CN110872219A - Method for synthesizing benzofluorenone compound through photocatalysis - Google Patents

Method for synthesizing benzofluorenone compound through photocatalysis Download PDF

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CN110872219A
CN110872219A CN201811001663.XA CN201811001663A CN110872219A CN 110872219 A CN110872219 A CN 110872219A CN 201811001663 A CN201811001663 A CN 201811001663A CN 110872219 A CN110872219 A CN 110872219A
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formula
solvent
compound
photosensitizer
benzofluorenone
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CN110872219B (en
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刘运奎
郑立孟
鲍汉扬
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Zhejiang University of Technology ZJUT
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
    • C07C45/76—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton with the aid of ketenes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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Abstract

A method for photocatalytic synthesis of a benzofluorenone compound, the method comprising: mixing a compound shown as a formula (I), a compound shown as a formula (II), a photosensitizer and a solvent, reacting for 1-3 h at 30-50 ℃ under the irradiation of 15W blue LED light, and then carrying out post-treatment on a reaction solution to obtain a benzofluorenone compound shown as a formula (III); the invention is safe and environment-friendly, does not generate waste gas and has low operation risk; the substrate has good adaptability, and various substituents can realize oxidative cyclization; the reaction condition is mild; meanwhile, the reaction adopts a photocatalysis mode to synthesize the benzofluorenone, so that the method is more environment-friendly and green and is closer to the idea of green chemistry;

Description

Method for synthesizing benzofluorenone compound through photocatalysis
(I) technical field
The invention relates to a method for synthesizing a benzofluorenone compound by photocatalysis.
(II) background of the invention
Fluorenones and benzofluorenones are important and useful carbocyclic rings that have received much attention due to their unique biological and pharmaceutical activities as well as optical and electronic properties. For example, the fluorenone alkaloid cauliphine (shown in formula A below), an alkaloid isolated from the natural product Caulophyllum robustum, has been tested to exhibit good anti-myocardial ischemia activity. And kinafluorenone (shown as the following formula B) is an intermediate for synthesizing antibiotics prekinamycin and stephanin; the chiral compound Fluostatin B (shown as formula C below) is a novel inhibitor of dipeptidyl peptidase III from human placenta, and the like. In addition, the benzofluorenone is widely applied to the fields of photoelectric materials and dyes.
The traditional methods for synthesizing the benzofluorenone mainly comprise the oxidation reaction of benzofluorene, the Friedel-crafts acylation reaction of aryl carboxylic acid and derivatives thereof, and the intramolecular Diels-Alder reaction of (o-arylethynyl aryl) propiophenone compounds, but all of the methods have various defects, such as the use of toxic or seriously polluted oxidants, high reaction temperature, poor functional group tolerance and the like.
Figure BDA0001783103520000011
Disclosure of the invention
Aiming at the defects of the prior art, the invention provides a general, simple and efficient method for synthesizing the benzofluorenone compound. Compared with the traditional synthesis method, the method has the following advantages that the method related to the invention adopts a photocatalysis mode, realizes the synthesis of the benzofluorenone compound under the conditions of a small amount of photosensitizer and lower temperature, greatly reduces the problems of high energy consumption and the like caused by heating, does not need to use additional oxidant, and increases the control on the reaction selectivity, so the method has higher industrial application prospect.
The technical scheme of the invention is as follows:
a method for photocatalytic synthesis of a benzofluorenone compound, the method comprising:
mixing a compound shown as a formula (I), a compound shown as a formula (II), a photosensitizer and a solvent, reacting for 1-3 h (preferably 2h) at 30-50 ℃ (40 ℃) under the irradiation of 15W blue LED light, and then carrying out post-treatment on a reaction solution to obtain a benzofluorenone compound shown as a formula (III);
the ratio of the amount of the compound shown in the formula (I), the amount of the compound shown in the formula (II) and the amount of the photosensitizer is 1: 2-4: 0.05-0.15, preferably 1: 3: 0.1;
the volume usage amount of the solvent is 10-20 mL/mmol based on the amount of the compound shown in the formula (I);
the solvent is one or a mixed solvent of more than two of ethanol, methanol and N, N-dimethylformamide in any proportion, preferably ethanol;
the photosensitizer is represented by formula (IV) or (V):
Figure BDA0001783103520000021
the post-treatment method comprises the following steps: after the reaction is finished, cooling the reaction liquid to room temperature (20-30 ℃), adding 100-200-mesh silica gel, uniformly stirring, evaporating under reduced pressure to remove the solvent, then separating and purifying on a column, taking 100-200-mesh silica gel as column filler, and using petroleum ether/ethyl acetate in a volume ratio of 20:1 as eluent, collecting eluent containing a target compound, evaporating the solvent and drying to obtain a product shown in a formula (III);
Figure BDA0001783103520000022
in the formula (I), (II) or (III),
R1hydrogen, C1-C4 alkyl or halogen, preferably hydrogen, methyl, fluorine or chlorine;
R2is hydrogen or halogen, preferably hydrogen or chlorine;
R3hydrogen, C1-C4 alkyl, C1-C4 alkoxy or halogen, preferably hydrogen, methyl, tert-butyl, methoxy, fluorine, chlorine or bromine.
Preferably, the benzofluorenone compound represented by the formula (III) in the invention is one of the following compounds:
Figure BDA0001783103520000031
compared with the prior art, the invention has the beneficial effects that:
(1) the method is safe and environment-friendly, does not generate waste gas, and has low operation risk;
(2) the substrate has good adaptability, and various substituents can realize oxidative cyclization;
(3) the reaction condition is mild;
(4) meanwhile, the reaction adopts a photocatalysis mode to synthesize the benzofluorenone, so that the method is more environment-friendly and green and is closer to the idea of green chemistry.
(IV) detailed description of the preferred embodiments
The invention will be further illustrated by the following examples, without limiting the scope of the invention:
in the following examples, 15W blue LED lamps are used which are commercially available from conventional sources, such as commercial photovoltaics.
Example 1
Figure BDA0001783103520000041
0.3mmol of 1- (2- (phenylethynyl) phenyl) prop-2-en-1-one, 0.03mmol of copper photosensitizer (IV) and 0.9mmol of phenyl tetrafluoroborate diazonium salt are added into a 15mL thick-wall pressure-resistant reaction tube and are reacted for 2 hours at the temperature of 40 ℃ in 3mL of solvent ethanol under the irradiation of 15W blue LED light. After cooling to room temperature, two spoons (0.5g, the same applies hereinafter) of column chromatography silica gel (100-. The material was a yellow solid in 68% yield.
1H NMR(500MHz,CDCl3):δ＝8.26(s,1H),7.97(dd,J＝7.5,J＝1.5Hz,1H),7.76(dd,J＝ 6.5,J＝0.9Hz,1H),7.65–7.60(m,3H),7.51–7.42(m,5H),7.26–7.19(m,2H),6.35(d,J＝7.5 Hz,1H)ppm.13C NMR(125MHz,CDCl3):δ＝193.2,145.2,137.4,136.9,136.5,135.3, 134.70,134.66,133.4,132.6,130.8,129.7,129.3,128.9,128.6,128.3,127.1,126.8,125.2,124.2, 123.8ppm.
Example 2
Figure BDA0001783103520000042
0.3mmol of 1- (2- (phenylethynyl) phenyl) prop-2-en-1-one, 0.03mmol of copper photosensitizer (V) and 0.9mmol of p-methylphenyl tetrafluoroborate diazonium salt are added into a 15mL thick-wall pressure-resistant reaction tube and reacted for 2 hours at 40 ℃ in 3mL of solvent ethanol under the irradiation of 15W blue LED light. After cooling to room temperature, two-spoon column chromatography silica gel (100-200 mesh) was added to the reaction solution, and the solvent was removed by distillation under reduced pressure, followed by column chromatography to obtain a pure product represented by the structural formula (III-2) (with petroleum ether/ethyl acetate 20:1 as eluent). The material was a yellow solid in 60% yield.
1H NMR(500MHz,CDCl3):δ＝8.21(s,1H),7.85(d,J＝8.5Hz,1H),7.74(dd,J＝6.5,J＝ 1.0Hz,1H),7.65–7.61(m,3H),7.43–7.40(m,2H),7.32(dd,J＝8.0,J＝1.5Hz,1H),7.23–7.17 (m,3H),6.29(d,J＝7.5Hz,1H),2.40(s,3H)ppm.13C NMR(125MHz,CDCl3):δ＝193.3, 145.2,139.4,137.6,137.1,136.6,135.6,134.6,134.1,131.9,131.6,130.6,129.8,129.3,129.0, 128.5,128.3,126.4,125.1,124.1,123.8,22.1ppm.
Example 3
Figure BDA0001783103520000051
0.3mmol of 1- (2- (phenylethynyl) phenyl) prop-2-en-1-one, 0.015mmol of copper photosensitizer (IV) and 0.9mmol of p-chlorophenyl tetrafluoroborate diazonium salt are added into a 15mL thick-wall pressure-resistant reaction tube and are reacted for 2 hours at the temperature of 40 ℃ in 3mL of solvent ethanol under the irradiation of 15W blue LED light. After cooling to room temperature, two-spoon column chromatography silica gel (100-200 mesh) was added to the reaction solution, and the solvent was removed by distillation under reduced pressure, followed by column chromatography to obtain a pure product represented by the structural formula (III-3) (with petroleum ether/ethyl acetate 20:1 as eluent). The material was a yellow solid in 63% yield.
1H NMR(500MHz,CDCl3):δ＝8.21(s,1H),7.89(d,J＝9.0Hz,1H),7.75(d,J＝7.0Hz,1 H),7.66–7.62(m,3H),7.45–7.39(m,4H),7.26–7.19(m,2H),6.33(d,J＝7.5Hz,1H)ppm.13C NMR(125MHz,CDCl3):δ＝192.8,144.8,137.8,136.7,136.53,136.51,135.3,134.8,133.9,132.8, 132.0,131.7,129.7,129.5,129.0,128.7,127.7,126.2,124.8,124.3,124.0ppm.
Example 4
Figure BDA0001783103520000052
0.3mmol of 1- (2- (phenylethynyl) phenyl) prop-2-en-1-one, 0.045mmol of copper photosensitizer (IV) and 0.9mmol of p-bromophenyl tetrafluoroborate diazonium salt are added into a 15mL thick-wall pressure-resistant reaction tube and are reacted for 2 hours at the temperature of 40 ℃ in 3mL solvent ethanol under the irradiation of 15W blue LED light. After cooling to room temperature, two-spoon column chromatography silica gel (100-200 mesh) was added to the reaction solution, and the solvent was removed by distillation under reduced pressure, followed by column chromatography to obtain a pure product represented by the structural formula (III-4) (with petroleum ether/ethyl acetate 20:1 as eluent). The material was a yellow solid in 66% yield.
1H NMR(500MHz,CDCl3):δ＝8.19(s,1H),7.81(d,J＝8.5Hz,1H),7.75(d,J＝7.0Hz,1 H),7.66–7.62(m,3H),7.60–7.55(m,2H),7.42–7.39(m,2H),7.26–7.19(m,2H),6.31(d,J＝ 7.5Hz,1H)ppm.13C NMR(125MHz,CDCl3):δ＝192.7,144.7,138.1,136.6,136.48,136.46, 134.8,133.7,132.9,132.0,131.9,130.2,129.6,129.5,129.4,129.0,128.7,124.8,124.3,124.0, 123.8ppm.
Example 5
Figure BDA0001783103520000061
0.3mmol of 1- (2- (phenylethynyl) phenyl) prop-2-en-1-one, 0.03mmol of copper photosensitizer (IV) and 0.9mmol of p-tert-butylphenyl tetrafluoroborate diazonium salt are added into a 15mL thick-walled pressure-resistant reaction tube, and the mixture is reacted for 3 hours at 40 ℃ in 3mL solvent ethanol under the irradiation of 15W blue LED light. After cooling to room temperature, two-spoon column chromatography silica gel (100-200 mesh) was added to the reaction solution, and the solvent was removed by distillation under reduced pressure, followed by column chromatography to give the pure product represented by the structural formula (III-15) (with petroleum ether/ethyl acetate 20:1 as eluent), which was a yellow solid in 68% yield.
1H NMR(500MHz,CDCl3):δ＝8.21(s,1H),7.90(d,J＝8.5Hz,1H),7.74(d,J＝6.5Hz,1 H),7.64–7.56(m,4H),7.44–7.41(m,3H),7.24–7.18(m,2H),6.35(d,J＝7.5Hz,1H),1.27(s,9 H)ppm.13C NMR(126MHz,CDCl3):δ＝193.3,152.2,145.3,137.6,136.9,136.6,135.3,134.8, 134.6,132.1,131.5,130.4,129.7,129.2,128.5,128.3,125.5,124.8,124.1,123.8,122.6,35.2,31.0 ppm.
Example 6
Figure BDA0001783103520000062
0.3mmol of 1- (2- (phenylethynyl) phenyl) prop-2-en-1-one, 0.03mmol of copper photosensitizer (IV) and 0.6mmol of phenyl tetrafluoroborate diazonium salt are added into a 15mL thick-wall pressure-resistant reaction tube and are reacted for 2 hours at the temperature of 40 ℃ in 3mL of solvent ethanol under the irradiation of 15W blue LED light. After cooling to room temperature, two-spoon column chromatography silica gel (100-200 mesh) was added to the reaction solution, and the solvent was removed by distillation under reduced pressure, followed by column chromatography to obtain a pure product represented by the structural formula (III-6) (with petroleum ether/ethyl acetate 20:1 as eluent). The material was a yellow solid in 64% yield.
1H NMR(500MHz,CDCl3):δ＝8.18(s,1H),7.86(d,J＝9.0Hz,1H),7.73(d,J＝7.5Hz,1 H),7.65–7.59(m,3H),7.43(dd,J＝8.0,J＝2.0Hz,2H),7.24–7.12(m,3H),6.78(d,J＝2.5Hz,1 H),6.30(d,J＝7.5Hz,1H),3.72(s,3H)ppm.13C NMR(125MHz,CDCl3):δ＝193.2,160.3, 145.0,138.8,137.7,136.8,136.2,134.4,133.6,132.3,130.7,129.7,129.4,128.6,128.5,128.4, 125.1,124.1,123.7,118.2,107.1,55.3ppm.
Example 7
Figure BDA0001783103520000071
0.3mmol of 1- (2- (phenylethynyl) phenyl) prop-2-en-1-one, 0.03mmol of copper photosensitizer (IV) and 1.2mmol of 2-methylphenyl tetrafluoroborate diazonium salt are added into a 15mL thick-wall pressure-resistant reaction tube and reacted for 2 hours at 40 ℃ in 3mL of solvent ethanol under the irradiation of 15W blue LED light. After cooling to room temperature, two-spoon column chromatography silica gel (100-200 mesh) was added to the reaction solution, and the solvent was removed by distillation under reduced pressure, followed by column chromatography to obtain a pure product represented by the structural formula (III-7) (with petroleum ether/ethyl acetate 20:1 as eluent). The material was a yellow solid in 66% yield.
1H NMR(500MHz,CDCl3):δ＝8.48(s,1H),7.76(dd,J＝6.5,J＝1.0Hz,1H),7.63–7.59 (m,3H),7.43–7.40(m,2H),7.35–7.32(m,3H),7.25–7.18(m,2H),6.31(d,J＝7.5Hz,1H),2.79 (s,3H)ppm.13C NMR(125MHz,CDCl3):δ＝193.6,145.2,137.9,137.6,137.3,136.6,135.2, 135.1,134.7,132.6,132.2,129.8(2C),129.2,128.6,128.3,127.9,125.6,124.2,123.8,121.6,19.8 ppm.
Example 8
Figure BDA0001783103520000072
0.3mmol of 1- (2- (phenylethynyl) phenyl) prop-2-en-1-one, 0.03mmol of copper photosensitizer (IV) and 0.9mmol of 2-bromophenyl tetrafluoroborate diazonium salt are added into a 15mL thick-wall pressure-resistant reaction tube and are reacted for 2 hours at the temperature of 40 ℃ in 3mL of methanol solvent under the irradiation of 15W blue LED light. After cooling to room temperature, two-spoon column chromatography silica gel (100-200 mesh) was added to the reaction solution, and the solvent was removed by distillation under reduced pressure, followed by column chromatography to obtain a pure product represented by the structural formula (III-8) (with petroleum ether/ethyl acetate 20:1 as eluent). The material was a yellow solid in 57% yield.
1H NMR(500MHz,CDCl3):δ＝8.71(s,1H),7.79–7.77(m,2H),7.64–7.62(m,3H),7.44 (d,J＝8.5Hz,1H),7.42–7.40(m,2H),7.30–7.29(m,1H),7.26–7.20(m,2H),6.33(d,J＝8.0Hz, 1H)ppm.13C NMR(125MHz,CDCl3):δ＝192.8,144.7,138.6,137.2,136.6,136.2,134.9,134.8, 133.6,132.4,131.0,129.7,129.4,129.1,190.0,128.6,127.0,126.0,124.5,124.4,124.1ppm.
Example 9
Figure BDA0001783103520000081
0.3mmol of 1- (4-methyl-2- (phenylethynyl) phenyl) prop-2-en-1-one, 0.03mmol of copper photosensitizer (IV) and 0.9mmol of phenyl tetrafluoroborate diazonium salt are added into a 15mL thick-wall pressure-resistant reaction tube and are reacted for 2 hours at the temperature of 40 ℃ in 3mL of solvent N, N-dimethylformamide under the irradiation of 15W blue LED light. After cooling to room temperature, two-spoon column chromatography silica gel (100-200 mesh) was added to the reaction solution, and the solvent was removed by distillation under reduced pressure, followed by column chromatography to obtain a pure product represented by the structural formula (III-9) (with petroleum ether/ethyl acetate 20:1 as eluent). The material was a yellow solid in 51% yield.
1H NMR(500MHz,CDCl3):δ＝8.23(s,1H),7.96–7.94(m,1H),7.65–7.60(m,4H),7.50–7.45(m,3H),7.43–7.41(m,2H),7.04(d,J＝7.5Hz,1H),6.10(s,1H),2.14(s,3H)ppm.13C NMR(125MHz,CDCl3):δ＝192.9,145.7,145.5,137.6,136.8,135.3,134.5,134.3,133.4, 133.2,130.7,129.8,129.4,129.2,128.8,128.2,127.1,126.7,124.9,124.7,124.1,22.3ppm.
Example 10
Figure BDA0001783103520000082
0.3mmol of 1- (4-fluoro-2- (phenylethynyl) phenyl) prop-2-en-1-one, 0.03mmol of copper photosensitizer (IV) and 0.9mmol of phenyl tetrafluoroborate diazonium salt are added into a 15mL thick-wall pressure-resistant reaction tube and are reacted for 2 hours at the temperature of 30 ℃ in 3mL solvent ethanol under the irradiation of 15W blue LED light. After cooling to room temperature, two-spoon column chromatography silica gel (100-200 mesh) was added to the reaction solution, and the solvent was removed by distillation under reduced pressure, followed by column chromatography to obtain a pure product represented by the structural formula (III-10) (with petroleum ether/ethyl acetate 20:1 as eluent). The material was a yellow solid in 67% yield.
1H NMR(500MHz,CDCl3):δ＝8.25(s,1H),7.97(d,J＝8.0Hz,1H),7.75(dd,J＝8.5,J＝ 5.5Hz,1H),7.65–7.63(m,2H),7.52–7.48(m,3H),7.43–7.40(m,2H),7.26–7.21(m,1H), 6.93–6.89(m,1H),5.97(dd,J＝9.5,J＝2.5Hz,1H)ppm.13C NMR(125MHz,CDCl3):δ＝191.5, 166.9(d,J＝252.5Hz),148.0,147.9,136.8,136.75,135.3,134.0(d,J＝2.5Hz),133.6,132.7, 130.8,129.5,129.4,129.0,128.6,128.3,127.2(d,J＝10.0Hz),126.2(d,J＝10.0Hz),125.2,115.6 (d,J＝23.8Hz),111.4(d,J＝25.0Hz)ppm.
Example 11
Figure BDA0001783103520000091
0.3mmol of 1- (4-chloro-2- (phenylethynyl) phenyl) prop-2-en-1-one, 0.03mmol of copper photosensitizer (IV) and 0.9mmol of phenyl tetrafluoroborate diazonium salt are added into a 15mL thick-wall pressure-resistant reaction tube and are reacted for 2 hours at 50 ℃ in 3mL solvent ethanol under the irradiation of 15W blue LED light. After cooling to room temperature, two-spoon column chromatography silica gel (100-200 mesh) was added to the reaction solution, and the solvent was removed by distillation under reduced pressure, followed by column chromatography to obtain a pure product represented by the structural formula (III-11) (with petroleum ether/ethyl acetate 20:1 as eluent). The material was a yellow solid in 58% yield.
1H NMR(500MHz,CDCl3):δ＝8.26(s,1H),7.97(d,J＝7.5Hz,1H),7.67–7.63(m,4H), 7.54–7.48(m,3H),7.43–7.39(m,2H),7.21(dd,J＝8.0,J＝1.5Hz,1H),6.25(s,1H)ppm.13C NMR(125MHz,CDCl3):δ＝191.8,146.7,140.9,136.84,136.78,135.4,134.8,134.1,133.6,132.5, 130.8,129.6,129.49,129.2,128.72 128.66,127.3,127.2,125.5,125.2,124.3ppm.
Example 12
Figure BDA0001783103520000092
0.3mmol of 1- (5-fluoro-2- (phenylethynyl) phenyl) prop-2-en-1-one, 0.03mmol of copper photosensitizer (IV) and 0.9mmol of phenyl tetrafluoroborate diazonium salt are added into a 15mL thick-wall pressure-resistant reaction tube and reacted for 1 hour at 40 ℃ in 3mL solvent ethanol under the irradiation of 15W blue LED light. After cooling to room temperature, two-spoon column chromatography silica gel (100-200 mesh) was added to the reaction solution, and the solvent was removed by distillation under reduced pressure, followed by column chromatography to obtain a pure product represented by the structural formula (III-12) (with petroleum ether/ethyl acetate 20:1 as eluent). The material was a yellow solid in 51% yield.
1HNMR(500MHz,CDCl3):δ＝8.23(s,1H),7.94(dd,J＝6.5,J＝2.0Hz,1H),7.65–7.59(m, 3H),7.49–7.45(m,3H),7.43–7.37(m,3H),6.90–6.86(m,1H),6.28(dd,J＝8.5,J＝5.0Hz,1H) ppm.13C NMR(125MHz,CDCl3):δ＝191.9(d,J＝2.5Hz),163.1(d,J＝250.0Hz),141.0(d,J＝ 2.5Hz),138.7(d,J＝6.3Hz),137.2,137.0,134.6,134.3,133.1,132.6,130.9,129.7,129.4,129.2, 128.5,127.1,126.9,125.6,125.2(d,J＝7.5Hz),121.2(d,J＝23.8Hz),111.2(d,J＝22.5Hz)ppm.
Example 13
Figure BDA0001783103520000101
0.3mmol of 1- (2- (4-chloro-phenylethynyl) phenyl) prop-2-en-1-one, 0.03mmol of copper photosensitizer (IV) and 0.9mmol of phenyl tetrafluoroborate diazonium salt are added into a 15mL thick-wall pressure-resistant reaction tube and are reacted for 2 hours at 40 ℃ in 3mL solvent ethanol under the irradiation of 15W blue LED light. After cooling to room temperature, two-spoon column chromatography silica gel (100-200 mesh) was added to the reaction solution, and the solvent was removed by distillation under reduced pressure, followed by column chromatography to obtain a pure product represented by the structural formula (III-13) (with petroleum ether/ethyl acetate 20:1 as eluent). The material was a yellow solid in 68% yield.
1H NMR(500MHz,CDCl3):δ＝8.24(s,1H),7.97-7.93(m,1H),7.76-7.72(m,1H),7.62-7.59 (m,2H),7.49-7.44(m,2H),7.41-7.35(m,3H),7.26(s,1H),7.25-7.24(m,1H),6.43e6.41(m,1H)；13C NMR(125MHz,CDCl3)δ＝193.0,144.8,136.7,136.5,135.9,135.4,134.8,134.5,133.4, 133.2,132.5,131.2,130.9,129.6,129.1,128.9,127.0,126.8,125.5,124.4,123.7ppm。

Claims (5)

1. A method for synthesizing a benzofluorenone compound by photocatalysis is characterized by comprising the following steps:
mixing a compound shown as a formula (I), a compound shown as a formula (II), a photosensitizer and a solvent, reacting for 1-3 h at 30-50 ℃ under the irradiation of 15W blue LED light, and then carrying out post-treatment on a reaction solution to obtain a benzofluorenone compound shown as a formula (III);
the ratio of the amount of the compound shown in the formula (I), the amount of the compound shown in the formula (II) and the amount of the photosensitizer is 1: 2-4: 0.05 to 0.15;
the solvent is one or a mixed solvent of more than two of ethanol, methanol and N, N-dimethylformamide in any proportion;
the photosensitizer is represented by formula (IV) or (V):
Figure FDA0001783103510000011
in the formula (I), (II) or (III),
R1hydrogen, C1-C4 alkyl or halogen;
R2is hydrogen or halogen;
R3hydrogen, C1-C4 alkyl, C1-C4 alkoxy or halogen.
2. The method according to claim 1, wherein the ratio of the amounts of the compound of formula (I), the compound of formula (II), and the photosensitizer is 1: 3: 0.1.
3. the method according to claim 1, wherein the solvent is used in a volume of 10 to 20mL/mmol based on the amount of the compound represented by formula (I).
4. The method of claim 1, wherein the solvent is ethanol.
5. The method of claim 1, wherein the post-processing is by: after the reaction is finished, cooling the reaction liquid to room temperature, adding 100-200 mesh silica gel, uniformly stirring, evaporating under reduced pressure to remove the solvent, then separating and purifying on a column, taking 100-200 mesh silica gel as a column filler, and using petroleum ether/ethyl acetate in a volume ratio of 20:1 as eluent, collecting the eluent containing the target compound, evaporating the solvent and drying to obtain the product shown in the formula (III).
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112441936A (en) * 2019-08-27 2021-03-05 浙江工业大学 Method for synthesizing enaminone compounds
CN112441940A (en) * 2019-08-27 2021-03-05 浙江工业大学 Method for synthesizing trifluoroethoxy alkene iodine compound
CN112441935A (en) * 2019-08-27 2021-03-05 浙江工业大学 Synthesis method of beta-aminoketone compound

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104892387A (en) * 2015-05-20 2015-09-09 浙江工业大学 Method for synthesizing fluorofluorenone compound
CN105085217A (en) * 2014-08-29 2015-11-25 浙江工业大学 Method for synthesis of benzfluorenone and its derivative by copper as catalyst
CN105085208A (en) * 2014-08-29 2015-11-25 浙江工业大学 Method for preparing benzfluorenone compound by palladium as catalyst
CN106278856A (en) * 2015-05-20 2017-01-04 浙江工业大学 A kind of synthetic method replacing benzfluorenone compounds

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105085217A (en) * 2014-08-29 2015-11-25 浙江工业大学 Method for synthesis of benzfluorenone and its derivative by copper as catalyst
CN105085208A (en) * 2014-08-29 2015-11-25 浙江工业大学 Method for preparing benzfluorenone compound by palladium as catalyst
CN104892387A (en) * 2015-05-20 2015-09-09 浙江工业大学 Method for synthesizing fluorofluorenone compound
CN106278856A (en) * 2015-05-20 2017-01-04 浙江工业大学 A kind of synthetic method replacing benzfluorenone compounds

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
JIAN ZHANG等: "Facile and Diverse Synthesis of Benzo[b]fluorenone Derivatives through a Copper/Selectfluor-Catalyzed Tandem Annulation of 1,6-Enynes", 《EUR. J. ORG. CHEM.》 *
YI-MING LI等: "Iron-Catalyzed α-Methylenation of Ketones with N,N-Dimethylacetamide: An Approach for α,β-Unsaturated Carbonyl Compounds", 《EUR. J. ORG. CHEM.》 *
YU-FENG LIU等: "Transition Metal-Free α‑Csp3‑H Methylenation of Ketones to Form CC Bond Using Dimethyl Sulfoxide as Carbon Source", 《J. ORG. CHEM.》 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112441936A (en) * 2019-08-27 2021-03-05 浙江工业大学 Method for synthesizing enaminone compounds
CN112441940A (en) * 2019-08-27 2021-03-05 浙江工业大学 Method for synthesizing trifluoroethoxy alkene iodine compound
CN112441935A (en) * 2019-08-27 2021-03-05 浙江工业大学 Synthesis method of beta-aminoketone compound
CN112441936B (en) * 2019-08-27 2022-07-22 浙江工业大学 Method for synthesizing enaminone compound
CN112441940B (en) * 2019-08-27 2022-07-22 浙江工业大学 Method for synthesizing trifluoroethoxy alkene iodine compound
CN112441935B (en) * 2019-08-27 2022-07-22 浙江工业大学 Synthesis method of beta-aminoketone compound

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