Novel method for synthesizing 1, 3-diketone organic matter

Abstract

The invention discloses a novel method for synthesizing 1, 3-diketone organic matters, which comprises the following steps: by taking acyl chloride and silyl enol ether as raw materials, generating acyl free radicals through photo-induced copper catalysis, and carrying out free radical addition reaction on the acyl free radicals and silyl enol ether, thereby efficiently constructing 1, 3-diketone compounds. Compared with strong base, oxidant, high temperature and expensive metal catalyst required by the existing method, the method provided by the invention adopts the cheap and high-yield copper catalyst, so that the production cost is reduced, and the economic benefit is improved. In addition, the method has mild reaction conditions, easily available catalysts and raw materials, utilizes clean and sustainable light energy as driving force, is simple and convenient to operate, and is suitable for large-scale production. The invention provides an economic and environment-friendly innovative way for synthesizing the 1, 3-diketone compound, and has a wide application prospect.

Description

Technical Field

[0001] The invention belongs to the technical field of chemical synthesis, and in particular relates to a novel method for synthesizing 1,3-diketone organic compounds. Technical Background

[0002] 1,3-diketones are widely present in natural products and drug molecules, playing a vital role in carbon-carbon bond formation, heterocyclic synthesis, and the construction of various aromatic frameworks. As key structural units in medicinal chemistry, 1,3-diketones exhibit rich biological activities and have significant antibacterial, antioxidant, anti-inflammatory, and anticancer properties. For example, the molecular structures of the drugs avobenzone and nitisinone both contain 1,3-diketone structural units, and some natural flavonoid derivatives (such as curcumin analogs) also rely on the 1,3-diketone skeleton to exert their anti-inflammatory and neuroprotective effects. In addition, 1,3-diketones as ligands also have important applications in the fields of metal complex catalysis and functional materials. Therefore, the development of efficient and green 1,3-diketone synthesis strategies is of great significance to both medicinal chemistry and materials science.

[0003] Traditionally, 1,3-diketones have been synthesized primarily via the Claisen condensation reaction, which relies on a hard enolate strategy under strongly basic conditions. However, these harsh reaction conditions limit the tolerance of substrates with sensitive functional groups and are accompanied by excessive consumption of the acylating agent and the formation of over-acylated byproducts. While soft enolate approaches offer better substrate compatibility, they often require more complex synthetic steps, increase costs, and are prone to oxidative acylation side reactions. Furthermore, alternative pathways have been explored, including the reaction of α-bromoketones with α-oxycarboxylates, the oxidation of β-hydroxyketones, the carbonyl insertion reaction of ketones with aryl iodides, and rearrangement strategies. However, these methods often suffer from the use of strong bases or oxidants, high temperatures, expensive metal catalysts, complex substrate prefunctionalization, and poor atom economy, which are inconsistent with the principles of green and sustainable chemistry. Therefore, there is an urgent need to develop a mild, efficient, and widely applicable catalytic method for the synthesis of 1,3-diketones.

[0004] In summary, developing a method for synthesizing 1,3-diketones that does not require precious metals, has mild conditions, and is highly atom-economical, especially by utilizing inexpensive metal catalytic systems, will become a key direction for breaking through existing bottlenecks and providing more practical solutions for drug development and the construction of functional molecules. Summary of the Invention

[0005] The technical problem to be solved by the present invention is to develop a mild and inexpensive method for synthesizing 1,3-diketone compounds from acyl chlorides and enol silyl ethers by light-induced copper catalysis.

[0006] To solve the above technical problems, the present invention adopts the following technical solution: a new method for synthesizing 1,3-diketone organic compounds, using acyl chloride and enol silyl ether as raw materials, generating acyl radicals from acyl chloride under a photoinduced copper catalyst, and then undergoing a free radical addition reaction with enol silyl ether to obtain 1,3-diketone compounds.

[0007] This method conforms to the following reaction equation:

[0008]

[0009] The acyl chloride is Enol silyl ether is Among them, R 1 and R 2 It represents an alkyl group, an alkoxy group, a phenyl group, a halogen group, an ester group, etc. containing one or more substitutions; Si represents an alkylsilyl group, such as trimethylsilyl, triethylsilyl, and dimethyl-tert-butylsilyl.

[0010] The synthesis method of the 1,3-diketone compound is carried out as follows: silyl enol ether, acyl chloride, copper catalyst, ligand, and solvent are added to a reaction tube. Under nitrogen protection, the reaction is stirred at room temperature under light irradiation for 6 hours. After the reaction is completed, extraction is performed with ethyl acetate, and the solvent is removed under reduced pressure to obtain a crude product. The crude product is then purified by column chromatography to obtain the 1,3-diketone compound.

[0011] The copper catalyst is one or a mixture of two or more of CuCl, CuBr, CuI, Cu2O and CuO.

[0012] The light is blue light or sunlight.

[0013] The molar ratio of acyl chloride to enol silyl ether is 3:2.

[0014] The ligand is 1,1'-binaphthyl-2,2'-bis(diphenylphosphine) (BINAP).

[0015] The solvent is one or a mixture of two or more of N,N-dimethylacetamide, tetrahydrofuran, toluene, N,N-dimethylformamide, 1,2-dichloroethane, n-heptane, p-xylene, 1,4-dioxane and N-methylpyrrolidone.

[0016] The reaction tube is a quartz tube or a glass tube.

[0017] The eluent in the column chromatography is petroleum ether or a mixed solvent of petroleum ether and ethyl acetate with a volume ratio of (20-100):1

[0018] To address the current challenges in 1,3-diketone synthesis, the inventors have developed a method for synthesizing 1,3-diketone compounds. Using acyl chloride and silyl enol ether as raw materials, the free radical addition reaction of the acyl chloride and silyl enol ether is catalyzed by light-induced copper to produce the 1,3-diketone compound. Directly utilizing clean, sustainable light energy significantly improves energy efficiency and reduces process costs. Compared to expensive metal catalysts such as iridium, palladium, and ruthenium, copper is more abundant, more environmentally friendly, and more cost-effective. Therefore, compared to existing methods, the present invention offers advantages such as ease of operation, readily available raw materials, high efficiency, cost-effectiveness, and environmental friendliness. DETAILED DESCRIPTION

[0019] Example 1

[0020] To a reaction tube, add 0.75 mmol of benzoyl chloride, 0.50 mmol of 1-phenyl-1-triethylsilylene, 1.5 mol% of CuI, 1.5 mol% of 1,1'-binaphthyl-2,2'-bis(diphenylphosphine), and 1.5 mL of N,N-dimethylacetamide. Stir the reaction under nitrogen and sunlight at room temperature for 6 hours. After the reaction, extract with ethyl acetate, remove the solvent under reduced pressure, and obtain a crude product. Purify the crude product by column chromatography to obtain the desired product. The column chromatography eluent used was a 20:1 volume ratio of petroleum ether to ethyl acetate.

[0021] The structural characterization data of the obtained product are as follows:

[0022] 1 H NMR (600MHz, Chloroform-d) δ16.92(s,1H),8.04–8.02(m,4H),7.59(t,J=7.4Hz,2H),7.52(t,J=7.5Hz,4H),6.89(s,1H).

[0023] 13 C NMR (151MHz, Chloroform-d) δ185.80,135.57,132.49,128.72,127.20,93.19.

[0024] According to the above data, the structure of the obtained product is as follows:

[0025]

[0026] Example 2

[0027] To a reaction tube, add 0.75 mmol of 4-methylbenzoyl chloride, 0.50 mmol of 1-phenyl-1-trimethylsilyloxyethylene, 1.5 mol% of CuI, 1.5 mol% of 1,1'-binaphthyl-2,2'-bis(diphenylphosphine), and 1.5 mL of N,N-dimethylacetamide. Stir the reaction at room temperature under nitrogen protection and sunlight for 6 hours. After completion of the reaction, extract with ethyl acetate, and remove the solvent under reduced pressure to obtain a crude product. The crude product is then purified by column chromatography to obtain the desired product. The column chromatography eluent used is a 20:1 volume ratio of petroleum ether to ethyl acetate.

[0028] The structural characterization data of the obtained product are as follows:

[0029] 1 H NMR(600MHz,Chloroform-d)δ17.04(s,1H),8.02(d,J=7.2Hz,2H),7.93(d,J=8.0Hz,2H),7. 57(t,J=7.3Hz,1H),7.51(t,J=7.5Hz,2H),7.31(d,J=7.9Hz,2H),6.87(s,1H),2.45(s,3H).

[0030] 13 C NMR (151MHz, Chloroform-d) δ186.01,185.10,143.25,135.53,132.78,132.28,129.37,128.60,127.21,127.06,92.76,21.59.

[0031] According to the above data, the structure of the obtained product is as follows:

[0032]

[0033] Example 3

[0034] To a reaction tube, add 0.75 mmol of 4-tert-butylbenzoyl chloride, 0.50 mmol of 1-phenyl-1-trimethylsilyloxyethylene, 1.5 mol% of CuI, 1.5 mol% of 1,1'-binaphthyl-2,2'-bis(diphenylphosphine), and 1.5 mL of N,N-dimethylacetamide. Stir the reaction under nitrogen and sunlight for 6 hours at room temperature. After completion of the reaction, extract with ethyl acetate, remove the solvent under reduced pressure, and obtain a crude product. The crude product is then purified by column chromatography to obtain the desired product. The column chromatography eluent used is a 20:1 volume ratio of petroleum ether to ethyl acetate.

[0035] The structural characterization data of the obtained product are as follows:

[0036] 1H NMR (600MHz, Chloroform-d) δ17.01(s,1H),8.04(d,J=7.2Hz,2H),7.99(d,J=8.4Hz,2H),7.60–7.51(m,5H),6.90(s,1H),1.41(s,9H).

[0037] 13 C NMR (151MHz, Chloroform-d) δ185.92,185.34,156.29,135.66,132.79,132.34,128.68,127.14,125.69,92.93,35.09,31.14.

[0038] According to the above data, the structure of the obtained product is as follows:

[0039]

[0040] Example 4

[0041] To a reaction tube, add 0.75 mmol of 4-methoxybenzoyl chloride, 0.50 mmol of 1-phenyl-1-trimethylsilyloxyethylene, 1.5 mol% of CuI, 1.5 mol% of 1,1'-binaphthyl-2,2'-bis(diphenylphosphine), and 1.5 mL of N,N-dimethylacetamide. Under nitrogen protection, stir and react at room temperature under sunlight for 6 hours. After completion of the reaction, extract with ethyl acetate, and remove the solvent under reduced pressure to obtain a crude product. The crude product is then purified by column chromatography to obtain the desired product. The column chromatography eluent used is a mixed solvent of petroleum ether and ethyl acetate in a volume ratio of 20:1.

[0042] The structural characterization data of the obtained product are as follows:

[0043] 1 H NMR(600MHz,Chloroform-d)δ17.03(s,1H),7.99–7.96(m,4H),7.53(d,J=7.0H z,1H),7.48(t,J=7.5Hz,2H),6.98(d,J=8.9Hz,2H),6.80(s,1H),3.87(s,3H).

[0044] 13 C NMR (151MHz, Chloroform-d) δ185.90,185.32,156.27,135.64,132.77,132.32,128.66,127.12,125.67,92.91,35.07,31.12.

[0045] According to the above data, the structure of the obtained product is as follows:

[0046]

[0047] Example 5

[0048] To a reaction tube, add 0.75 mmol of 4-chlorobenzoyl chloride, 0.50 mmol of tert-butyldimethyl((1-phenylvinyl)oxy)silane, 1.5 mol% of CuI, 1.5 mol% of 1,1'-binaphthyl-2,2'-bis(diphenylphosphine), and 1.5 mL of N,N-dimethylacetamide. Under nitrogen protection, irradiate with blue light and stir at room temperature for 6 hours. After completion of the reaction, extract with ethyl acetate, and remove the solvent under reduced pressure to obtain a crude product. The crude product is purified by column chromatography to obtain the desired product. The column chromatography eluent used is a mixed solvent of petroleum ether and ethyl acetate in a volume ratio of 20:1.

[0049] The structural characterization data of the obtained product are as follows:

[0050] 1 H NMR (600MHz, Chloroform-d) δ16.88(s,1H),8.00(d,J=7.7Hz,2H),7.93(d,J=8.4Hz,2H),7.58(t,J=7.3Hz,1H),7.49(dd,J=28.7,8.1Hz,4H),6.82(s,1H).

[0051] 13 C NMR (151MHz, Chloroform-d) δ185.77,184.50,138.70,135.25,133.95,132.61,128.96,128.71,128.50,127.18,92.97.

[0052] According to the above data, the structure of the obtained product is as follows:

[0053]

[0054] Example 6

[0055] To a reaction tube, add 0.75 mmol of 3-bromobenzoyl chloride, 0.50 mmol of 1-phenyl-1-trimethylsilyloxyethylene, 1.5 mol% of CuI, 1.5 mol% of 1,1'-binaphthyl-2,2'-bis(diphenylphosphine), and 1.5 mL of N,N-dimethylacetamide. Under nitrogen protection, irradiate with blue light and stir at room temperature for 6 hours. After completion of the reaction, extract with ethyl acetate, and remove the solvent under reduced pressure to obtain a crude product. The crude product is then purified by column chromatography to obtain the desired product. The column chromatography eluent used is a 20:1 volume ratio of petroleum ether to ethyl acetate.

[0056] The structural characterization data of the obtained product are as follows:

[0057] 1 H NMR(600MHz,Chloroform-d)δ16.78(s,1H),8.12(s,1H),8.01(d,J=7.5Hz,2H),7.92(d,J=7.7Hz ,1H),7.68(d,J=8.2Hz,1H),7.59(t,J=7.3Hz,1H),7.51(t,J=7.6Hz,2H),7.37(t,J=7.9Hz,1H).

[0058] 13 C NMR (151MHz, Chloroform-d) δ186.06,183.99,137.53,135.19,135.16,132.74,130.21,130.16,128.74,127.25,125.68,122.94,93.26.

[0059] According to the above data, the structure of the obtained product is as follows:

[0060]

[0061] Example 7

[0062] To a reaction tube, add 0.75 mmol of 3-iodobenzoyl chloride, 0.50 mmol of 1-phenyl-1-trimethylsilyloxyethylene, 1.5 mol% of CuI, 1.5 mol% of 1,1'-binaphthyl-2,2'-bis(diphenylphosphine), and 1.5 mL of N,N-dimethylacetamide. Under nitrogen protection, irradiate with blue light and stir at room temperature for 6 hours. After completion of the reaction, extract with ethyl acetate, and remove the solvent under reduced pressure to obtain a crude product. The crude product is then purified by column chromatography to obtain the desired product. The column chromatography eluent used is a 20:1 volume ratio of petroleum ether to ethyl acetate.

[0063] The structural characterization data of the obtained product are as follows:

[0064] 1 H NMR(600MHz,Chloroform-d)δ16.79(s,1H),8.31(s,1H),8.00(d,J=7.1Hz,2H),7.95(d,J=7.8Hz,1H), 7.88(d,J=7.7Hz,1H),7.58(t,J=7.4Hz,1H),7.51(t,J=7.6Hz,2H),7.23(t,J=7.8Hz,1H),6.80(s,1H).

[0065] 13 C NMR (151MHz, Chloroform-d) δ185.97,183.94,141.10,137.52,136.02,135.15,132.71,130.30,128.73,127.25,126.28,94.45,93.21.

[0066] According to the above data, the structure of the obtained product is as follows:

[0067]

[0068] Example 8

[0069] To a reaction tube, add 0.75 mmol of 4-methylbenzoyl chloride, 0.50 mmol of trimethyl((1-(p-tolyl)vinyl)oxy)silane, 1.5 mol% of CuI, 1.5 mol% of 1,1'-binaphthyl-2,2'-bis(diphenylphosphine), and 1.5 mL of N,N-dimethylacetamide. Under nitrogen protection, irradiate with blue light and stir at room temperature for 6 hours. After completion of the reaction, extract with ethyl acetate, and remove the solvent under reduced pressure to obtain a crude product. The crude product is purified by column chromatography to obtain the desired product. The column chromatography eluent used is a mixed solvent of petroleum ether and ethyl acetate in a volume ratio of 20:1.

[0070] The structural characterization data of the obtained product are as follows:

[0071] 1 H NMR (500MHz, Chloroform-d) δ17.03 (s, 1H), 7.92 (d, J = 8.2Hz, 4H), 7.31 (d, J = 8.0Hz, 4H), 6.84 (s, 1H), 2.45 (s, 6H).

[0072] 13 C NMR (126MHz, Chloroform-d) δ185.49,143.12,132.91,129.39,127.18,92.48,77.33,77.07,76.82,21.64.

[0073] According to the above data, the structure of the obtained product is as follows:

[0074]

[0075] Example 9

[0076] To a reaction tube, add 0.75 mmol of 4-methylbenzoyl chloride, 0.50 mmol of trimethyl((1-(p-tert-butylphenyl)vinyl)oxy)silane, 1.5 mol% of CuI, 1.5 mol% of 1,1'-binaphthyl-2,2'-bis(diphenylphosphine), and 1.5 mL of N,N-dimethylacetamide. Under nitrogen protection, irradiate with blue light and stir at room temperature for 6 hours. After completion of the reaction, extract with ethyl acetate, and remove the solvent under reduced pressure to obtain a crude product. The crude product is purified by column chromatography to obtain the desired product. The column chromatography eluent used is a mixed solvent of petroleum ether and ethyl acetate in a volume ratio of 20:1.

[0077] The structural characterization data of the obtained product are as follows:

[0078] 1 H NMR (500MHz, Chloroform-d) δ16.99(s,1H),7.94(dd,J=17.5,8.3Hz,4H),7.53(d,J=8.5Hz,2H),7.32(d,J=8.0Hz,2H),2.46(s,3H),1.39(s,9H).

[0079] 13 C NMR (126MHz, Chloroform-d) δ185.69,185.37,156.16,143.15,133.02,132.89,129.43,127.23,127.06,125.68,92.64,35.12,31.18,21.68.

[0080] According to the above data, the structure of the obtained product is as follows:

[0081]

[0082] Example 10

[0083] To a reaction tube, add 0.75 mmol of 4-methylbenzoyl chloride, 0.50 mmol of trimethyl((1-(p-methoxyphenyl)vinyl)oxy)silane, 1.5 mol% of CuI, 1.5 mol% of 1,1'-binaphthyl-2,2'-bisdiphenylphosphine, and 1.5 mL of N,N-dimethylacetamide. Stir the reaction at room temperature under sunlight for 6 hours. After completion of the reaction, extract with ethyl acetate, and remove the solvent under reduced pressure to obtain a crude product. The crude product is then purified by column chromatography to obtain the desired product. The column chromatography eluent used is a mixed solvent of petroleum ether and ethyl acetate in a volume ratio of 20:1.

[0084] The structural characterization data of the obtained product are as follows:

[0085] 1 H NMR(500MHz,Chloroform-d)δ17.15(s,1H),8.00(d,J=8.4Hz,2H),7.92(d,J=8.0Hz,2H ),7.31(d,J=7.8Hz,2H),7.00(d,J=8.3Hz,2H),6.81(s,1H),3.89(s,3H),2.45(s,3H).

[0086] 13 C NMR (126MHz, Chloroform-d) δ185.60,184.30,163.10,142.89,132.75,129.31,129.17,127.00,113.90,91.92,55.38,21.55.

[0087] According to the above data, the structure of the obtained product is as follows:

[0088]

[0089] Example 11

[0090] To a reaction tube, add 0.75 mmol of 4-methylbenzoyl chloride, 0.50 mmol of trimethyl((1-(3-methylphenyl)vinyl)oxy)silane, 1.5 mol% of CuI, 1.5 mol% of 1,1'-binaphthyl-2,2'-bis(diphenylphosphine), and 1.5 mL of N,N-dimethylacetamide. Under nitrogen protection, irradiate with blue light and stir at room temperature for 6 hours. After completion of the reaction, extract with ethyl acetate, and remove the solvent under reduced pressure to obtain a crude product. The crude product is purified by column chromatography to obtain the desired product. The column chromatography eluent used is a mixed solvent of petroleum ether and ethyl acetate in a volume ratio of 20:1.

[0091] The structural characterization data of the obtained product are as follows:

[0092] 1 H NMR(600MHz,Chloroform-d)δ17.01(s,1H),7.93(d,J=8.3Hz,2H),7.82(d,J=15.5Hz,2 H),7.39(d,J=7.2Hz,2H),7.32(d,J=8.0Hz,2H),6.85(s,1H),2.47(s,3H),2.46(s,3H).

[0093] 13 C NMR(151MHz,Chloroform-d)δ185.94,185.44,143.23,138.43,135.58,133.14,132.89,129.40,128.54,127.67,127.24,124.30,92.86,21.64,21.43.

[0094] According to the above data, the structure of the obtained product is as follows:

[0095]

[0096] Example 12

[0097] To a reaction tube, add 0.75 mmol of 4-methylbenzoyl chloride, 0.50 mmol of trimethyl((1-(p-chlorophenyl)vinyl)oxy)silane, 1.5 mol% of CuI, 1.5 mol% of 1,1'-binaphthyl-2,2'-bis(diphenylphosphine), and 1.5 mL of N,N-dimethylacetamide. Under nitrogen protection, irradiate with blue light and stir at room temperature for 6 hours. After completion of the reaction, extract with ethyl acetate, and remove the solvent under reduced pressure to obtain a crude product. The crude product is purified by column chromatography to obtain the desired product. The column chromatography eluent used is a mixed solvent of petroleum ether and ethyl acetate in a volume ratio of 20:1.

[0098] The structural characterization data of the obtained product are as follows:

[0099] 1 H NMR (600MHz, Chloroform-d) δ16.90(s,1H),7.92(dd,J=18.6,8.1Hz,4H),7.47(d,J=8.1Hz,2H),7.31(d,J=7.6Hz,2H),6.81(s,1H),2.46(s,3H).

[0100] 13C NMR (151MHz, Chloroform-d) δ186.14,184.00,143.54,138.59,134.11,132.65,129.50,128.99,128.49,127.31,92.73,21.71.

[0101] According to the above data, the structure of the obtained product is as follows:

[0102]

[0103] Example 13

[0104] To a reaction tube, add 0.75 mmol of 4-methylbenzoyl chloride, 0.50 mmol of trimethyl((1-(p-bromophenyl)vinyl)oxy)silane, 1.5 mol% of CuI, 1.5 mol% of 1,1'-binaphthyl-2,2'-bis(diphenylphosphine), and 1.5 mL of N,N-dimethylacetamide. Under nitrogen protection, irradiate with blue light and stir at room temperature for 6 hours. After completion of the reaction, extract with ethyl acetate, and remove the solvent under reduced pressure to obtain a crude product. The crude product is purified by column chromatography to obtain the desired product. The column chromatography eluent used is a mixed solvent of petroleum ether and ethyl acetate in a volume ratio of 20:1.

[0105] The structural characterization data of the obtained product are as follows:

[0106] 1 H NMR (600MHz, Chloroform-d) δ16.88 (s, 1H), 7.91 (d, J = 8.0Hz, 2H), 7.87

[0107] (d,J=8.5Hz,2H),7.64(d,J=8.5Hz,2H),7.32(d,J=7.9Hz,2H),6.81(s,

[0108] 1H),2.46(s,3H).

[0109] 13 C NMR (151MHz, Chloroform-d) δ186.27,184.04,143.59,134.57,132.68,131.99,129.52,128.65,127.33,127.17,92.74,21.73.

[0110] According to the above data, the structure of the obtained product is as follows:

[0111]

[0112] Example 14

[0113] To a reaction tube, add 0.75 mmol of 4-methylbenzoyl chloride, 0.50 mmol of trimethyl((1-(p-acetoxyphenyl)vinyl)oxy)silane, 1.5 mol% of CuI, 1.5 mol% of 1,1'-binaphthyl-2,2'-bis(diphenylphosphine), and 1.5 mL of N,N-dimethylacetamide. Under nitrogen protection, the reaction was stirred at room temperature under blue light irradiation for 6 hours. After completion of the reaction, the mixture was extracted with ethyl acetate, and the solvent was removed under reduced pressure to obtain a crude product. The crude product was purified by column chromatography to obtain the desired product. The column chromatography eluent used was a mixed solvent of petroleum ether and ethyl acetate in a volume ratio of 20:1.

[0114] The structural characterization data of the obtained product are as follows:

[0115] 1 H NMR(500MHz,Chloroform-d)δ16.93(s,1H),8.03(d,J=8.7Hz,2H),7.92–7.89(m,2H) ,7.31(d,J=7.5Hz,2H),7.25(d,J=8.7Hz,2H),6.82(s,1H),2.45(s,3H),2.35(s,3H).

[0116] 13 C NMR (126MHz, Chloroform-d) δ185.85,184.39,168.98,153.81,143.39,133.26,132.72,129.46,128.62,127.26,121.88,92.73,21.68,21.19.

[0117] According to the above data, the structure of the obtained product is as follows:

[0118]

Claims

1. A novel method for synthesizing 1,3-diketone organic compounds, characterized by: Using acyl chloride and enol silyl ether as raw materials, the free radical addition reaction of acyl chloride and enol silyl ether is carried out under photoinduced copper catalyst to obtain 1,3-diketone compound.

2. The novel method for synthesizing 1,3-diketone organic compounds according to claim 1, characterized in that This method conforms to the following reaction equation: The acyl chloride is Enol silyl ether is Among them, R 1 and R 2 It represents an alkyl group, an alkoxy group, a phenyl group, a halogen group, an ester group, etc. containing one or more substitutions; Si represents a silicon group, such as trimethylsilyl, triethylsilyl, and dimethyl-tert-butylsilyl.

3. The novel method for synthesizing 1,3-diketone organic compounds according to claim 1, characterized in that The following steps were followed: silyl enol ether, acyl chloride, copper catalyst, ligand, and solvent were added to a reaction tube. The reaction was stirred under nitrogen and irradiated with light for 6 hours. After completion of the reaction, the reaction was extracted with ethyl acetate and the solvent removed under reduced pressure to obtain a crude product, which was then purified by column chromatography to yield the 1,3-diketone compound.

4. The novel method for synthesizing 1,3-diketone organic compounds according to claim 4, characterized in that: The copper catalyst is one or a mixture of two or more of CuCl, CuBr, CuI, Cu2O and CuO.

5. The novel method for synthesizing 1,3-diketone organic compounds according to claim 4, characterized in that: The light is blue light or sunlight.

6. The novel method for synthesizing 1,3-diketone organic compounds according to claim 4, characterized in that: The molar ratio of the acyl chloride to the enol silyl ether is 3:

2.

7. The novel method for synthesizing 1,3-diketone organic compounds according to claim 4, characterized in that: The ligand is 1,1'-binaphthyl-2,2'-bisdiphenylphosphine (BINAP).

8. The novel method for synthesizing 1,3-diketone organic compounds according to claim 4, characterized in that: The solvent is one or a mixture of two or more of N,N-dimethylacetamide, tetrahydrofuran, toluene, N,N-dimethylformamide, 1,2-dichloroethane, n-heptane, p-xylene, 1,4-dioxane and N-methylpyrrolidone.

9. The novel method for synthesizing 1,3-diketone organic compounds according to claim 4, characterized in that: The reaction tube is a quartz tube or a glass tube.

10. The novel method for synthesizing 1,3-diketone organic compounds according to claim 4, characterized in that: The eluent in the column chromatography is petroleum ether or a mixed solvent of petroleum ether and ethyl acetate in a volume ratio of (20-100):1.

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