Synthesis method of unsaturated ketone or arone compound

Abstract

The invention discloses a synthesis method of an unsaturated ketone or arone compound, which comprises the following steps: at a certain temperature, taking unsaturated hydrocarbon or aromatic hydrocarbon as a raw material, taking an N-hydroxyimide compound as a catalyst, adding an organic solvent for dissolving, introducing oxygen or air into a reaction solution under the irradiation of visible light, and carrying out oxidation reaction to obtain the unsaturated ketone or arone compound. And carrying out post-treatment separation to obtain the unsaturated ketone or arone. According to the method, air, oxygen-enriched gas or oxygen is used as a harmless oxidizing agent, visible light is used as an energy source to promote the reaction, and the method has the advantages that the reaction process is green and efficient, the cost is low, the dosage of the catalyst is small, and most of the catalyst can be recycled and reused; the atom economy is high.

Description

Technical Field

[0001] The present invention relates to a new method for green synthesis of unsaturated ketones or aromatic ketones, which uses air, oxygen-rich gas or oxygen as a harmless oxidant and visible light as an energy source to promote the reaction. The synthesis strategy has broad application prospects and is suitable for the synthesis of medicines, pesticides and dyes, showing significant economic value and practicality. Background Art

[0002] The allylic oxidation of olefins or aromatic hydrocarbons to generate unsaturated ketones or aromatic ketone compounds has important application value in organic synthesis. It exists in the synthesis of more than one hundred natural products and chemical drugs, but more than 80% of the reactions involve toxic metals, precious metals and transition metals. These catalysts are widely used in organic synthesis, but there are also certain environmental and safety risks.

[0003] At present, the existing technology mainly obtains the required unsaturated ketones or aromatic ketone compounds through high-valent chromium salts, high-valent iodides and chromium trioxide, but the disadvantages of this type of synthesis method are also obvious, such as large amount of catalyst used, serious pollution risks, high cost and so on. Therefore, it is urgent to develop a new green and efficient allylic oxidation method.

[0004] Su Wei Ke et al. reported an air-involved allylic oxidation method (CN100494149C), proposing to use dibenzoyl peroxide (BPO) as an initiator, oxygen as an oxidant, 1.2 equivalents of imide as a catalyst, ethyl acetate / cyclohexanone as a solvent, and 55°C insulation reaction to obtain an allylic oxidation product with a yield of more than 80%. The reaction is green and efficient, using cheap and recyclable imide as a catalyst, and by bubbling air or oxygen as an oxidant, a green and environmentally friendly method is achieved to obtain unsaturated ketones or aromatic ketone compounds. Although the reaction has a good effect, there is still room for optimization, such as whether it is possible to reduce the higher equivalent of imide and replace the higher boiling point cyclohexanone. Therefore, the present invention has developed a green, mild, efficient, novel and low-cost photocatalytic allylic oxidation strategy. Summary of the invention

[0005] In view of the above problems existing in the prior art, the present invention designs a green synthesis method for unsaturated ketones or aromatic ketone compounds which is green, efficient, low-cost, uses less catalyst and can be mostly recycled.

[0006] The invention discloses a method for synthesizing unsaturated ketone or aromatic ketone compounds. At a certain temperature, unsaturated hydrocarbon or aromatic hydrocarbon is used as a raw material, N-hydroxyimide compound is used as a catalyst, an organic solvent is added to dissolve, oxygen or air is introduced into the reaction liquid under visible light irradiation to carry out oxidation reaction, and the unsaturated ketone or aromatic ketone is obtained by post-treatment and separation.

[0007] The green synthesis method of the unsaturated ketone or aromatic ketone is characterized in that the unsaturated ketone is a chain or ring structure containing a C=CC=O bond; the aromatic ketone is an aromatic ketone or heterocyclic ketone containing a C=CC=O bond, and the heterocyclic ring is a five-membered heterocyclic ring containing O, or N, or S.

[0008] The green synthesis method of the unsaturated ketone or aromatic ketone is characterized in that the structural formula of the unsaturated ketone or aromatic ketone is one of the following formulas:

[0009]

[0010] The structural formula of the corresponding unsaturated hydrocarbon or aromatic hydrocarbon is one of the following:

[0011]

[0012] wherein R1 is hydrogen, or an alkyl group containing 1 to 6 carbon atoms, or an acyl group containing 2 to 4 carbon atoms, or a benzoyl group or a benzenesulfonyl group, or a silane group containing 1 to 6 carbon atoms;

[0013] R2 is hydrogen or an alkyl group containing 1 to 10 carbon atoms;

[0014] R3 is hydrogen or an alkyl group containing 1 to 10 carbon atoms;

[0015] R4, R5 are alkyl groups containing 1 to 3 carbon atoms;

[0016] R6 is hydrogen, or an alkyl group containing 1 to 6 carbon atoms, or a phenyl group;

[0017] R7 is hydrogen, or an alkyl or alkoxy group containing 1 to 6 carbon atoms, or a cyano group, or a halogen;

[0018] R8 is hydrogen or an alkyl group containing 1 to 6 carbon atoms;

[0019] Y is S, or O, or NH, or NCH3.

[0020] The method for synthesizing unsaturated ketones or aromatic ketone compounds is characterized in that the organic solvent is one of the following: dichloromethane, toluene, ethyl acetate, ethanol, methanol, 1,4-dioxane, tetrahydrofuran, ether, petroleum ether, 1,2-dichloroethane, acetone, butanone, 1,1-dichloroethane, cyclohexanone; the organic solvent is preferably cyclohexanone, ethyl acetate or tetrahydrofuran; the dispersion concentration of the unsaturated hydrocarbon or aromatic hydrocarbon raw material in the organic solvent is 0.1-1 mol / L.

[0021] The synthesis method of an unsaturated ketone or aromatic ketone compound is characterized in that the N-hydroxyimide compound is one of the following: N-hydroxysuccinimide, N-hydroxymaleimide, N-hydroxyphthalimide;

[0022] The ratio of the unsaturated hydrocarbon or aromatic hydrocarbon raw material to the catalyst substance is 1:0.1 to 2.0, preferably 1:0.3 to 0.45.

[0023] The method for synthesizing unsaturated ketone or aromatic ketone compounds is characterized in that the wavelength range of the visible light is 370nm to 455nm, preferably 405 to 455nm, and the power range of the visible light source is 10-100W, preferably 60-100W.

[0024] The method for synthesizing an unsaturated ketone or aromatic ketone compound is characterized in that the reaction temperature is 0 to 120°C, preferably room temperature to 60°C; the reaction time is 1 to 24 hours, preferably 2 to 10 hours.

[0025] The synthesis method of the unsaturated ketone or aromatic ketone compound is characterized in that the post-treatment method is as follows:

[0026] (1) After washing with water and saturated brine, the organic phase is dried by rotation, dichloromethane is added and cooled to 0° C., the catalyst is recovered by filtration, a dehydrating agent is added to the filtrate, the reaction is allowed to stand at 0° C. for 20-30 hours, the solvent is dried by rotation, and the unsaturated ketone or aromatic ketone compound is obtained by recrystallization, distillation or pulping;

[0027] (2) Cooling the reaction liquid to below 0° C., filtering and recovering the catalyst, adding a dehydrating agent to the filtrate, stirring the reaction at 0° C. for 20-30 hours, spinning the solvent to dryness, and subjecting the reaction to recrystallization, beating, distillation or beating to obtain the unsaturated ketone or aromatic ketone compound.

[0028] The method for synthesizing an unsaturated ketone or aromatic ketone compound is characterized in that the dehydrating agent is one of the following: ① a mixture of ferrous sulfate and pyridine or triethylamine, the mass of ferrous sulfate being 1-1.6 g / mL based on the volume of pyridine or triethylamine; ② triethylamine-acetic anhydride in a volume ratio of 1-2:1-3, preferably triethylamine-acetic anhydride in a volume ratio of 2:1.

[0029] The method for synthesizing unsaturated ketone or aromatic ketone compounds is characterized in that the recrystallization or pulping solvent is an aqueous solution of at least one of methanol, ethanol and acetone with a mass fraction of 70-90%.

[0030] The catalyst used in this study has good recyclability. The specific recovery method includes cooling the solution after the reaction to below 0°C to precipitate the catalyst, and then washing it by suction filtration to obtain a filter cake of the catalyst. The recovery process is highly efficient, with a recovery rate of 80% to 95%. The recovered catalyst can be directly used in the next round of reaction without further purification and refining.

[0031] The advantages of the present invention are as follows: 1. It is green and environmentally friendly, requiring only oxygen-containing air as an oxidant, without the need for heavy polluting reagents, and is environmentally friendly. 2. The process is advanced, using visible light of 370 to 455 nm as an energy source, and the reaction conditions are mild and safe. 3. The amount of catalyst used is small and can be recycled. 4. The reaction yield is high. 5. The method of the present invention does not require the participation of reagents such as heavy metals, photocatalysts, and high-valent iodine oxidants, and has high atom economy.

[0032] The present invention will be further described below in conjunction with specific embodiments, however, the protection scope of the present invention is not limited thereto:

[0033] Embodiment 1: 10mmol diphenylmethane, 3mmol N-hydroxysuccinimide, are added to a 25mL single-mouth flask, and 20mL ethyl acetate is added thereto, stirred until turbid, placed under a 100W 435nm ultraviolet lamp, air is introduced at 1mL / min, reacted for 5h, the solution becomes clear and transparent, and the reaction ends. After washing with water, ethyl acetate is spin-dried after washing with saturated salt water, dichloromethane is added to cool to 0°C and stirred for 30min, and after standing for 15min, 0.40g of catalyst is recovered by suction filtration, and the catalyst mass recovery rate is 82%. The filtrate is transferred to a 25mL single-mouth eggplant bottle, 0.5mL triethylamine and acetic anhydride are added in a volume ratio of 2:1 mixture, 0°C is stood for 24h, spin-dried, and recrystallized from 80% ethanol aqueous solution to obtain the final product benzophenone 1.51g, with a molar yield of 83%. 1 H NMR(400MHz,Chloroform-d)δ7.82(d,J=1.2Hz,2H),7.80(d,J=1.6Hz,2H),7.62–7.56(m,2H),7.48(dd,J=8.3,6.9Hz,4H); 13 C NMR (100MHz, Chloroform-d) δ196.8,137.6,132.5,130.1,128.3.

[0034] Embodiment 2: At room temperature, 5mmol cholesterol acetate, 1.5mmol N-hydroxyphthalimide, are added to a 100mL single-mouth flask, and 20mL ethyl acetate is added thereto, stirred until turbid, placed under a 80W 435nm ultraviolet lamp, air is introduced at 1mL / min, reacted for 6h, the solution becomes clear and transparent, and the reaction ends. After washing, ethyl acetate is spin-dried after washing with saturated common salt water, the reaction liquid temperature is cooled to below 0°C, filtered to recover 0.20g of catalyst, the catalyst mass recovery rate is 82%, the filtrate is transferred to a 50mL single-mouth eggplant bottle, 0.25g triethylamine and 0.25g acetic anhydride mixture are added, 0°C is left to stand for 24h, spin-dried, and recrystallized from 70% acetone aqueous solution to obtain 1.73g of product 7-ketocholesterol acetate, with a yield of 80%. 1 H NMR(400MHz,Chloroform-d)δ5.69(d,J=1.8Hz,1H),4.70(t,J=4.8Hz,1H),2.58–2.34(m,3H),2 .22(t,J=11.1Hz,1H),2.04(s,3H),1.97(ddd,J=17.1,8.2,3.3Hz,3H),1.74–1.61(m,2H),1.60–

[0035] 1.45(m,4H),1.40–1.26(m,6H),1.24(t,J=5.2Hz,2H),1.20(s,3H),1.17–1 .03(m,6H),0.91(d,J=6.4Hz,3H),0.85(dd,J=6.6,1.9Hz,6H),0.67(s,3H); 13 C NMR(100MHz,Chloroform-d)δ126.7,72.2,54.8,49.9,49.8,45.4,43.1,39.5,38.7,38.3,37 .8,36.2,36.0,35.7,28.6,28.00,27.4,26.3,23.8,22.8,22.6,21.3,21.2,18.9,17.3,12.0.

[0036] Example 3: At 60°C, 20mmol cyclohexene and 6mmol N-hydroxyphthalimide were added to a 100mL single-mouth flask, and 20mL ethyl acetate was added thereto, stirred until turbid, placed under a 100W 435nm ultraviolet lamp, air was introduced at 1mL / min, reacted for 6h, the solution became clear and transparent, and the reaction was completed. After washing with water, ethyl acetate was spin-dried after washing with saturated salt water, dichloromethane was added to cool to 0°C and stirred for 30min, and after standing for 15min, 0.91g of catalyst was recovered by suction filtration, and the catalyst mass recovery rate was 93%. The filtrate was transferred to a 25mL single-mouth eggplant bottle, 0.5mL triethylamine and 0.75g ferrous sulfate were added, and the product cyclohexenone 1.71g was obtained by distillation separation, and the molar yield was 89%. 1 H NMR(400MHz,Chloroform-d)δ6.89(ddd,J=10.2,5.0,2.8Hz,1H),5.87(ddt,J=10.1,3.6,2.1Hz,1H), 2.29(ddt,J=7.5,5.0,2.3Hz,2H), 2.23(ddp,J=6.4,4.4,2.1Hz,2H), 1.89(qq,J=6.1,3.7,3.0Hz,2H); 13 CNMR(100MHz,Chloroform-d)δ199.6,150.8,129.7,38.0,25.6,22.6.

[0037] Example 4: At 50°C, 5mmol compound 1, 1.5mmol N-hydroxyphthalimide, added to a 100mL single-mouth flask, and 20mL tetrahydrofuran was added thereto, stirred until turbid, placed under a 100W 455nm ultraviolet lamp, air was introduced at 1mL / min, reacted for 5h, the solution became clear and transparent, and the reaction was completed. After washing with water, the solvent was spin-dried after washing with saturated salt water, dichloromethane was added to cool to 0°C and stirred for 30min, and after standing for 15min, 0.20g of catalyst was recovered by suction filtration, and the catalyst mass recovery rate was 82%. The filtrate was transferred to a 25mL single-mouth eggplant bottle, 0.7mL pyridine, 1g ferrous sulfate were added, and 0°C was stood for 24h, concentrated, and recrystallized from 90% methanol aqueous solution to obtain 21.79g of product compound, with a molar yield of 78%. 1H NMR(600MHz,Chloroform-d)δ5.65(d,J=1.9Hz,1H),4.11(q,J=7.2Hz,2H),4.01–3.89(m,4H),2.6 6(dd,J=14.8,2.1Hz,1H),2.42(ddd,J=12.7,6.7,3.8Hz,1H),2.37–2.29(m,2H),2.25–2.16(m,2H) ,2.01(dt,J=12.7,3.4Hz,1H),1.96–1.79(m,4H),1.76–1.70(m,1H),1.65–1.52(m,4H),1.38–1.27 (m,5H),1.24(d,J=7.1Hz,3H),1.19(s,3H),1.15–1.06(m,2H),0.93(d,J=6.5Hz,3H),0.68(s,3H); 13 CNMR(150MHz,Chloroform-d)δ126.7,108.9,64.6,64.5,60.2,54.5,50.1,49.6,45.4,43. 2,41.7,38.7,38.3,35.6,35.3,31.3,31.1,31.0,28.4,26.3,21.2,18.5,16.9,14.3,12.0.

[0038]

[0039] Embodiment five: 15mmol 2-ethylfuran, 4.5mmol N-hydroxyphthalimide, are added to a 100mL single-mouth flask, and 20mL cyclohexanone is added thereto, stirred until turbid, placed under a 100W 435nm ultraviolet lamp, air is introduced at 1mL / min, reacted for 6h, the solution becomes clear and transparent, and the reaction ends. After washing with water, the solvent is spin-dried after washing with saturated common salt water, dichloromethane is added to cool to 0°C and stirred for 30min, and after standing for 15min, 0.65g of catalyst is recovered by suction filtration, and the catalyst mass recovery rate is 88%. The filtrate is transferred to a 25mL single-mouth eggplant bottle, 0.4mL triethylamine is added, 0.63g ferrous sulfate is added, and 0°C is stood for 24h, spin-dried and separated by column chromatography (petroleum ether: ethyl acetate = 4:1, volume ratio) to obtain pure 2-acetylfuran 1.35g, molar yield 83%. 1 H NMR (400MHz, DMSO-d6) δ7.97(dd,J=1.7,0.8Hz,1H),7.44(dd,J=3.5,0.8Hz,1H),6.70(dd,J=3.6,1.7Hz,1H),2.41(s,3H). 13C NMR (100MHz, DMSO-d6) δ186.3,152.5,148.1,119.0,112.9,26.4.

[0040] Example 6: The reaction solvent was replaced with 20 mL of 1,2-dichloroethane, and other operations were the same as in Example 1. The product molar yield was 61%, and the catalyst mass recovery rate was 80%.

[0041] Example 7: The solvent was replaced with 20 mL of acetone, and other operations were the same as in Example 1. The product molar yield was 56%, and the catalyst mass recovery rate was 81%.

[0042] Example 8: The solvent was replaced with 20 mL of 1,4-dioxane, and other operations were the same as in Example 1. The product molar yield was 60%, and the catalyst mass recovery rate was 82%.

[0043] Example 9: The light source is replaced with a 100 W 405 nm ultraviolet lamp, the reaction time is shortened to 4 h, and the other operations are the same as in Example 1. The product molar yield is 91%, and the catalyst mass recovery rate is 81%.

[0044] Example 10: The light source was replaced with a 100 W 370 nm ultraviolet lamp, the reaction time was shortened to 2 h, and the other operations were the same as in Example 1. The product molar yield was 76%, and the catalyst mass recovery rate was 82%.

[0045] Example 11: The light source was replaced with a 100 W 390 nm ultraviolet lamp, the reaction time was shortened to 3 h, and the other operations were the same as in Example 1. The product molar yield was 78%, and the catalyst mass recovery rate was 81%.

[0046] Example 12: The light source was replaced with a 100 W 455 nm ultraviolet lamp, the reaction time was extended to 6 h, and the other operations were the same as in Example 1. The product molar yield was 84%, and the catalyst mass recovery rate was 81%.

[0047] Example 13: The amount of catalyst N-hydroxysuccinimide used was 0.2 g, and other operations were the same as in Example 1. The product molar yield was 61% and the catalyst mass recovery rate was 68%.

[0048] Example 14: The amount of catalyst N-hydroxysuccinimide used was 0.4 g, and other operations were the same as in Example 1. The product molar yield was 87% and the catalyst mass recovery rate was 86%.

[0049] Example 15: The amount of catalyst N-hydroxysuccinimide used was 0.5 g, and other operations were the same as in Example 1. The product molar yield was 90%, and the catalyst mass recovery rate was 89%.

[0050] Example 16: The catalyst N-hydroxysuccinimide was replaced by an equal molar amount of N-hydroxymaleic acid imide, and other operations were the same as those in Example 1. The molar yield of the product was 76%, and the mass recovery rate of the catalyst was 81%.

[0051] Example 17: The oxidation reaction time was shortened to 2 h, and other operations were the same as in Example 1. The product molar yield was 31%, and the catalyst mass recovery rate was 80%.

[0052] Example 18: The oxidation reaction time was shortened to 3 h, and other operations were the same as in Example 1. The product molar yield was 73%, and the catalyst mass recovery rate was 80%.

[0053] Example 19: The oxidation reaction time was shortened to 4 h. Other operations were the same as those in Example 1. The product molar yield was 82% and the catalyst mass recovery rate was 81%.

[0054] Example 20: The volume ratio of the triethylamine and acetic anhydride mixture was adjusted to 1:1, and the other operations were the same as in Example 1. The product molar yield was 76%, and the catalyst mass recovery rate was 82%.

[0055] Example 21: The volume ratio of the mixture of triethylamine and acetic anhydride was adjusted to 1:2. The other operations were the same as in Example 1. The molar yield of the product was 74% and the catalyst mass recovery rate was 82%.

[0056] Example 22: The volume ratio of the mixture of triethylamine and acetic anhydride was adjusted to 1:3, and the other operations were the same as in Example 1. The product yield was 73% and the catalyst mass recovery rate was 82%.

[0057] Example 23: The air introduction rate was 2 mL / min, and other operations were the same as in Example 1. The product molar yield was 90%, and the catalyst mass recovery rate was 82%.

[0058] Example 24: The air introduction rate was 3 mL / min, and other operations were the same as in Example 1. The product molar yield was 88%, and the catalyst mass recovery rate was 83%.

[0059] Example 25: The light source power was replaced from 100 W to 60 W, the reaction time was extended to 6 h, and other operations were the same as in Example 1. The product molar yield was 80%, and the catalyst mass recovery rate was 82%.

[0060] Example 26: The light source power was replaced from 100 W to 20 W, the reaction time was extended to 12 h, and other operations were the same as in Example 1. The product molar yield was 67%, and the catalyst mass recovery rate was 83%.

[0061] Embodiments 27 to 39:

[0062] At 60°C, add 10mmol of aromatic hydrocarbon or olefin, 3mmol of N-hydroxysuccinimide to a 100mL three-necked flask, add 30mL of ethyl acetate, stir until turbid, place it under a 100W 435nm ultraviolet lamp, introduce air V=1mL / min, react for 5h, the solution becomes clear and transparent, and the reaction is over. After washing with water and saturated salt water, spin dry ethyl acetate, add 20mL of dichloromethane, cool to below 0°C, stir well for 30min, then let stand for 10min, filter, and recover the catalyst by filter cake. Transfer the filtrate to a 100mL three-necked flask, add 0.2mL of triethylamine and 0.1mL of acetic anhydride, and let stand at 0°C for 24h. After recrystallization, distillation or chromatography column separation, the pure product is obtained.

[0063] The detailed results are shown in the table below:

[0064]

[0065]

Claims

1. A method for synthesizing an unsaturated ketone or aromatic ketone compound, characterized in that At a certain temperature, unsaturated hydrocarbons or aromatic hydrocarbons are used as raw materials, N-hydroxyimide compounds are used as catalysts, an organic solvent is added to dissolve, oxygen or air is introduced into the reaction solution under visible light irradiation to carry out an oxidation reaction, and the unsaturated ketone or aromatic ketone is obtained by post-treatment and separation.

2. The method for synthesizing an unsaturated ketone or aromatic ketone compound according to claim 1, characterized in that The unsaturated ketone is a chain or ring structure containing a C=CC=O bond; the aromatic ketone is an aromatic ketone or a heterocyclic ketone containing a C=CC=O bond, and the heterocyclic ring is a five-membered heterocyclic ring containing O, N, or S.

3. The method for synthesizing an unsaturated ketone or aromatic ketone compound according to claim 1, characterized in that The unsaturated ketone or aromatic ketone structural formula is one of the following: The structural formula of the corresponding unsaturated hydrocarbon or aromatic hydrocarbon is one of the following: wherein R1 is hydrogen, or an alkyl group containing 1 to 6 carbon atoms, or an acyl group containing 2 to 4 carbon atoms, or a benzoyl group or a benzenesulfonyl group, or a silane group containing 1 to 6 carbon atoms; R2 is hydrogen or an alkyl group containing 1 to 10 carbon atoms; R3 is hydrogen or an alkyl group containing 1 to 10 carbon atoms; R4, R5 are alkyl groups containing 1 to 3 carbon atoms; R6 is hydrogen, or an alkyl group containing 1 to 6 carbon atoms, or a phenyl group; R7 is hydrogen, or an alkyl or alkoxy group containing 1 to 6 carbon atoms, or a cyano group, or a halogen; R8 is an alkyl group containing 1 to 3 carbon atoms; R9 is hydrogen or an alkyl group containing 1 to 6 carbon atoms; Y is S, or O, or NH, or NCH3.

4. The method for synthesizing an unsaturated ketone or aromatic ketone compound according to claim 1, characterized in that The organic solvent is one of the following: dichloromethane, toluene, ethyl acetate, ethanol, methanol, 1,4-dioxane, tetrahydrofuran, ether, petroleum ether, 1,2-dichloroethane, acetone, butanone, 1,1-dichloroethane, cyclohexanone; the organic solvent is preferably cyclohexanone, ethyl acetate or tetrahydrofuran; the dispersion concentration of the unsaturated hydrocarbon or aromatic hydrocarbon raw material in the organic solvent is 0.1-1 mol / L.

5. The method for synthesizing an unsaturated ketone or aromatic ketone compound according to claim 1, characterized in that The N-hydroxyimide compound is one of the following: N-hydroxysuccinimide, N-hydroxymaleimide, N-hydroxyphthalimide; The ratio of the unsaturated hydrocarbon or aromatic hydrocarbon raw material to the catalyst substance is 1:0.1 to 2.0, preferably 1:0.3 to 0.

45.

6. The method for synthesizing an unsaturated ketone or aromatic ketone compound according to claim 1, characterized in that The wavelength range of the visible light is 370nm to 455nm, preferably 405 to 455nm, and the power range of the visible light source is 10-100W, preferably 60-100W.

7. The method for synthesizing an unsaturated ketone or aromatic ketone compound according to claim 1, characterized in that The reaction temperature is 0 to 120° C., preferably room temperature to 60° C.; the reaction time is 1 to 24 hours, preferably 2 to 10 hours.

8. The method for synthesizing an unsaturated ketone or aromatic ketone compound according to claim 1, characterized in that The post-processing method is as follows: (1) After washing with water and saturated brine, the organic phase is dried by rotation, dichloromethane is added and cooled to 0° C., the catalyst is recovered by filtration, a dehydrating agent is added to the filtrate, the reaction is allowed to stand at 0° C. for 20-30 hours, the solvent is dried by rotation, and the unsaturated ketone or aromatic ketone compound is obtained by recrystallization, distillation or pulping; (2) Cooling the reaction liquid to below 0° C., filtering and recovering the catalyst, adding a dehydrating agent to the filtrate, stirring the reaction at 0° C. for 20-30 hours, spinning the solvent to dryness, and subjecting the reaction to recrystallization, beating, distillation or beating to obtain the unsaturated ketone or aromatic ketone compound.

9. The method for synthesizing an unsaturated ketone or aromatic ketone compound according to claim 8, characterized in that The dehydrating agent is one of the following: ① a mixture of ferrous sulfate and pyridine or triethylamine, wherein the mass of ferrous sulfate is 1-1.6 g / mL based on the volume of pyridine or triethylamine; ② triethylamine-acetic anhydride in a volume ratio of 1-2:1-3.

10. The method for synthesizing an unsaturated ketone or aromatic ketone compound according to claim 8, characterized in that The recrystallization or pulping solvent is an aqueous solution of at least one of methanol, ethanol and acetone with a mass fraction of 70-90%.

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