CN110872218B - Method for synthesizing benzofluorenone compound under catalysis of Cu - Google Patents
Method for synthesizing benzofluorenone compound under catalysis of Cu Download PDFInfo
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- C07—ORGANIC CHEMISTRY
- 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
- C07C45/68—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 by increase in the number of carbon atoms
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/02—Ortho- or ortho- and peri-condensed systems
- C07C2603/40—Ortho- or ortho- and peri-condensed systems containing four condensed rings
Abstract
A method for synthesizing a benzofluorenone compound by Cu catalysis comprises the following steps: mixing a compound shown as a formula (I), a compound shown as a formula (II), a catalyst and a solvent, heating to 70-90 ℃, reacting for 1-3 h, and then carrying out aftertreatment on reaction liquid to obtain a benzofluorenone compound shown as a formula (III); the invention is safe and environment-friendly, does not produce waste gas and has low operation risk; the substrate has good adaptability, and various substituents can realize oxidative aromatization; the reaction condition is mild; meanwhile, the reaction adopts a free radical ring addition mode to synthesize the benzofluorenone, has relatively high atom economy, and is more environment-friendly by adopting nontoxic ethanol as a solvent;
Description
(I) technical field
The invention relates to a method for synthesizing benzofluorenone compounds by Cu catalysis.
(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 benzofluorenone mainly comprise oxidation reaction of benzofluorene, friedel-crafts acylation reaction of aryl carboxylic acid and derivatives thereof, and intramolecular Diels-Alder reaction of (o-arylethynylaryl) propiophenone compounds, but all of the methods have various defects, such as use of toxic or seriously polluted oxidants, high reaction temperature, poor tolerance of functional groups and the like.
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 free radical ring addition mode, realizes the synthesis of the benzofluorenone compound under the conditions of a small amount of catalyst and mild temperature, does not need to add extra oxidant, is more environment-friendly, and simultaneously 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 synthesizing a benzofluorenone compound under the catalysis of Cu comprises the following steps:
mixing a compound shown as a formula (I), a compound shown as a formula (II), a catalyst and a solvent, heating to 70-90 ℃ (preferably 80 ℃) to react for 1-3 h (preferably 2 h), and then carrying out aftertreatment on reaction liquid to obtain a benzofluorenone compound shown as a formula (III);
the mass ratio of the compound shown in the formula (I), the compound shown in the formula (II) and the catalyst is 1:1 to 3:0.05 to 0.15, preferably 1:3:0.1;
the volume usage of the solvent is 10-20 mL/mmol based on the substance 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 catalyst is cuprous iodide or cuprous bromide;
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, stirring uniformly, 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);
in the formula (I), (II) or (III),
R 1 hydrogen, C1-C4 alkyl or halogen, preferably hydrogen, methyl, fluorine or chlorine;
R 2 is hydrogen or halogen, preferably hydrogen or chlorine;
R 3 hydrogen, C1-C4 alkyl, C1-C4 alkoxy or halogen, preferably hydrogen, methyl, tert-butyl, methoxy, fluorine, chlorine or bromine.
Preferably, the benzofluorenone compound shown in the formula (III) is one of the following compounds:
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 aromatization;
(3) The reaction condition is mild;
(4) Meanwhile, the reaction adopts a free radical ring addition mode to synthesize the benzofluorenone, has relatively high atom economy, and adopts nontoxic ethanol as a solvent, so that the reaction is more environment-friendly.
(IV) detailed description of the invention
The invention will be further illustrated by the following examples, without limiting the scope of the invention:
example 1
0.3mmol of 1- (2- (phenylethynyl) phenyl) prop-2-en-1-one, 0.03mmol of cuprous iodide and 0.9mmol of phenyl tetrafluoroborate diazonium salt are added into a 15mL thick-wall pressure-resistant reaction tube and reacted for 2 hours at 80 ℃ in 3mL solvent ethanol. After cooling to room temperature, two spoons (0.5 g, the same applies hereinafter) of column chromatography silica gel (100-200 mesh) were 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-1) (with petroleum ether/ethyl acetate = 20. The material was a yellow solid in 65% yield.
1 H 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. 13 C 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
0.3mmol of 1- (2- (phenylethynyl) phenyl) prop-2-en-1-one, 0.03mmol of cuprous bromide 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 the temperature of 80 ℃ in 3mL solvent ethanol. 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 as an eluent. The material was a yellow solid in 52% yield.
1 H 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. 13 C 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
1 H 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. 13 C 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
0.3mmol of 1- (2- (phenylethynyl) phenyl) prop-2-en-1-one, 0.03mmol of cuprous iodide and 0.9mmol of p-bromophenyl tetrafluoroborate diazonium salt are added into a 15mL thick-walled pressure-resistant reaction tube and reacted for 2 hours at the temperature of 80 ℃ in 3mL solvent ethanol. 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 as an eluent. The material was a yellow solid in 47% yield.
1 H 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. 13 C 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
0.3mmol of 1- (2- (phenylethynyl) phenyl) prop-2-en-1-one, 0.015mmol of cuprous iodide and 0.9mmol of p-tert-butylphenyl tetrafluoroborate diazonium salt are introduced into a 15mL thick-walled pressure-resistant reaction tube, and reacted in 3mL of ethanol as a solvent at 80 ℃ for 2 hours. 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-5) (with petroleum ether/ethyl acetate = 20. The material was a yellow solid in 58% yield.
1 H 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. 13 C 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
0.3mmol of 1- (2- (phenylethynyl) phenyl) prop-2-en-1-one, 0.03mmol of cuprous iodide and 0.9mmol of p-methoxyphenyltetrafluoroboric acid diazonium salt are added into a 15mL thick-walled pressure-resistant reaction tube and reacted in 3mL of solvent methanol at 80 ℃ for 2 hours. 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 as an eluent. The material was a yellow solid in 49% yield.
1 H 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. 13 C 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
0.3mmol of 1- (2- (phenylethynyl) phenyl) prop-2-en-1-one, 0.03mmol of cuprous iodide and 0.9mmol of o-methylphenyl tetrafluoroborate diazonium salt are added into a 15mL thick-wall pressure-resistant reaction tube and reacted in 3mL of N, N-dimethylformamide serving as a solvent at the temperature of 80 ℃ for 2 hours. 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 as an eluent. The material was a yellow solid in 51% yield.
1 H 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. 13 C 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
0.3mmol of 1- (2- (phenylethynyl) phenyl) prop-2-en-1-one, 0.03mmol of cuprous iodide and 0.9mmol of o-bromophenyl tetrafluoroborate diazonium salt are added into a 15mL thick-walled pressure-resistant reaction tube and reacted for 2 hours at 90 ℃ in 3mL solvent ethanol. 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. The material was a yellow solid in 43% yield.
1 H 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. 13 C 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
0.3mmol of 1- (4-methyl-2- (phenylethynyl) phenyl) prop-2-en-1-one, 0.03mmol of cuprous iodide and 0.9mmol of phenyl tetrafluoroborate diazonium salt are added into a 15mL thick-wall pressure-resistant reaction tube and reacted for 2 hours at the temperature of 70 ℃ in 3mL solvent ethanol. 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 as an eluent. The material was a yellow solid in 59% yield.
1 H 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. 13 C 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
0.3mmol of 1- (4-fluoro-2- (phenylethynyl) phenyl) prop-2-en-1-one, 0.03mmol of cuprous iodide 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 the temperature of 80 ℃ in 3mL solvent ethanol. 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 as an eluent. The material was a yellow solid in 54% yield.
1 H 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. 13 C 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
0.3mmol of 1- (4-chloro-2- (phenylethynyl) phenyl) prop-2-en-1-one, 0.03mmol of cuprous iodide and 0.9mmol of phenyl tetrafluoroborate diazonium salt are added into a 15mL thick-wall pressure-resistant reaction tube and reacted for 3 hours at the temperature of 80 ℃ in 3mL solvent ethanol. 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. The material was a yellow solid in 53% yield.
1 H 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. 13 C 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
0.3mmol of 1- (5-fluoro-2- (phenylethynyl) phenyl) prop-2-en-1-one, 0.03mmol of cuprous iodide and 0.9mmol of phenyl tetrafluoroborate diazonium salt are added into a 15mL thick-wall pressure-resistant reaction tube and reacted for 2 hours at the temperature of 80 ℃ in 3mL solvent ethanol. 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 as an eluent. The material was a yellow solid in 56% yield.
1 HNMR(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. 13 C 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
0.3mmol of 1- (2- (4-chlorophenylethynyl) phenyl) prop-2-en-1-one, 0.03mmol of cuprous iodide and 0.9mmol of phenyl tetrafluoroborate diazonium salt are added into a 15mL thick-walled pressure-resistant reaction tube and reacted for 2 hours at the temperature of 80 ℃ in 3mL solvent ethanol. 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. The material was a yellow solid in 65% yield.
1 H 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)； 13 C 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 under the catalysis of Cu is characterized by comprising the following steps:
mixing a compound shown as a formula (I), a compound shown as a formula (II), a catalyst and a solvent, heating to 70-90 ℃, reacting for 1-3 h, and then carrying out aftertreatment on reaction liquid to obtain a benzofluorenone compound shown as a formula (III);
the mass ratio of the compound shown in the formula (I), the compound shown in the formula (II) and the catalyst is 1:1 to 3:0.05 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 catalyst is cuprous iodide or cuprous bromide;
in the formula (I), (II) or (III),
R 1 is hydrogen, C1-C4 alkyl or halogen;
R 2 is hydrogen or halogen;
R 3 is hydrogen, C1-C4 alkyl, C1-C4 alkaneOxy or halogen.
2. The method of claim 1, wherein the ratio of the amounts of the compound of formula (I), the compound of formula (II), and the catalyst 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 substance 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, and then separating and purifying on a column, wherein the silica gel with 100-200 mesh is used as a column filler, and the volume ratio of petroleum ether to ethyl acetate is 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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| 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 |
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| 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 |
Non-Patent Citations (1)
| Title |
|---|
| Facile and Diverse Synthesis of Benzo[b]fluorenone Derivatives via Copper/Selectfluor System-Catalyzed Tandem Annulation of 1,6-Enynes;Jian Zhang等;《European Journal of Organic Chemistry》;20160905;全文 * |
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