL, 0.3 mol: 1.6 mL, 0.5 mol: 1.6 mL, 0.1 mol: 2.0 mL, 0.3 mol: 2.0 mL, 0.5 mol: 2.0 mL, or any two of the above ratios. The ratio within the range formed by the endpoint; when the compound containing saturated carbon-hydrogen bonds described in the present application is in a gaseous state at room temperature, such as methane, ethane, propane and butane, the ratio of the amount of the compound containing saturated carbon-hydrogen bonds and the volume of the solvent is (0.3-0.7)atm:(1.3-2.0)mL, which can be 0.3atm:1.3mL, 0.5atm:1.3mL, 0.7atm:1.3mL, 0.3atm:1.6mL, 0.5atm:1.6mL, 0.7atm:1.6mL, 0.3atm:2.0mL, 0.5atm:2.0mL, 0.7atm:2.0mL or any two of the above ratios as the ratio within the range formed by the endpoint.

[0062] In some embodiments of the present application, when the compound containing saturated carbon-hydrogen bonds is liquid at room temperature, the oxidation reaction uses acetonitrile as a solvent and dichloromethane as a catalyst and solvent. In some embodiments of the present application, the ratio of the mole of the compound containing saturated carbon-hydrogen bonds described in the present application to the total volume of acetonitrile and dichloromethane is (0.1-0.5) mol: 2.0 mL, which can be 0.1 mol: 2.0 mL, 0.2 mol: 2.0 mL, 0.3 mol: 2.0 mL, 0.4 mol: 2.0 mL, 0.5 mol: 2.0 mL or any two of the above ratios as endpoints. In some embodiments of the present application, the volume ratio of dichloromethane to acetonitrile is 0.7: (0.5-2.5), preferably 0.7: 1.3. The volume ratio of dichloromethane to acetonitrile described in the present application can be 0.7:0.5, 0.7:0.7, 0.7:0.9, 0.7:1.0, 0.7:1.1, 0.7:1.3, 0.7:1.5, 0.7:1.7, 0.7:1.9, 0.7:2.1, 0.7:2.3, 0.7:2.5 or a ratio within the range formed by any two of the above ratios as endpoints. In some embodiments of the present application, the ratio of the number of moles of the compound containing a saturated carbon-hydrogen bond to the volume of dichloromethane is (0.1-0.5) mol:0.7 mL. The ratio of the molar number of the compound containing a saturated carbon-hydrogen bond described in the present application to the volume of dichloromethane can be 0.1 mol: 0.7 mL, 0.2 mol: 0.7 mL, 0.3 mol: 0.7 mL, 0.4 mol: 0.7 mL, 0.5 mol: 0.7 mL or a ratio within the range formed by any two of the above ratios as endpoints.

[0063] In some embodiments of the present application, when the compound containing saturated carbon-hydrogen bonds is gaseous at room temperature, such as methane, ethane, propane and butane, the oxidation reaction uses deuterated acetonitrile as a solvent and deuterated dichloromethane as a catalyst and solvent. In some embodiments of the present application, the ratio of the amount of the compound containing saturated carbon-hydrogen bonds described in the present application to the total volume of deuterated acetonitrile and deuterated dichloromethane is (0.3-0.7) atm: 2.0 mL, which can be 0.3atm: 2.0 mL, 0.4atm: 2.0 mL, 0.5atm: 2.0 mL, 0.6atm: 2.0 mL, 0.7atm: 2.0 mL or any two of the above ratios as the ratio within the range formed by the endpoints. In some embodiments of the present application, the volume ratio of deuterated dichloromethane to deuterated acetonitrile is 0.7:(0.5-2.5), preferably 0.7:1.3; the volume ratio of deuterated dichloromethane to deuterated acetonitrile can be 0.7:0.5, 0.7:0.7, 0.7:0.9, 0.7:1.0, 0.7:1.1, 0.7:1.3, 0.7:1.5, 0.7:1.7, 0.7:1.9, 0.7:2.1, 0.7:2.3, 0.7:2.5 or a ratio within the range formed by any two of the above ratios as endpoints. In some embodiments of the present application, the ratio of the amount of the compound containing a saturated carbon-hydrogen bond to the volume of deuterated dichloromethane is (0.3-0.7) atm: 0.7 mL; the ratio of the amount of the compound containing a saturated carbon-hydrogen bond to the volume of deuterated dichloromethane can be 0.3 atm: 0.7 mL, 0.4 atm: 0.7 mL, 0.5 atm: 0.7 mL, 0.6 atm: 0.7 mL, 0.7 atm: 0.7 mL or a ratio within the range formed by any two of the above ratios as endpoints.

[0064] The present application uses compounds containing saturated carbon-hydrogen bonds as starting materials, and uses cheap, green and easily available oxygen or air as an oxidant. Since the solvent itself, such as dichloromethane, can generate chlorine or bromine free radicals in situ, the chlorine or bromine free radicals generated in situ in the solvent can be directly used as a catalyst. The present application has the advantages of abundant and readily available sources of reaction raw materials, mild reaction conditions, good compatibility of raw material functional groups, simple operation, high reaction safety, green environmental protection and low production cost.

[0065] Example

[0066] The following examples and comparative examples are given to more specifically describe the embodiments of the present application. Various tests and evaluations were performed according to the following methods. In addition, unless otherwise specified, "parts" and "%" are based on mass. The room temperature in the following examples refers to 25°C.

[0067] Example 1

[0068] In a 25 mL quartz tube, 18.4 mg of toluene, 0.7 mL of dichloromethane and 1.3 mL of acetonitrile were added in sequence to obtain a mixed solution; 1 atm of oxygen was introduced, and the mixed solution was irradiated at 35°C and 400 nm for 12 h. Dichloromethane was removed under reduced pressure, and the target product, benzoic acid (20.5 mg, yield 82%), was obtained by column chromatography.

[0069] The structural formula of the target product:

[0070] The H NMR spectrum of the target product is shown in Figure 1 As shown, the carbon NMR spectrum is as follows Figure 2 As shown, NMR data: 1 HNMR (400 MHz, DMSO-d 6 )δ12.94(s,1H),7.95(d,J=7.4Hz,2H),7.62(t,J=7.4Hz,1H),7.49(t,J=7.6Hz,2H).; 13 C NMR (100 MHz, DMSO-d 6 )δ167.78,133.32,131.22,129.72,129.02.

[0071] Example 2

[0072] In a 25 mL quartz tube, 41.1 mg of toluene, 0.7 mL of dichloromethane and 1.3 mL of acetonitrile were added in sequence to obtain a mixed solution; 1 atm of oxygen was introduced, and the obtained mixed solution was irradiated at 35°C and 400 nm for 12 h. Dichloromethane was removed under reduced pressure, and the target product benzoic acid (42.1 mg, yield 77%) was obtained by column chromatography.

[0073] The structural formula of the target product identified by NMR is:

[0074] Example 3

[0075] In a 25 mL quartz tube, 18.4 mg of toluene, 0.7 mL of dichloromethane and 1.3 mL of acetonitrile were added in sequence to obtain a mixed solution; 1 atm of oxygen was introduced, and the mixed solution was irradiated at 35°C and 390 nm for 12 h. Dichloromethane was removed under reduced pressure, and the target product, benzoic acid (21.0 mg, yield 84%), was obtained by column chromatography.

[0076] The structural formula of the target product identified by NMR is:

[0077] Example 4

[0078] In a 25 mL quartz tube, 24.3 mg of 4-chlorotoluene, 0.7 mL of dichloromethane and 1.3 mL of acetonitrile were added in sequence to obtain a mixed solution; 1 atm of oxygen was introduced, and the obtained mixed solution was irradiated at 35°C and 400 nm for 12 h. Dichloromethane was removed under reduced pressure, and the target product 4-chlorobenzoic acid (24.6 mg, yield 82%) was obtained by column chromatography.

[0079] The structural formula of the target product:

[0080] NMR data of the target product: 1 H NMR (400 MHz, DMSO-d 6 )δ13.15(s,1H),7.94(d,J=8.6Hz,2H),7.56(d,J=8.4Hz,2H).; 13 C NMR (100 MHz, DMSO-d 6 )δ166.92,138.26,131.61,130.12,129.21.

[0081] Example 5

[0082] In a 25 mL quartz tube, 23.5 mg of 4-cyanotoluene, 0.7 mL of dichloromethane and 1.3 mL of acetonitrile were added in sequence to obtain a mixed solution; 1 atm of oxygen was introduced, and the obtained mixed solution was irradiated at 35°C and 400 nm for 12 h. Dichloromethane was removed under reduced pressure, and the target product 4-cyanobenzoic acid (25.1 mg, yield 85%) was obtained by column chromatography.

[0083] The structural formula of the target product:

[0084] NMR data of the target product: 1 H NMR (400 MHz, DMSO-d 6 )δ13.54(s,1H),8.08(d,J=8.2Hz,2H),7.98(d,J=8.2Hz,2H).; 13 C NMR (100 MHz, DMSO-d 6 )δ166.45,135.37,133.16,130.42,118.65,115.54.

[0085] Example 6

[0086] In a 25 mL quartz tube, 24.6 mg of 3-cyanotoluene, 0.7 mL of dichloromethane and 1.3 mL of acetonitrile were added in sequence to obtain a mixed solution; 1 atm of oxygen was introduced, and the obtained mixed solution was irradiated at 35°C and 400 nm for 12 h. Dichloromethane was removed under reduced pressure, and the target product 3-cyanobenzoic acid (30.9 mg, yield 78%) was obtained by column chromatography.

[0087] The structural formula of the target product:

[0088] NMR data of the target product: 1 H NMR (400 MHz, DMSO-d 6 )δ8.27(s,1H),8.23(d,J=8.0Hz,1H),8.07(d,J=8.0Hz,1H),7.71(t,J=8.0Hz,1H).; 13 C NMR (100 MHz, DMSO-d 6 )δ165.77,135.98,133.72,132.72,129.98,118.12,111.81.

[0089] Example 7

[0090] In a 25 mL quartz tube, 30.0 mg of 4-acetoxytoluene, 0.7 mL of dichloromethane and 1.3 mL of acetonitrile were added in sequence to obtain a mixed solution; 1 atm of oxygen was introduced, and the obtained mixed solution was irradiated at 35°C and 400 nm for 12 h. Dichloromethane was removed under reduced pressure, and the target product 4-acetoxybenzoic acid (23.4 mg, yield 65%) was obtained by column chromatography.

[0091] The structural formula of the target product:

[0092] NMR data of the target product: 1 H NMR (400 MHz, DMSO-d 6 )δ12.99(s,1H),7.98(d,J=6.0Hz,2H),7.26(d,J=6.2Hz,2H),2.29(s,3H).; 13 C NMR (100 MHz, DMSO-d 6 )δ168.83,166.59,153.93,130.84,128.28,122.04,20.86.

[0093] Example 8

[0094] In a 25 mL quartz tube, 34.2 mg of 2-bromotoluene, 0.7 mL of dichloromethane and 1.3 mL of acetonitrile were added in sequence to obtain a mixed solution; 1 atm of oxygen was introduced, and the mixed solution was irradiated at 35°C and 400 nm for 12 h. Dichloromethane was removed under reduced pressure, and the target product 2-bromobenzoic acid (26.5 mg, yield 66%) was obtained by column chromatography.

[0095] The structural formula of the target product:

[0096] NMR data of the target product: 1 H NMR (400 MHz, DMSO-d 6 )δ13.37(s,1H),7.73(m,2H),7.45(m,2H).; 13 C NMR (100 MHz, DMSO-d 6 )δ167.34,133.74,132.49,130.56,127.69,119.90.

[0097] Example 9

[0098] In a 25 mL quartz tube, 22.0 mg of 2-fluorotoluene, 0.7 mL of dichloromethane and 1.3 mL of acetonitrile were added in sequence to obtain a mixed solution; 1 atm of oxygen was introduced, and the obtained mixed solution was irradiated at 35°C and 400 nm for 12 h. Dichloromethane was removed under reduced pressure, and the target product 2-fluorobenzoic acid (25.5 mg, yield 91%) was obtained by column chromatography.

[0099] The structural formula of the target product:

[0100] NMR data of the target product: 1 H NMR (400 MHz, DMSO-d 6 )δ13.21(s,1H),7.86(t,J=8.0Hz,1H),7.63(m,1H),7.30(m,2H).; 13 C NMR (100 MHz, DMSO-d 6 )δ165.03,162.36,134.72,134.63,131.87,124.41,117.00,116.96,116.78,116.74.

[0101] Example 10

[0102] In a 25 mL quartz tube, 22.0 mg of 4-fluorotoluene, 0.7 mL of dichloromethane and 1.3 mL of acetonitrile were added in sequence to obtain a mixed solution; 1 atm of oxygen was introduced, and the obtained mixed solution was irradiated at 35°C and 400 nm for 12 h. Dichloromethane was removed under reduced pressure, and the target product 4-fluorobenzoic acid (26.3 mg, yield 94%) was obtained by column chromatography.

[0103] The structural formula of the target product:

[0104] NMR data of the target product: 1 H NMR (400 MHz, DMSO-d 6 )δ13.21(s,1H),7.86(t,J=8.0Hz,1H),7.63(m,1H),7.30(m,2H).; 13 C NMR (100 MHz, DMSO-d 6 )δ165.03,162.36,134.72,134.63,131.87,124.41,117.00,116.96,116.78,116.74.

[0105] Embodiment 11

[0106] In a 25 mL quartz tube, 27.4 mg of 4-nitrotoluene, 0.7 mL of dichloromethane and 1.3 mL of acetonitrile were added in sequence to obtain a mixed solution; 1 atm of oxygen was introduced, and the mixed solution was irradiated at 35°C and 400 nm for 12 h. Dichloromethane was removed under reduced pressure, and the target product 4-nitrobenzoic acid (7.4 mg, yield 22%) was obtained by column chromatography.

[0107] The structural formula of the target product:

[0108] NMR data of the target product: 1 H NMR (400 MHz, DMSO-d 6 )δ13.65(s,1H),8.32(d,J=8.0Hz,2H),8.17(d,J=8.0Hz,2H).; 13 C NMR (100 MHz, DMSO-d 6 )δ165.78,150.03,136.36,130.68,123.72.

[0109] Example 12

[0110] In a 25 mL quartz tube, 32.0 mg of 4-trifluoromethyltoluene, 0.7 mL of dichloromethane and 1.3 mL of acetonitrile were added in sequence to obtain a mixed solution; 1 atm of oxygen was introduced, and the obtained mixed solution was irradiated at 35°C and 400 nm for 12 h. Dichloromethane was removed under reduced pressure, and the target product 4-trifluoromethylbenzoic acid (35.0 mg, yield 92%) was obtained by column chromatography.

[0111] The structural formula of the target product:

[0112] NMR data of the target product: 1 H NMR (400 MHz, DMSO-d 6 )δ13.45(s,1H),8.13(d,J=8.0Hz,2H),7.87(d,J=8.0Hz,2H).; 13 C NMR (100 MHz, DMSO-d 6 )δ166.18,134.60,132.95,132.64,132.32,132.00,130.09,125.57,125.54,122.45.

[0113] Example 13

[0114] In a 25 mL quartz tube, 32.0 mg of 3-trifluoromethyltoluene, 0.7 mL of dichloromethane and 1.3 mL of acetonitrile were added in sequence to obtain a mixed solution; 1 atm of oxygen was introduced, and the obtained mixed solution was irradiated at 35°C and 400 nm for 12 h. Dichloromethane was removed under reduced pressure, and the target product 3-trifluoromethylbenzoic acid (31.1 mg, yield 82%) was obtained by column chromatography.

[0115] The structural formula of the target product:

[0116] NMR data of the target product: 1 H NMR (400 MHz, DMSO-d 6 )δ13.48(s,1H),8.22(d,J=8.0Hz,1H),8.17(s,1H),7.99(d,J=8.0Hz,1H),7.76(t,J=8.2Hz,1H).; 13 C NMR (100 MHz, DMSO-d 6 )δ166.00,133.20,131.90,130.07,129.38,129.35,129.31,125.55,125.51,125.47,125.43,122.43.

[0117] Embodiment 14

[0118] In a 25 mL quartz tube, 39.3 mg of 4-benzoyltoluene, 0.7 mL of dichloromethane and 1.3 mL of acetonitrile were added in sequence to obtain a mixed solution; 1 atm of oxygen was introduced, and the obtained mixed solution was irradiated at 35°C and 400 nm for 12 h. Dichloromethane was removed under reduced pressure, and the target product 4-benzoylbenzoic acid (38.0 mg, yield 84%) was obtained by column chromatography.

[0119] The structural formula of the target product:

[0120] NMR data of the target product: 1 H NMR (400 MHz, DMSO-d 6 )δ13.32(s,1H),8.10(d,J=8.2Hz,2H),7.82(d,J=8.0Hz,2H),7.76(d,J=8.0Hz,2H),7.73(t,J=8.2Hz,1H),7.58(t,J=8.-Hz,2H).; 13 C NMR (100 MHz, DMSO-d 6 )δ193.38,164.63,138.54,134.48,131.96,131.09,127.71,127.61,127.39,126.68.

[0121] Embodiment 15

[0122] In a 25 mL quartz tube, 29.6 mg of 4-tert-butyltoluene, 0.7 mL of dichloromethane and 1.3 mL of acetonitrile were added in sequence to obtain a mixed solution; 1 atm of oxygen was introduced, and the obtained mixed solution was irradiated at 35°C and 400 nm for 12 hours. Dichloromethane was removed under reduced pressure, and the target product 4-tert-butylbenzoic acid (11.4 mg, yield 32%) was obtained by column chromatography.

[0123] The structural formula of the target product:

[0124] NMR data of the target product: 1 H NMR (400 MHz, DMSO-d 6 )δ12.76(s,1H),7.87(d,J=8.0Hz,2H),7.51(d,J=8.0Hz,2H),1.30(s,9H).; 13 C NMR (100 MHz, DMSO-d 6 )δ167.21,155.77,129.16,128.01,125.33,34.74,30.84.

[0125] Example 16

[0126] In a 25 mL quartz tube, 24.4 mg of 4-methoxytoluene, 0.7 mL of dichloromethane and 1.3 mL of acetonitrile were added in sequence to obtain a mixed solution; 1 atm of oxygen was introduced, and the obtained mixed solution was irradiated at 35°C and 400 nm for 12 h. Dichloromethane was removed under reduced pressure, and the target product 4-methoxybenzoic acid (7.9 mg, yield 26%) was obtained by column chromatography.

[0127] The structural formula of the target product:

[0128] NMR data of the target product: 1 H NMR (400 MHz, DMSO-d 6 )δ12.59(s,1H),7.89(d,J=8.0Hz,2H),7.01(d,J=8.0Hz,2H),3.82(s,3H).; 13 C NMR (100 MHz, DMSO-d 6 )δ166.97,162.81,131.31,122.95,113.78,55.41.

[0129] Embodiment 17

[0130] In a 25mL quartz tube, 26.4mg of tetralin, 0.7mL of dichloromethane and 1.3mL of acetonitrile were added in sequence to obtain a mixed solution; 1atm of oxygen was introduced, and the obtained mixed solution was irradiated at 35°C and 400nm light source for 12h. Dichloromethane was removed under reduced pressure, and the target product benzocyclohexanone (23.4mg, yield 80%) was obtained by column chromatography.

[0131] The structural formula of the target product:

[0132] NMR data of the target product: 1 H NMR (400 MHz, CDCl 3 )δ8.04(d,J=7.7Hz,1H),7.46(d,J=7.5Hz,1H),7.32(t,J=7.5Hz,1H),7.25(s,1H),2.98(t,J=6.0Hz,2H),2.70-2.62(m,2H),2.15(q,2H); 13 C NMR (101 MHz, CDCl 3 )δ198.5,144.5,133.4,132.6,128.8,127.2,126.7,39.2,29.7,23.3.

[0133] Embodiment 18

[0134] In a 25mL quartz tube, 21.2mg of ethylbenzene, 0.7mL of dichloromethane and 1.3mL of acetonitrile were added in sequence to obtain a mixed solution; 1atm of oxygen was introduced, and the obtained mixed solution was irradiated at 35°C and 400nm light source for 12h. Dichloromethane was removed under reduced pressure, and the target product acetophenone (18.9mg, yield 79%) was obtained by column chromatography.

[0135] The structural formula of the target product:

[0136] NMR data of the target product: 1 H NMR (400 MHz, CDCl 3 )δ8.13(d,J=8.0Hz,2H),7.62(t,J=7.4Hz,1H),7.49(t,J=7.6Hz,2H); 13 C NMR (101 MHz, CDCl 3 )δ172.4,133.9,130.2,129.3,128.5.

[0137] Embodiment 19

[0138] A stirring bar was added to a 25 mL sealed tube, and 0.7 mL of deuterated dichloromethane and 1.3 mL of deuterated acetonitrile were added in sequence to obtain a mixed solution. The mixture was then vacuumed and degassed under freezing conditions (-20°C), and a mixed gas of methane and oxygen (the total mixed gas pressure was 1 atm, CH 4 :O 2 The sealed tube was then placed in front of a 400 nm LED light and reacted at room temperature for 24 hours. After the reaction was stopped, the yield of methanol was 4% and the yield of formic acid was 21% as determined by nuclear magnetic resonance.

[0139] H NMR spectrum data of formic acid: 1 H NMR (400MHz, CD 3 CN)δ8.08(s,1H).

[0140] Methanol H NMR spectrum data: 1 H NMR (400MHz, CD 3 CN) δ 3.31 (s, 0.6H).

[0141] Embodiment 20

[0142] A stirring bar was added to a 25 mL sealed tube, and 0.7 mL of deuterated dichloromethane and 1.3 mL of deuterated acetonitrile were added in sequence to obtain a mixed solution. The mixture was then vacuumed and degassed under freezing conditions (-20°C), and a mixed gas of ethane and oxygen (total pressure of the mixed gas was 1 atm, ethane:O 2The volume ratio of the reaction mixture is 1:1). The sealed tube was then placed in front of a 400 nm LED light and reacted at room temperature for 24 hours. After the reaction was stopped, nuclear magnetic resonance detection was performed to obtain the corresponding oxidation products and their yields, as shown in Table 1.

[0143] Table 1 Oxidation products of ethane

[0144] Oxidation products Formic acid Acetic acid Ethanol Methanol Total yield Yield 18％ 30％ 2％ 5％ 55％

[0145] Embodiment 21

[0146] A stirring bar was added to a 25 mL sealed tube, and 0.7 mL of deuterated dichloromethane and 1.3 mL of deuterated acetonitrile were added in sequence to obtain a mixed solution. The mixture was then vacuumed and degassed under freezing conditions (-20°C), and a mixed gas of propane and oxygen (total pressure of the mixed gas was 1 atm, propane:O 2 The volume ratio of the reaction mixture is 1:1). The sealed tube was then placed in front of a 400 nm LED light and reacted at room temperature for 24 hours. After the reaction was stopped, nuclear magnetic resonance detection was performed to obtain the corresponding oxidation products and their yields, as shown in Table 2.

[0147] Table 2 Oxidation products of propane

[0148] Oxidation products acetone Propionic acid Acetic acid Formic acid n-Propanol Isopropyl alcohol Total yield Yield 25％ 15％ 5％ 8％ 5％ 5％ 63％

[0149] Embodiment 22

[0150] A stirring bar was added to a 25 mL sealed tube, and 0.7 mL of deuterated dichloromethane and 1.3 mL of deuterated acetonitrile were added in sequence to obtain a mixed solution. The mixture was then vacuumed and degassed under freezing conditions (-20°C), and a mixed gas of butane and oxygen (total pressure of the mixed gas was 1 atm, butane:O 2 The volume ratio of the reaction mixture is 1:1). The sealed tube was then placed in front of a 400 nm LED light and reacted at room temperature for 24 hours. After the reaction was stopped, nuclear magnetic resonance detection was performed to obtain the corresponding oxidation products and their yields, as shown in Table 3.

[0151] Table 3 Oxidation products of butane

[0152] Oxidation products 2-Butanone Butyric acid Acetic acid Acetaldehyde Formic acid Total yield Yield 20％ 5％ 15％ 20％ 15％ 75％

[0153] Embodiment 23

[0154] In a 25 mL quartz tube, 16.8 mg of cyclohexane, 0.7 mL of dichloromethane and 1.3 mL of acetonitrile were added in sequence to obtain a mixed solution; 1 atm of oxygen was introduced, and the obtained mixed solution was irradiated at 35°C and 400 nm for 12 h. After the reaction was stopped, gas phase detection was used to obtain the corresponding oxidation products and their yields, as shown in Table 4.

[0155] Table 4 Oxidation products of cyclohexane

[0156] Oxidation products Formic acid Acetaldehyde Cyclohexanone Cyclohexanol Total yield Yield 2％ 2％ 25％ 21％ 50％

[0157] Embodiment 24

[0158]

[0159] In a 25 mL quartz tube, 22.4 mg of n-octane, 0.7 mL of dichloromethane and 1.3 mL of acetonitrile were added in sequence to obtain a mixed solution; 1 atm of oxygen was introduced, and the obtained mixed solution was irradiated at 35°C and 400 nm for 12 h. After the reaction was stopped, gas phase detection was used to obtain the corresponding oxidation products and their yields, as shown in Table 5.

[0160] Table 5 Oxidation products of n-octane

[0161] Oxidation products acetone Acetic acid Acetaldehyde 2-Octanone Total yield Yield 8％ 12％ 5％ 20％ 45％

[0162] Examples 25-29

[0163] Except for adjusting the parameters as shown in Table 6, the rest is the same as Example 1.

[0164] Comparative Example 1-2

[0165] Except for adjusting the parameters as shown in Table 6, the rest is the same as Example 1.

[0166] The relevant parameters in the above-mentioned Examples 1-3, Examples 25-29 and Comparative Examples 1-2 are shown in the following Table 6.

[0167] Table 6 Related parameters in Examples 1-3, Examples 25-29 and Comparative Examples 1-2

[0168]

[0169]

[0170] It can be seen from Table 6 above that the oxygen pressure, light source wavelength and reaction temperature in Examples 1-3 and Examples 25-29 are within the scope of the present application, and the yield of the target product is relatively high.

[0171] Compared with Example 1, the reaction temperature of Example 25 was reduced to 10°C, and the yield of the target product was reduced; the reaction temperature of Example 26 was increased to 80°C, and the yield of the target product was also reduced; the reaction temperature of Comparative Example 2 was increased to 120°C, which is not within the scope of this application, resulting in the yield of the target product further reduced to 30%. Without being limited to any theory, the inventors of this application believe that when the reaction temperature is too low, the reaction speed and efficiency will be reduced; and when the reaction temperature is too high, dichloromethane will volatilize, affecting the reaction efficiency.

[0172] The wavelength of the light source in Comparative Example 1 was set to 600 nm, which is not within the scope of the present application, resulting in a reduction in the yield of the target product to 10%.

[0173] The method for synthesizing alcohol, aldehyde, ketone or acid compounds from compounds containing saturated carbon-hydrogen bonds provided in the present application uses compounds containing saturated carbon-hydrogen bonds as starting materials, uses safe, cheap, green and easily available oxygen or air as oxidant, and uses chlorine or bromine free radicals generated in situ in the solvent as catalyst; it has the advantages of abundant and easily available sources of reaction raw materials, mild reaction conditions, good compatibility of raw material functional groups, simple operation, high reaction safety, green environmental protection and low production cost. In addition, because the solvent itself, such as dichloromethane, can generate chlorine or bromine free radicals in situ and can be used as a catalyst, no additional catalyst needs to be added, thereby saving reaction costs and improving reaction efficiency.

[0174] The above description is only a preferred embodiment of the present application and is not intended to limit the present application. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present application shall be included in the scope of protection of the present application.

Claims

1. A method for synthesizing alcohol, aldehyde, ketone or acid compounds from compounds containing saturated carbon-hydrogen bonds, It is characterized in that include: Under visible light conditions, compounds containing saturated carbon-hydrogen bonds and oxidants undergo oxidation reactions under the action of catalysts to obtain alcohols, aldehydes, ketones or acid compounds; Wherein, the catalyst is a compound that can generate chlorine or bromine free radicals in situ; The oxidant is selected from oxygen or air; The compound containing saturated carbon-hydrogen bonds is selected from C 1 -C 20 Alkanes, C 4 -C 20 At least one of cycloalkane or arylalkane compounds; the arylalkane compound is selected from at least one of the compounds represented by formula I; R 1 -R 7 Each independently selected from H, C 1 -C 10 Hydrocarbon, C 1 -C 10 Hydrocarbyloxy, C 6 -C 20 Aryl, C 5 -C 20 Heteroaryl, C 5 -C 20 Unsaturated cyclic group, C 2 -C 10 ester group, hydroxyl group, mercapto group, trifluoromethylthio group, trifluoromethoxy group, cyano group, nitro group, trifluoromethyl group, halogen group, benzoyl group, alcohol methyl group or aldehyde group; R 1 -R 7 Two adjacent groups in the heteroaryl group can be connected to form a five- to ten-membered ring; the heteroatoms on the heteroaryl group are each independently selected from O, S or N.

2. The method according to claim 1, It is characterized in that The compound containing saturated carbon-hydrogen bonds is selected from C 1 -C 8 Alkanes, C 5 -C 10 At least one of cycloalkane or arylalkane compounds; the arylalkane compound is selected from at least one of the compounds represented by formula IIa or the compounds represented by formula IIb; In the formula IIa, n is 1, 2 or 3.

3. The method according to claim 2, It is characterized in that In the formula IIa, R 1 -R 5 Each independently selected from H, C 1 -C 10 Hydrocarbon, C 1 -C 10 Hydrocarbyloxy, C 2 -C 10 Ester, cyano, nitro, trifluoromethyl, halogen or benzoyl; R 1 -R 5 Two adjacent groups in the can be connected to form a five- to eight-membered ring; Preferably, in the formula IIa, R 1 -R 5 Each independently selected from H, C 1 -C 5 Hydrocarbon, C 1 -C 3 Hydrocarbyloxy, C 2 -C 3 ester, cyano, nitro, trifluoromethyl, F, Cl, Br, I or benzoyl; R 1 -R 5 Two adjacent groups can be linked to form a five- to eight-membered ring.

4. The method according to claim 2, It is characterized in that In the formula IIa, R 1 -R 5 R is independently selected from H, F, Cl, Br, I, cyano, acetoxy, nitro, trifluoromethyl, benzoyl, methoxy or tert-butyl; 1 -R 5 Two adjacent groups in the can be connected to form a five- to seven-membered ring; Preferably, in the formula IIa, R 1 -R 5 One of them is selected from F, Cl, Br, I, cyano, acetoxy, nitro, trifluoromethyl, benzoyl, methoxy or tert-butyl, and the others are selected from H.

5. The method according to claim 2, It is characterized in that In the formula IIb, R 1 -R 4 Each is independently selected from H, F, Cl, Br, I, cyano, acetoxy, nitro, trifluoromethyl, benzoyl, methoxy or tert-butyl.

6. The method according to claim 1, It is characterized in that The compound containing a saturated carbon-hydrogen bond is selected from methane, ethane, propane, butane, cyclopentane, cyclohexane, n-octane, toluene, 4-chlorotoluene, 4-cyanotoluene, 3-cyanotoluene, 4-acetoxytoluene, 2-bromotoluene, 2-fluorotoluene, 4-fluorotoluene, 4-nitrotoluene, 4-trifluoromethyltoluene, 3-trifluoromethyltoluene, 4-benzoyltoluene, 4-methoxytoluene, 4-tert-butyltoluene, tetralin or ethylbenzene, preferably selected from methane, ethane, propane, butane, cyclopentane, cyclohexane, n-octane, toluene, 4 The invention relates to methylbenzene, ...

7. The method according to any one of claims 1 to 6, It is characterized in that The catalyst is selected from a halogen-containing organic solvent, and the halogen-containing organic solvent is selected from at least one of dichloromethane, deuterated dichloromethane, 1,1-dichloroethane, 1,2-dichloroethane, trichloroethane, tetrachloroethane, dibromomethane, 1,1-dibromoethane, 1,2-dibromoethane, trichloromethane, tribromomethane, tetrachloromethane, tetrabromomethane, chlorobenzene, bromobenzene, dichlorobenzene, dibromobenzene, trichlorobenzene and tribromobenzene.

8. The method according to any one of claims 1 to 6, It is characterized in that The reaction temperature of the oxidation reaction is 0°C-100°C, preferably 20°C-40°C; the reaction time of the oxidation reaction is 8h-48h.

9. The method according to any one of claims 1 to 6, It is characterized in that The pressure of the oxidant is 0.5atm-100atm, preferably 0.5atm-5atm; Preferably, the wavelength of the visible light is 330nm-550nm.

10. The method according to any one of claims 1 to 6, It is characterized in that The solvent used in the oxidation reaction is selected from at least one of acetonitrile, deuterated acetonitrile, dichloromethane, deuterated dichloromethane, 1,1-dichloroethane, 1,2-dichloroethane, trichloroethane, tetrachloroethane, dibromomethane, 1,1-dibromoethane, 1,2-dibromoethane, trichloromethane, tribromomethane, tetrachloromethane, tetrabromomethane, chlorobenzene, bromobenzene, dichlorobenzene, dibromobenzene, trichlorobenzene and tribromobenzene.

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