A method for synthesizing selenium-based dibenzocycloheptanone promoted by visible light

Abstract

The present invention relates to the technical field of organic synthetic chemistry, and specifically to a method for synthesizing selenium-based dibenzocycloheptanone promoted by visible light, which includes: using o-propynoyl biphenyl and diselenide as reaction raw materials, carrying out a stirring reaction under certain temperature conditions and under the irradiation of a light source to obtain a selenium-based dibenzocycloheptanone compound. The reaction conditions of the present invention are simple and the operation is convenient; the present invention does not need to use transition metals and has the advantages of being green and environmentally friendly, etc.; the present invention also has the advantages of being insensitive to air and having a wide substrate range, etc., opening up a new synthetic route and method for selenium-based dibenzocycloheptanone heterocyclic compounds, and having good application potential and research value.

Description

Technical Field

[0001] The present invention relates to the technical field of organic synthetic chemistry, and particularly to a method for synthesizing selenium-based dibenzocycloheptanone promoted by visible light. Background Art

[0002] Seven-membered carbon rings are important structural units in natural products and drug molecules. Among them, the 6 / 7 / 6 fused polycyclic ring is a classic skeleton, such as the dibenzocycloheptane ring, which exists in colchicine and its analogues. Therefore, the development of efficient methods for synthesizing such tricyclic skeletons has always attracted extensive attention from organic chemists and medicinal chemists. In the past few decades, chemists have developed various effective strategies for constructing such skeletons, such as enyne ring-closing metathesis / Diels-Alder reaction, catalytic C-H arylation reaction, intramolecular Nicholas reaction, oxidative coupling, and radical cyclization reaction, etc.

[0003] Selenium is a very important trace element in the human body, and its existence is closely related to people's health. Selenium-containing molecules have various biological activities. In addition, selenium-containing compounds have extensive applications in the fields of organic synthesis, medicine, and materials science. Therefore, a large amount of energy has been invested in developing various methods for introducing selenium atoms into organic molecules.

[0004] In view of the unique biological activities and physicochemical properties of the dibenzocycloheptane skeleton and selenium group, the development of new and efficient synthetic strategies for constructing selenium-containing dibenzocycloheptane compounds has always been the goal pursued by synthetic chemists. However, there are very few reported research methods for introducing selenium functional groups onto the dibenzocycloheptanone skeleton. In 2021, Chada Raji Reddy et al. achieved a method for synthesizing selenodibenzocycloheptanone derivatives using an electrochemical method (J. Org. Chem. 2021, 86, 17071-17081). The Gelson Perin research group reported the oxidation of diselenide by Oxone, which induced the selenocyclization of alkynones to obtain selenium-based dibenzocycloheptanone (J. Org. Chem. 2022, 87, 4273-4283).

[0005] Searching for a green and efficient method for synthesizing selenium-substituted dibenzocycloheptanone compounds is a very challenging and valuable research work, which provides the possibility for finding new compounds with pharmacological activities similar to colchicine. Herein, the present application provides a new synthetic method for selenium-based dibenzocycloheptanone compounds promoted by visible light. Summary of the Invention

[0006] The purpose of the present invention is to provide a method for synthesizing selenium-based dibenzocycloheptanone promoted by visible light to solve the problems raised in the above background art.

[0007] To achieve the above purpose, the present invention provides the following technical solutions:

[0008] A method for synthesizing selenium-based dibenzocycloheptanone promoted by visible light, the steps are as follows: In an organic solvent, using o-propynoyl biphenyl with the structure shown in formula (I) and diselenide with the structure shown in formula (II) as reaction raw materials, reacting under visible light irradiation. After the reaction is completed, the reaction solution is concentrated under reduced pressure to remove the solvent to obtain a crude product, and the crude product is purified by column chromatography to obtain a selenium-based dibenzocycloheptanone compound with the structure shown in formula (III);

[0009] The reaction equation is as shown below:

[0010]

[0011] Among them, the compound of formula (I) is o-propynoyl biphenyl, and the substituent R 1 is a hydrogen atom, a halogen, a C1-C10 straight-chain or branched-chain hydrocarbon group; the substituent R 2 is a C2-C10 straight-chain or branched-chain hydrocarbon group, a C3-C6 cycloalkyl group, a benzyl group, a phenyl group, a phenyl group substituted by one or more substituents, and the substituents are alkoxy groups, alkyl groups, cyano groups, nitro groups, trifluoromethyl groups, trifluoromethoxy groups.

[0012] The compound of formula (II) is diaryl diselenide, dialkyl diselenide.

[0013] Preferably, the molar ratio of o-propynoyl biphenyl with the structure shown in formula (I) to diselenide with the structure shown in formula (II) is 1:0.5 - 1:1, preferably 1:0.5.

[0014] Preferably, the organic solvent is dichloromethane, chloroform, carbon tetrachloride, nitromethane, acetonitrile, preferably dichloromethane.

[0015] Preferably, the irradiation light source for the reaction is one of sunlight, fluorescent lamp, tungsten lamp, LED lamp, preferably fluorescent lamp.

[0016] Preferably, the reaction time is 15h - 30h.

[0017] Preferably, after the reaction is completed, the reaction solution is concentrated under reduced pressure, and the concentrate is separated by column chromatography, using a mixed solution of petroleum ether and ethyl acetate as the eluent, wherein the volume ratio of petroleum ether:ethyl acetate is (1 - 40):1, collecting the eluate, and obtaining the selenium-based dibenzocycloheptanone shown in formula (III) after rotary evaporation of the solvent.

[0018] Compared with the prior art, the beneficial effects of the present invention are:

[0019] (1) The present invention can be operated under air conditions, is insensitive to water and oxygen, has mild reaction conditions and simple operation;

[0020] (2) The present invention uses visible light as an energy source, featuring low cost, safety, and environmental friendliness.

[0021] (3) The present invention can obtain the target product in only one step, with high yield, good functional group compatibility, and simple post-treatment, showing good application potential. Therefore, the present invention has great theoretical innovation value and implementation value. Detailed implementation manners

[0022] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all of them. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts shall fall within the protection scope of the present invention.

[0023] The present invention provides the following technical solution: A method for synthesizing selenyl dibenzocycloheptanone promoted by visible light, comprising the following steps: In an organic solvent, using o-propynoyl biphenyl with the structure shown in formula (I) and diselenide with the structure shown in formula (II) as reaction raw materials, reacting under visible light irradiation. After the reaction is completed, the solvent in the reaction solution is removed under reduced pressure to obtain a crude product, and the crude product is purified by column chromatography to obtain a selenyl dibenzocycloheptanone compound with the structure shown in formula (III);

[0024] The reaction equation is shown as follows:

[0025]

[0026] Among them, the compound of formula (I) is o-propynoyl biphenyl, and the substituent R 1 is a hydrogen atom, a halogen, a C1-C10 straight-chain or branched hydrocarbon group; the substituent R 2 is a C2-C10 straight-chain or branched hydrocarbon group, a C3-C6 cycloalkyl group, a benzyl group, a phenyl group, or a phenyl group substituted by one or more substituents, and the substituents are alkoxy groups, alkyl groups, cyano groups, nitro groups, trifluoromethyl groups, and trifluoromethoxy groups.

[0027] The compound of formula (II) is diaryl diselenide or dialkyl diselenide.

[0028] Example 1:

[0029] The reaction equation is shown as follows:

[0030]

[0031] Into a 20 mL test tube equipped with a magnetic stir bar, load propargyl o - biphenyl (0.2 mmol), diphenyl diselenide (0.1 mmol), and CH2Cl2 (5 mL). After addition, place a 23 W white compact fluorescent lamp 2 cm away from the reaction tube and react at room temperature for 20 hours under open - air conditions. After the reaction is completed, concentrate the organic phase by rotary evaporator, and purify the residue by silica gel column (silica gel specification: 200 - 300 mesh, eluent: petroleum ether / ethyl acetate = 10 / 1) to obtain 74 mg of the target compound with a yield of 85%.

[0032] The NMR spectral data of the obtained product are as follows: 1 H NMR(400MHz,CDCl3):δ7.78(d,J=7.8Hz,1H),7.65(dd,J=8.0,1.1Hz,1H),7.55(td,J=7.6,1.4Hz,1H),7.46 - 7.40(m,5H),7.37 - 7.19(m,8H),7.01(dd,J=8.0,1.4Hz,1H),6.31(dd,J=7.7,1.4Hz,1H); 13 C NMR(100MHz,CDCl3):δ195.5,143.9,143.6,142.4,137.8,137.4,136.7,136.5,136.1,132.1,131.2,131.0,129.5,129.1,128.7,128.6,128.5,128.4,128.3,128.1,127.5,125.6。

[0033] Example 2:

[0034] The reaction equation is shown as follows:

[0035]

[0036] Into a 20 mL test tube equipped with a magnetic stir bar, load propargyl o - biphenyl (0.2 mmol), diphenyl diselenide (0.1 mmol), and CH2Cl2 (5 mL). After addition, place a 23 W white compact fluorescent lamp 2 cm away from the reaction tube and react at room temperature for 20 hours under open - air conditions. After the reaction is completed, concentrate the organic phase by rotary evaporator, and purify the residue by silica gel column (silica gel specification: 200 - 300 mesh, eluent: petroleum ether / ethyl acetate = 15 / 1) to obtain 75 mg of the target compound with a yield of 83%.

[0037] The NMR spectral data of the obtained product are as follows: 11H NMR (400 MHz, CDCl3): δ 7.72 (d, J = 8.0 Hz, 1H), 7.55 - 7.50 (m, 2H), 7.46 - 7.40 (m, 5H), 7.33 - 7.24 (m, 3H), 7.22 - 7.18 (m, 4H), 6.82 (s, 1H), 6.29 (d, J = 7.6 Hz, 1H), 2.22 (s, 3H); 13 13C NMR (100 MHz, CDCl3): δ 195.6, 144.0, 143.4, 142.4, 137.5, 137.1, 136.7, 136.3, 136.0, 135.2, 132.3, 131.1, 131.0, 129.6, 129.2, 129.1, 128.8, 128.6, 128.5, 128.5, 127.8, 125.5, 21.4。

[0038] Example 3:

[0039] The reaction equation is shown as follows:

[0040]

[0041] Propargyl - phenyl ketone (0.2 mmol), diphenyl diselenide (0.1 mmol), and CH2Cl2 (5 mL) were charged into a 20 - mL test tube equipped with a magnetic stir bar. After addition, a 23 - watt white compact fluorescent lamp was placed 2 cm away from the reaction tube, and the reaction was carried out at room temperature for 20 hours under open - air conditions. After the reaction was completed, the organic phase was concentrated by a rotary evaporator, and the residue was purified by silica gel column chromatography (the silica gel specification was 200 - 300 mesh, and the eluent was petroleum ether / ethyl acetate = 10 / 1), obtaining 81 mg of the target compound with a yield of 86%.

[0042] The NMR spectral data of the obtained product are as follows: 1 1H NMR (400 MHz, CDCl3): δ 7.69 (d, J = 7.8 Hz, 1H), 7.55 - 7.40 (m, 7H), 7.35 - 7.32 (m, 2H), 7.27 - 7.20 (m, 5H), 6.98 (d, J = 2.4 Hz, 1H), 6.24 (dd, J = 7.8, 1.2 Hz, 1H); 13 13C NMR (100 MHz, CDCl3): δ 194.7, 143.4, 141.6, 141.2, 138.8, 137.5, 136.7, 136.0, 135.3, 133.1, 132.2, 131.4, 131.0, 129.4, 129.1, 129.0, 128.92, 128.9, 128.3, 128.2, 128.1, 128.0, 125.3。

[0043] Example 4:

[0044] The reaction equation is shown as follows:

[0045]

[0046] Propargyl biphenyl (0.2 mmol), diphenyl diselenide (0.1 mmol), and CH2Cl2 (5 mL) were charged into a 20 mL test tube equipped with a magnetic stir bar. After addition, a 23 W white compact fluorescent lamp was placed 2 cm away from the reaction tube, and the reaction was carried out at room temperature for 20 hours under open conditions. After the reaction was completed, the organic phase was concentrated by a rotary evaporator, and the residue was purified by a silica gel column (the silica gel specification was 200 mesh - 300 mesh, and the eluent was petroleum ether / ethyl acetate = 15 / 1) to obtain 81 mg of the target compound with a yield of 90%.

[0047] The NMR spectral data of the obtained product are as follows: 1 H NMR(400MHz,CDCl3):δ7.76(d,J=8.0Hz,1H),7.64(dd,J=8.0,1.2Hz,1H),7.54(td,J=7.8,1.4Hz,1H),7.47-7.44(m,2H),7.36-7.29(m,2H),7.26-7.14(m,8H),7.04(dd,J=8.0,1.4Hz,1H),6.28(dd,J=7.7,1.2Hz,1H),2.43(s,3H). 13 C NMR(100MHz,CDCl3):δ195.5,144.0,143.7,139.7,138.5,137.6,137.4,136.8,136.3,132.3,131.0,130.8,129.6,129.5,129.1,128.7,128.6,128.4,128.2,128.0,127.4,125.5,21.7。

[0048] Example 5:

[0049] The reaction equation is shown as follows:

[0050]

[0051] Into a 20 mL test tube equipped with a magnetic stir bar, load propargyl - o - biphenyl (0.2 mmol), diphenyl diselenide (0.1 mmol), and CH₂Cl₂ (5 mL). After addition, place a 23 - watt white compact fluorescent lamp 2 cm away from the reaction tube and react at room temperature for 20 hours under open - mouth conditions. After the reaction is completed, concentrate the organic phase by a rotary evaporator and purify the residue by silica gel column chromatography (silica gel specifications: 200 - 300 mesh, eluent: petroleum ether / ethyl acetate = 8 / 1) to obtain 76 mg of the target compound with a yield of 81%.

[0052] The NMR spectral data of the obtained product are as follows: 1 H NMR(400MHz,CDCl₃):δ7.74(d,J = 7.8Hz,1H),7.62(d,J = 7.8Hz,1H),7.54(dd,J = 11.0,4.2Hz,1H),7.42(d,J = 7.2Hz,2H),7.36 - 7.29(m,2H),7.25 - 7.16(m,6H),7.02(d,J = 8.0Hz,1H),6.95(d,J = 8.7Hz,2H),6.25(d,J = 7.6Hz,1H),3.85(s,3H); 13 C NMR(100MHz,CDCl₃):δ195.1,159.3,143.5,143.2,137.5,136.8,136.5,136.2,136.1,134.4,132.1,130.9,130.8,130.7,128.7,128.5,128.3,128.2,127.7,127.8,127.4,125.3,113.5,55.1。

[0053] Example 6:

[0054] The reaction equation is shown as follows:

[0055]

[0056] Into a 20 mL test tube equipped with a magnetic stir bar, load propargyl - o - biphenyl (0.2 mmol), diphenyl diselenide (0.1 mmol), and CH₂Cl₂ (5 mL). After addition, place a 23 - watt white compact fluorescent lamp 2 cm away from the reaction tube and react at room temperature for 20 hours under open - mouth conditions. After the reaction is completed, concentrate the organic phase by a rotary evaporator and purify the residue by silica gel column chromatography (silica gel specifications: 200 - 300 mesh, eluent: petroleum ether / ethyl acetate = 12 / 1) to obtain 61 mg of the target compound with a yield of 75%.

[0057] The NMR spectral data of the obtained product are as follows: 11H NMR (400 MHz, CDCl3): δ 7.70 - 7.65 (m, 2H), 7.60 - 7.58 (m, 1H), 7.53 - 7.38 (m, 5H), 7.33 - 7.29 (m, 1H), 7.24 - 7.20 (m, 3H), 6.45 (dd, J = 7.8, 1.2 Hz, 1H), 3.18 - 2.98 (m, 2H), 1.57 - 1.48 (m, 2H), 0.88 (t, J = 7.4 Hz, 3H); 13 13C NMR (100 MHz, CDCl3): δ 196.2, 146.4, 144.0, 137.2, 136.1, 135.6, 135.4, 135.2, 131.2, 130.7, 129.0, 128.9, 128.2, 128.1, 128.0, 127.9, 127.8, 127.7, 125.0, 39.8, 22.9, 13.9.

[0058] Example 7:

[0059] The reaction equation is as follows:

[0060]

[0061] Propargylbenzene (0.2 mmol), bis(4-tolyl) diselenide (0.1 mmol), and CH2Cl2 (5 mL) were loaded into a 20-mL test tube equipped with a magnetic stir bar. After addition, a 23-W white compact fluorescent lamp was placed 2 cm away from the reaction tube, and the reaction was carried out at room temperature for 20 h under open conditions. After the reaction was completed, the organic phase was concentrated by a rotary evaporator, and the residue was purified by a silica gel column (silica gel specification: 200 - 300 mesh, eluent: petroleum ether / ethyl acetate = 10 / 1) to obtain 79 mg of the target compound with a yield of 88%.

[0062] The NMR spectral data of the obtained product are as follows: 1 1H NMR (400 MHz, CDCl3): δ 7.64 (d, J = 7.8 Hz, 1H), 7.51 (d, J = 8.0 Hz, 1H), 7.46 (t, J = 8.0 Hz, 1H), 7.36 - 7.30 (m, 3H), 7.27 - 7.23 (m, 3H), 7.20 - 7.09 (m, 4H), 6.95 - 6.89 (m, 3H), 6.21 (dd, J = 7.7, 1.0 Hz, 1H), 2.25 (s, 3H). 1313C NMR (100 MHz, CDCl3): δ 195.2, 143.6, 143.1, 142.1, 138.7, 137.6, 137.4, 136.7, 136.1, 136.0, 131.9, 130.9, 130.6, 129.7, 129.4, 128.7, 128.5, 127.7, 127.5, 127.3, 125.2, 124.9, 21.2。

[0063] Example 8:

[0064] The reaction equation is shown as follows:

[0065]

[0066] Propargylbenzene (0.2 mmol), bis(4-methoxyphenyl) diselenide (0.1 mmol), and CH2Cl2 (5 mL) were placed into a 20 mL test tube equipped with a magnetic stir bar. After addition, a 23 W white compact fluorescent lamp was placed 2 cm away from the reaction tube, and the reaction was carried out at room temperature for 20 hours under open conditions. After the reaction was completed, the organic phase was concentrated by a rotary evaporator, and the residue was purified by a silica gel column (silica gel specification: 200 mesh - 300 mesh, eluent: petroleum ether / ethyl acetate = 7 / 1) to obtain 77 mg of the target compound with a yield of 82%.

[0067] The NMR spectral data of the obtained product are as follows: 1 1H NMR (400 MHz, CDCl3): δ 7.66 (d, J = 7.8 Hz, 1H), 7.52 (dd, J = 7.9, 1.2 Hz, 1H), 7.46 (td, J = 7.6, 1.6 Hz, 1H), 7.38 - 7.32 (m, 3H), 7.31 - 7.28 (m, 2H), 7.26 (td, J = 7.6, 1.3 Hz, 1H), 7.19 - 7.10 (m, 4H), 6.92 (dd, J = 8.1, 1.4 Hz, 1H), 6.70 - 6.67 (m, 2H), 6.20 (dd, J = 7.7, 1.2 Hz, 1H), 3.71 (s, 3H); 13 13C NMR (100 MHz, CDCl3): δ 195.3, 160.3, 143.7, 142.3, 142.2, 138.9, 138.1, 137.5, 136.2, 131.8, 130.7, 130.8, 129.5, 128.7, 128.6, 128.2, 127.8, 127.7, 127.4, 125.1, 118.5, 114.5, 55.2。

[0068] Example 9:

[0069] The reaction equation is shown as follows:

[0070]

[0071] Propargyl o - biphenyl (0.2 mmol), bis(3 - trifluoromethylphenyl) diselenide (0.1 mmol), and CH2Cl2 (5 mL) were placed into a 20 - mL test tube equipped with a magnetic stir bar. After addition, a 23 - watt white compact fluorescent lamp was placed 2 cm away from the reaction tube, and the reaction was carried out at room temperature for 20 hours under open - air conditions. After the reaction was completed, the organic phase was concentrated by a rotary evaporator, and the residue was purified by a silica gel column (silica gel specification: 200 mesh - 300 mesh, eluent: petroleum ether / ethyl acetate = 8 / 1) to obtain 77 mg of the target compound with a yield of 76%.

[0072] The NMR spectrum data of the obtained product are as follows: 1 H NMR(400MHz,CDCl3):δ7.80(d,J = 7.8Hz,1H),7.67 - 7.63(m,2H),7.59 - 7.52(m,3H),7.46 - 7.23(m,9H),7.02(dd,J = 8.0,1.1Hz,1H),6.40(dd,J = 7.8,1.2Hz,1H); 13 C NMR(100MHz,CDCl3):δ195.1,145.2,143.3,142.2,139.2,137.5,136.3,135.9,135.8,132.2,132.0,131.3,131.2,131.1,129.8,129.4,129.5,128.7,128.8,128.6,128.5,128.4,127.5,125.2,125.1,123.5.

[0073] Example 10:

[0074] The reaction equation is shown as follows:

[0075]

[0076] Propargyl o - biphenyl (0.2 mmol), dinaphthyl diselenide (0.1 mmol), and CH2Cl2 (5 mL) were placed into a 20 - mL test tube equipped with a magnetic stir bar. After addition, a 23 - watt white compact fluorescent lamp was placed 2 cm away from the reaction tube, and the reaction was carried out at room temperature for 20 hours under open - air conditions. After the reaction was completed, the organic phase was concentrated by a rotary evaporator, and the residue was purified by a silica gel column (silica gel specification: 200 mesh - 300 mesh, eluent: petroleum ether / ethyl acetate = 12 / 1) to obtain 83 mg of the target compound with a yield of 85%.

[0077] The NMR spectrum data of the obtained product are as follows: 1 H NMR(400MHz,CDCl3):δ7.86 - 7.83(m,3H),7.73(d,J=8.2Hz,1H),7.61(d,J=7.8Hz,1H),7.55(dd,J=7.9,1.2Hz,1H),7.51 - 7.43(m,3H),7.38 - 7.26(m,6H),7.18(td,8.1,1.4Hz,1H),7.12 - 7.08(m,1H),7.03(dd,J=8.0,1.2Hz,1H),6.77(td,J=7.6,1.0Hz,1H),5.59(dd,J=7.7,1.2Hz,1H). 13 C NMR(100MHz,CDCl3):δ195.1,143.9,143.1,142.3,137.8,136.7,136.7,136.0,135.7,134.7,133.8,132.0,130.8,130.3,130.0,129.4,128.7,128.6,128.3,128.1,128.0,127.8,127.6,127.4,126.6,126.3,125.8,124.6.

[0078] Example 11:

[0079] The reaction equation is as shown below:

[0080]

[0081] Propargyl - biphenyl (0.2 mmol), dibutyl diselenide (0.1 mmol) and CH2Cl2 (5 mL) were charged into a 20 - mL test tube equipped with a magnetic stir bar. After addition, a 23 - watt white compact fluorescent lamp was placed 2 cm away from the reaction tube, and the reaction was carried out at room temperature for 20 hours under open - mouth conditions. After the reaction was completed, the organic phase was concentrated by a rotary evaporator, and the residue was purified by a silica gel column (silica gel specification: 200 - 300 mesh, eluent: petroleum ether / ethyl acetate = 10 / 1) to obtain 68 mg of the target compound with a yield of 82%.

[0082] The NMR spectrum data of the obtained product are as follows: 11H NMR (400 MHz, CDCl3): δ 7.84 (d, J = 8.0 Hz, 1H), 7.68 - 7.64 (m, 2H), 7.56 - 7.49 (m, 2H), 7.42 - 7.34 (m, 4H), 7.25 - 7.16 (m, 3H), 7.1 (d, J = 8.0 Hz, 1H), 2.70 (t, J = 7.4 Hz, 2H), 1.44 (q, J = 7.4 Hz, 2H), 1.30 - 1.27 (m, 2H), 0.82 (t, J = 7.4 Hz, 3H); 13 13C NMR (100 MHz, CDCl3): δ 195.9, 143.9, 143.0, 142.6, 137.4, 136.8, 136.6, 135.0, 131.8, 131.3, 131.1, 129.5, 129.3, 128.9, 128.5, 128.3, 127.9, 127.5, 125.4, 32.2, 27.4, 23.5, 13.9。

[0083] In summary, in the present invention, visible light irradiation is used, and the carbon - selenization reaction occurs between o - propargylbenzoyl derivatives and diselenides to obtain seleno - dibenzocycloheptanones. The present invention can be operated under air conditions, is insensitive to water and oxygen, has relatively mild reaction conditions and simple operation; the present invention uses visible light as an energy source, which is low - cost, energy - saving and environmentally friendly; the present invention can obtain the target product in only one step, has good functional group compatibility and simple post - treatment, and has good application potential.

[0084] Although the embodiments of the present invention have been shown and described, for those of ordinary skill in the art, it can be understood that various changes, modifications, substitutions and variations can be made to these embodiments without departing from the principles and spirit of the present invention. The scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. A method for synthesizing selenium-based dibenzocycloheptanone promoted by visible light, characterized in that: The steps are as follows: In an organic solvent, using o-propynoyl biphenyl with the structure shown in formula (I) and diselenide with the structure shown in formula (II) as reaction raw materials, carry out the reaction under visible light irradiation. After the reaction is completed, remove the solvent from the reaction solution under reduced pressure to obtain a crude product, and the crude product is purified by column chromatography to obtain the selenyl dibenzocycloheptanone compound with the structure shown in formula (III). The reaction equation is shown as follows: ； Among them, the compound of formula (I) is o-propynoyl biphenyl, and the substituent R 1 is a hydrogen atom, a halogen, a C1-C10 straight-chain or branched hydrocarbon group; the substituent R 2 is a C2-C10 straight-chain or branched hydrocarbon group, a C3-C6 cycloalkyl group, a benzyl group, a phenyl group, a phenyl group substituted with one or more substituents, and the substituents are alkoxy groups, alkyl groups, cyano groups, nitro groups, trifluoromethyl groups, trifluoromethoxy groups; The compound of formula (II) is diaryl diselenide or dialkyl diselenide.

2. The method for synthesizing selenyl dibenzocycloheptanone promoted by visible light according to claim 1, wherein: The molar ratio of o-propynoyl biphenyl with the structure shown in formula (I) to diselenide with the structure shown in formula (II) is 1:0.

5.

3. A method for synthesizing selenium-based dibenzocycloheptanone promoted by visible light according to claim 1, characterized in that: The organic solvent is dichloromethane.

4. A method for synthesizing selenium-based dibenzocycloheptanone promoted by visible light according to claim 1, characterized in that: The irradiation light source for the reaction is a fluorescent lamp.

5. The synthesis method of selenyl dibenzocycloheptanone promoted by visible light according to claim 1, wherein: The reaction time is 15 h - 30 h.

6. A method for synthesizing selenyl dibenzocycloheptanone promoted by visible light according to claim 1, wherein: After the reaction is completed, concentrate the reaction solution under reduced pressure, separate the concentrate by column chromatography, using a mixed solution of petroleum ether and ethyl acetate as the eluent, where the volume ratio of petroleum ether to ethyl acetate is (1 - 40):

1. Collect the eluate, and after rotary evaporation of the solvent, obtain the selenyl dibenzocycloheptanone shown in formula (III).

Images