CN112441875A - Method for copper photocatalytic synthesis of 9-trifluoromethyl-9, 10-dihydrophenanthrene compound - Google Patents
Method for copper photocatalytic synthesis of 9-trifluoromethyl-9, 10-dihydrophenanthrene compound Download PDFInfo
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- C07C17/35—Preparation of halogenated hydrocarbons by reactions not affecting the number of carbon or of halogen atoms in the reaction
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Abstract
A method for copper photocatalytic synthesis of 9-trifluoromethyl-9, 10-dihydrophenanthrene compounds comprises the following steps: mixing a substrate (I), a photosensitizer, an alkaline substance and a solvent, reacting for 20-36 h under the conditions of illumination of a blue LED, temperature of 15-40 ℃ and protection of inert gas, and then carrying out aftertreatment on a reaction solution to obtain a 9-trifluoromethyl-9, 10-dihydrophenanthrene compound (II); the invention is safe and environment-friendly, does not generate waste gas and has low operation risk; good adaptability of the substrate, eachThe various substituents may all effect cyclization; the reaction condition is mild; meanwhile, the reaction has certain innovativeness and high atom economy, adopts a photocatalysis mode to replace the traditional heating mode, reduces energy consumption and better conforms to the modern green chemistry idea;
Description
(I) technical field
The invention relates to a method for synthesizing 9-trifluoromethyl-9, 10-dihydrophenanthrene compounds.
(II) background of the invention
As the name implies, the fluorine-containing compound is a so-called compound containing fluorine element, and the research of the fluorine-containing compound is a huge field which can relate to various fields of society. Fluorine-containing compounds play a crucial role in pharmaceutical, veterinary, agrochemical and material chemistry science, because the introduction of fluorine atoms greatly changes the steric, electrical and lipophilic properties of the compounds. During the development of a drug, therefore, drug researchers often introduce one or more fluorine atoms to improve the activity of the drug. Because of the uniqueness of fluorine element, researchers are dedicated to research on fluorine-containing compounds, and the research on the enthusiasm of organofluoro compounds is promoted.
Dihydrophenanthrenes, also known as 9, 10-dihydrophenanthrenes, are found in nature and are found in a wide variety of herbal medicine. Because of the structural particularity, the dihydrophenanthrene compound has unique application value in industry, and can effectively inhibit the generation of inflammatory factors and synthesize a series of anticancer drugs as an important medical intermediate, thereby being a main framework of a plurality of anticancer drugs.
Currently, many methods for synthesizing dihydrophenanthrene compounds are available, for example, in 2011, Daniela et al (org.lett.,2011,13,12) report that 2-phenethyliodobenzene is used as a substrate, potassium tert-butoxide is used as a base, pyridine is used as a solvent, and a dihydrophenanthrene compound (scheme 1) is synthesized by adopting a free radical addition cyclization mode under the microwave high-temperature condition of 160 ℃, but the synthesis mode has great limitation, needs to be carried out under the high-temperature condition, and meanwhile, pyridine, a solvent with high toxicity, has great influence on the environment and is not beneficial to industrial production. While the invention synthesizes the 9, 10-dihydrophenanthrene compound in one step, a special functional group (trifluoromethyl) is successfully introduced to the 9, 10-dihydrophenanthreneThe structure is further modified, so that the synthesized 9-trifluoromethyl-9, 10-dihydrophenanthrene compound has potential bioactivity. Meanwhile, the 9-trifluoromethyl-9, 10-dihydrophenanthrene compound has not been reported so far, but the invention adopts a photocatalysis mode, uses a 2-phenyl-alpha-trifluoromethyl-styrene compound which is relatively easy to synthesize as a substrate, adopts a photocatalysis mode which is currently in line with the current social development situation, uses a relatively cheap copper photosensitizer as a catalyst, uses tetrahydrofuran with relatively low toxicity as a solvent and uses common K3PO4The target product 9-trifluoromethyl-9, 10-dihydrophenanthrene compound is obtained with high yield at room temperature as alkali. The method does not need additional heating, has low energy consumption and simple operation, has 100 percent of atomic utilization rate, and accords with the theme of the development of the current green chemistry era.
Disclosure of the invention
Aiming at the defects of the prior art, the invention provides a universal, simple and efficient method for synthesizing 9-trifluoromethyl-9, 10-dihydrophenanthrene compounds.
The technical scheme of the invention is as follows:
a method for synthesizing 9-trifluoromethyl-9, 10-dihydrophenanthrene compounds, which comprises the following steps:
mixing a substrate (I), a photosensitizer, an alkaline substance and a solvent, reacting for 20-36 h (preferably 24h) under the conditions of illumination of a blue LED (15w), temperature of 15-40 ℃ (preferably 25 ℃), and protection of inert gas, and then carrying out aftertreatment on a reaction solution to obtain a 9-trifluoromethyl-9, 10-dihydrophenanthrene compound (II);
the ratio of the amounts of the substrate (I), the photosensitizer and the alkaline substance is 1: 0.01-0.1: 1-2, preferably 1: 0.05: 1.5;
the volume usage amount of the solvent is 10-20 mL/mmol based on the substance amount of the substrate (I);
the photosensitizer is one or a mixture of two of a formula (III) and a formula (IV) in any proportion;
the alkaline substance is one or a mixture of more than two of potassium phosphate, potassium carbonate and sodium carbonate in any proportion;
the solvent is one or a mixed solvent of more than two of acetonitrile, tetrahydrofuran and 1, 4-dioxane in any proportion, and tetrahydrofuran is preferred;
the post-treatment method comprises the following steps: after the reaction is finished, adding column chromatography silica gel (100-200 meshes) into the reaction solution, evaporating under reduced pressure to remove the solvent, and performing column chromatography separation, wherein the volume ratio of petroleum ether to ethyl acetate is 20:1 as eluent, collecting eluent containing target product, evaporating solvent to obtain 9-trifluoromethyl-9, 10-dihydrophenanthrene compound (II);
the reaction formula is as follows:
in the formula (I) or the formula (II),
R1is hydrogen, chlorine, methyl or methoxy;
R2is hydrogen, methyl or phenyl;
the structural formula of the photosensitizer is as follows:
specifically, the 9-trifluoromethyl-9, 10-dihydrophenanthrene compound (II) according to the present invention is preferably 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 cyclization;
(3) the reaction condition is mild;
(4) meanwhile, the reaction has certain innovativeness and high atom economy, adopts a photocatalysis mode to replace the traditional heating mode, reduces energy consumption, and better conforms to the modern green chemistry concept.
(IV) detailed description of the preferred embodiments
The invention will be further illustrated by the following examples, without limiting the scope of the invention:
example 1
Alpha-trifluoromethyl-2-phenylstyrene (0.3mmol, 0.0744g), photosensitizer (III) (0.015mmol, 0.0167g), potassium phosphate (0.45mmol, 0.0954g) were added to a 15mL sealed reaction tube, followed by 3mL of tetrahydrofuran as a solvent. Then, under the irradiation of 15w Blue LED, reacting for 24h at 25 ℃ in a nitrogen environment, after the reaction is finished, adding two spoons (0.5g) of column chromatography silica gel (100 meshes and 200 meshes) into the reaction liquid, removing the solvent by reduced pressure distillation, and separating by column chromatography to obtain a pure product (petroleum ether/ethyl acetate 20:1 is used as an eluent) shown in the structural formula. The material was a yellow liquid in 77% yield.
Characterization data:1H NMR(500MHz,CDCl3)δ7.84(d,J＝7Hz,1H),7.77(d,J＝8Hz,1H),7.43(td,J1＝7.6Hz,J2＝1.4Hz,1H),7.37(d,J＝7.4Hz,1H),7.34–7.28(m,2H),7.28–7.22(m,2H),3.61-3.54(m,1H),3.27(dd,J1＝16.2,J2＝6.5Hz,1H),3.20(dd,J1＝16.2Hz,J2＝3.2Hz,1H).13C NMR(125MHz,CDCl3)δ135.19,133.42,133.01,130.29,129.29,129.20,128.27,128.11,127.65,127.50,126.80(q,J＝280Hz).124.22,123.56,42.42(q,J＝27.0Hz),28.51(q,J＝2.5Hz).
example 2
Alpha-trifluoromethyl-2-phenylstyrene (0.3mmol, 0.0744g), photosensitizer (IV) (0.015mmol, 0.0172g), potassium phosphate (0.45mmol, 0.0954g) were added to a 15mL tube-sealed reaction tube, and 3mL of tetrahydrofuran was added as a solvent. And then, reacting for 24 hours under the condition of 25 ℃ and nitrogen atmosphere under the irradiation of 15w Blue LED, adding two-spoon column chromatography silica gel (100-200 meshes) into the reaction liquid after the reaction is finished, removing the solvent through reduced pressure distillation, and separating by column chromatography to obtain a pure product (petroleum ether/ethyl acetate-20: 1 is used as an eluent) shown in the structural formula. The material was a yellow liquid in 67% yield.
Characterization data:1H NMR(500MHz,CDCl3)δ7.84(d,J＝7Hz,1H),7.77(d,J＝8Hz,1H),7.43(td,J1＝7.6Hz,J2＝1.4Hz,1H),7.37(d,J＝7.4Hz,1H),7.34–7.28(m,2H),7.28–7.22(m,2H),3.61-3.54(m,1H),3.27(dd,J1＝16.2,J2＝6.5Hz,1H),3.20(dd,J1＝16.2Hz,J2＝3.2Hz,1H).13C NMR(125MHz,CDCl3)δ135.19,133.42,133.01,130.29,129.29,129.20,128.27,128.11,127.65,127.50,126.80(q,J＝280Hz).124.22,123.56,42.42(q,J＝27.0Hz),28.51(q,J＝2.5Hz).
example 3
Alpha-trifluoromethyl-2-phenylstyrene (0.3mmol, 0.0744g), photosensitizer (III) (0.003mmol, 0.0034g) and potassium phosphate (0.45mmol, 0.0954g) are added to a 15mL tube-sealed reaction tube, followed by 3mL of tetrahydrofuran as a solvent. And then, reacting for 24 hours under the condition of 25 ℃ and nitrogen atmosphere under the irradiation of 15w Blue LED, adding two-spoon column chromatography silica gel (100-200 meshes) into the reaction liquid after the reaction is finished, removing the solvent through reduced pressure distillation, and separating by column chromatography to obtain a pure product (petroleum ether/ethyl acetate-20: 1 is used as an eluent) shown in the structural formula. The material was a yellow liquid in 51% yield.
Number of tokensAccording to the following steps:1H NMR(500MHz,CDCl3)δ7.84(d,J＝7Hz,1H),7.77(d,J＝8Hz,1H),7.43(td,J1＝7.6Hz,J2＝1.4Hz,1H),7.37(d,J＝7.4Hz,1H),7.34–7.28(m,2H),7.28–7.22(m,2H),3.61-3.54(m,1H),3.27(dd,J1＝16.2,J2＝6.5Hz,1H),3.20(dd,J1＝16.2Hz,J2＝3.2Hz,1H).13C NMR(125MHz,CDCl3)δ135.19,133.42,133.01,130.29,129.29,129.20,128.27,128.11,127.65,127.50,126.80(q,J＝280Hz).124.22,123.56,42.42(q,J＝27.0Hz),28.51(q,J＝2.5Hz).
example 4
Alpha-trifluoromethyl-2-phenyl-4-methylstyrene (0.3mmol, 0.0786g), photosensitizer (III) (0.03mmol, 0.0335g), and potassium phosphate (0.45mmol, 0.0954g) were charged into a 15mL blocked reaction tube, and 3mL of tetrahydrofuran was added as a solvent. And then, reacting for 24 hours under the condition of 25 ℃ and nitrogen atmosphere under the irradiation of 15w Blue LED, adding two-spoon column chromatography silica gel (100-200 meshes) into the reaction liquid after the reaction is finished, removing the solvent through reduced pressure distillation, and separating by column chromatography to obtain a pure product (petroleum ether/ethyl acetate-20: 1 is used as an eluent) shown in the structural formula. The material was a yellow liquid in 75% yield.
Characterization data:1H NMR(500MHz,CDCl3)δ7.80(d,J＝8Hz,1H),7.68(s,1H),7.35-7.32(m,1H),7.29-7.25(m,3H),7,16-7.14(m,1H),3.61-3.53(m,1H),3.27(dd,J1＝16Hz,J2＝6Hz,1H),3.21(dd,J1＝16Hz,J2＝3Hz,1H),2.45(s,3H).13C NMR(125MHz,CDCl3)δ138.19,134.95,133.50,133.14,130.14,128.45,128.26,127.97,127.41,126.87(q,J＝280Hz),126.39,124.88,123.48,42.08(q,J＝27Hz),28.65(q,J＝2.5Hz).
example 5
Alpha-trifluoromethyl-2-phenyl-4-methylstyrene (0.3mmol, 0.0786g), photosensitizer (III) (0.015mmol, 0.0167g) and potassium carbonate (0.45mmol, 0.0621g) were added to a 15mL sealed reaction tube, followed by 3mL of tetrahydrofuran as a solvent. And then, reacting for 24 hours under the condition of 25 ℃ and nitrogen atmosphere under the irradiation of 15w Blue LED, adding two-spoon column chromatography silica gel (100-200 meshes) into the reaction liquid after the reaction is finished, removing the solvent through reduced pressure distillation, and separating by column chromatography to obtain a pure product (petroleum ether/ethyl acetate-20: 1 is used as an eluent) shown in the structural formula. The material was a yellow liquid in 73% yield.
Characterization data:1H NMR(500MHz,CDCl3)δ7.80(d,J＝8Hz,1H),7.68(s,1H),7.35-7.32(m,1H),7.29-7.25(m,3H),7,16-7.14(m,1H),3.61-3.53(m,1H),3.27(dd,J1＝16Hz,J2＝6Hz,1H),3.21(dd,J1＝16Hz,J2＝3Hz,1H),2.45(s,3H).13C NMR(125MHz,CDCl3)δ138.19,134.95,133.50,133.14,130.14,128.45,128.26,127.97,127.41,126.87(q,J＝280Hz),126.39,124.88,123.48,42.08(q,J＝27Hz),28.65(q,J＝2.5Hz).
example 6
Alpha-trifluoromethyl-2-phenyl-4-methylstyrene (0.3mmol, 0.0786g), photosensitizer (III) (0.015mmol, 0.0167g) and sodium carbonate (0.45mmol, 0.0477g) were added to a 15mL tube-sealed reaction tube, and 3mL of tetrahydrofuran was added as a solvent. And then, reacting for 24 hours under the condition of 25 ℃ and nitrogen atmosphere under the irradiation of 15w Blue LED, adding two-spoon column chromatography silica gel (100-200 meshes) into the reaction liquid after the reaction is finished, removing the solvent through reduced pressure distillation, and separating by column chromatography to obtain a pure product (petroleum ether/ethyl acetate-20: 1 is used as an eluent) shown in the structural formula. The material was a yellow liquid in 63% yield.
Characterization data:1H NMR(500MHz,CDCl3)δ7.80(d,J＝8Hz,1H),7.68(s,1H),7.35-7.32(m,1H),7.29-7.25(m,3H),7,16-7.14(m,1H),3.61-3.53(m,1H),3.27(dd,J1＝16Hz,J2＝6Hz,1H),3.21(dd,J1＝16Hz,J2＝3Hz,1H),2.45(s,3H).13C NMR(125MHz,CDCl3)δ138.19,134.95,133.50,133.14,130.14,128.45,128.26,127.97,127.41,126.87(q,J＝280Hz),126.39,124.88,123.48,42.08(q,J＝27Hz),28.65(q,J＝2.5Hz).
example 7
Alpha-trifluoromethyl-2-phenyl-5-chlorostyrene (0.3mmol, 0.0846g), photosensitizer (III) (0.015mmol, 0.0167g), potassium phosphate (0.3mmol, 0.0636g) were added to a 15mL sealed reaction tube, and 3mL of tetrahydrofuran was added as a solvent. And then, reacting for 24 hours under the condition of 25 ℃ and nitrogen atmosphere under the irradiation of 15w Blue LED, adding two-spoon column chromatography silica gel (100-200 meshes) into the reaction liquid after the reaction is finished, removing the solvent through reduced pressure distillation, and separating by column chromatography to obtain a pure product (petroleum ether/ethyl acetate-20: 1 is used as an eluent) shown in the structural formula. The material was a yellow liquid in 52% yield.
Characterization data:1H NMR(500MHz,CDCl3)δ7.78(d,J＝8.5Hz,1H),7.74(d,J＝8.0Hz,1H),7.44(d,J＝2Hz,1H),7.42(d,J＝2Hz,1H),7.39(s,1H),7.35-7.34(m,1H),7.32-7.26(m,1H),3.60-3.53(m,1H),3.27(dd,J1＝16Hz,J2＝6.5Hz,1H),3.22(dd,J1＝16.2Hz,J2＝3.2Hz,1H).13C NMR(125MHz,CDCl3)δ133.80,133.27,132.71,132.49,130.92,130.14,129.36,128.46,128.36,127.67,126.47(q,J＝280Hz),125.55,123.49,42.31(q,J＝27Hz),28.32(q,J＝2.5Hz).
example 8
Alpha-trifluoromethyl-2-phenyl-5-chlorostyrene (0.3mmol, 0.0846g), photosensitizer (III) (0.015mmol, 0.0167g), potassium phosphate (0.6mmol, 0.1272g) were added to a 15mL sealed reaction tube, and 3mL of tetrahydrofuran was added as a solvent. And then, reacting for 24 hours under the condition of 25 ℃ and nitrogen atmosphere under the irradiation of 15w Blue LED, adding two-spoon column chromatography silica gel (100-200 meshes) into the reaction liquid after the reaction is finished, removing the solvent through reduced pressure distillation, and separating by column chromatography to obtain a pure product (petroleum ether/ethyl acetate-20: 1 is used as an eluent) shown in the structural formula. The material was a yellow liquid in 77% yield.
Characterization data:1H NMR(500MHz,CDCl3)δ7.78(d,J＝8.5Hz,1H),7.74(d,J＝8.0Hz,1H),7.44(d,J＝2Hz,1H),7.42(d,J＝2Hz,1H),7.39(s,1H),7.35-7.34(m,1H),7.32-7.26(m,1H),3.60-3.53(m,1H),3.27(dd,J1＝16Hz,J2＝6.5Hz,1H),3.22(dd,J1＝16.2Hz,J2＝3.2Hz,1H).13C NMR(125MHz,CDCl3)δ133.80,133.27,132.71,132.49,130.92,130.14,129.36,128.46,128.36,127.67,126.47(q,J＝280Hz),125.55,123.49,42.31(q,J＝27Hz),28.32(q,J＝2.5Hz).
example 9
Alpha-trifluoromethyl-2-phenyl-5-chlorostyrene (0.3mmol, 0.0846g), photosensitizer (III) (0.015mmol, 0.0167g), potassium phosphate (0.45mmol, 0.0954g) were added to a 15mL sealed reaction tube, and 3mL acetonitrile was added as a solvent. And then, reacting for 24 hours under the condition of 25 ℃ and nitrogen atmosphere under the irradiation of 15w Blue LED, adding two-spoon column chromatography silica gel (100-200 meshes) into the reaction liquid after the reaction is finished, removing the solvent through reduced pressure distillation, and separating by column chromatography to obtain a pure product (petroleum ether/ethyl acetate-20: 1 is used as an eluent) shown in the structural formula. The material was a yellow liquid in 56% yield.
Characterization data:1H NMR(500MHz,CDCl3)δ7.78(d,J＝8.5Hz,1H),7.74(d,J＝8.0Hz,1H),7.44(d,J＝2Hz,1H),7.42(d,J＝2Hz,1H),7.39(s,1H),7.35-7.34(m,1H),7.32-7.26(m,1H),3.60-3.53(m,1H),3.27(dd,J1＝16Hz,J2＝6.5Hz,1H),3.22(dd,J1＝16.2Hz,J2＝3.2Hz,1H).13C NMR(125MHz,CDCl3)δ133.80,133.27,132.71,132.49,130.92,130.14,129.36,128.46,128.36,127.67,126.47(q,J＝280Hz),125.55,123.49,42.31(q,J＝27Hz),28.32(q,J＝2.5Hz).
example 10
Alpha-trifluoromethyl-2-phenyl-4-methoxystyrene (0.3mmol, 0.0834g), photosensitizer (III) (0.015mmol, 0.0167g), potassium phosphate (0.45mmol, 0.0954g) were added to a 15mL sealed reaction tube, followed by 3mL of 1, 4-dioxane as solvent. And then, reacting for 24 hours under the condition of 25 ℃ and nitrogen atmosphere under the irradiation of 15w Blue LED, adding two-spoon column chromatography silica gel (100-200 meshes) into the reaction liquid after the reaction is finished, removing the solvent through reduced pressure distillation, and separating by column chromatography to obtain a pure product (petroleum ether/ethyl acetate-20: 1 is used as an eluent) shown in the structural formula. The material was a yellow liquid in 69% yield.
Characterization data:1H NMR(500MHz,CDCl3)δ7.76(d,J＝7.7Hz,1H),7.38(d,J＝2.6Hz,1H),7.36–7.32(m,1H),7.31(d,J＝8.2Hz,1H),7.28(dd,J＝6.7,1.1Hz,2H),6.88(dd,J1＝8.4Hz,J2＝2.6Hz,1H),3.90(s,3H),3.59-3.51(m,1H),3.27(dd,J1＝16.2Hz,J2＝6.5Hz,1H),3.20(dd,J1＝16.2Hz,J2＝3.0Hz,1H).13C NMR(126MHz,CDCl3)δ160.35,136.38,133.34,133.24,131.36,128.30,128.22,127.44,126.88(q,J＝280Hz),123.57,121.59,113.03,109.85,77.29,77.04,76.78,55.42,41.71(q,J＝27Hz),28.73(q,J＝2.5Hz).
example 11
Alpha-trifluoromethyl-2-phenyl-4-methoxystyrene (0.3mmol, 0.0834g), photosensitizer (III) (0.015mmol, 0.0167g), potassium phosphate (0.45mmol, 0.0954g) were added to a 15mL sealed reaction tube, and 3mL of tetrahydrofuran was added as a solvent. And then, reacting for 24 hours under the condition of 15w of Blue LED irradiation and 15 ℃ in a nitrogen environment, adding two-spoon column chromatography silica gel (100-200 meshes) into the reaction liquid after the reaction is finished, removing the solvent through reduced pressure distillation, and separating through column chromatography to obtain a pure product (petroleum ether/ethyl acetate-20: 1 is used as an eluent) shown in the structural formula. The material was a yellow liquid in 70% yield.
Characterization data:1H NMR(500MHz,CDCl3)δ7.76(d,J＝7.7Hz,1H),7.38(d,J＝2.6Hz,1H),7.36–7.32(m,1H),7.31(d,J＝8.2Hz,1H),7.28(dd,J＝6.7,1.1Hz,2H),6.88(dd,J1＝8.4Hz,J2＝2.6Hz,1H),3.90(s,3H),3.59-3.51(m,1H),3.27(dd,J1＝16.2Hz,J2＝6.5Hz,1H),3.20(dd,J1＝16.2Hz,J2＝3.0Hz,1H).13C NMR(126MHz,CDCl3)δ160.35,136.38,133.34,133.24,131.36,128.30,128.22,127.44,126.88(q,J＝280Hz),123.57,121.59,113.03,109.85,77.29,77.04,76.78,55.42,41.71(q,J＝27Hz),28.73(q,J＝2.5Hz).
example 12
Alpha-trifluoromethyl-2-phenyl-4-methoxystyrene (0.3mmol, 0.0834g), photosensitizer (III) (0.015mmol, 0.0167g), potassium phosphate (0.45mmol, 0.0954g) were added to a 15mL sealed reaction tube, and 3mL of tetrahydrofuran was added as a solvent. And then, reacting for 24 hours under the condition of 40 ℃ and nitrogen atmosphere under the irradiation of 15w Blue LED, adding two-spoon column chromatography silica gel (100-200 meshes) into the reaction liquid after the reaction is finished, removing the solvent through reduced pressure distillation, and separating by column chromatography to obtain a pure product (petroleum ether/ethyl acetate-20: 1 is used as an eluent) shown in the structural formula. The material was a yellow liquid in 68% yield.
Characterization data:1H NMR(500MHz,CDCl3)δ7.76(d,J＝7.7Hz,1H),7.38(d,J＝2.6Hz,1H),7.36–7.32(m,1H),7.31(d,J＝8.2Hz,1H),7.28(dd,J＝6.7,1.1Hz,2H),6.88(dd,J1＝8.4Hz,J2＝2.6Hz,1H),3.90(s,3H),3.59-3.51(m,1H),3.27(dd,J1＝16.2Hz,J2＝6.5Hz,1H),3.20(dd,J1＝16.2Hz,J2＝3.0Hz,1H).13C NMR(126MHz,CDCl3)δ160.35,136.38,133.34,133.24,131.36,128.30,128.22,127.44,126.88(q,J＝280Hz),123.57,121.59,113.03,109.85,77.29,77.04,76.78,55.42,41.71(q,J＝27Hz),28.73(q,J＝2.5Hz).
example 13
Alpha-trifluoromethyl-2- (4-phenyl) styrene (0.3mmol, 0.0972g), photosensitizer (III) (0.015mmol, 0.0167g), potassium phosphate (0.45mmol, 0.0954g) were added to a 15mL tube-sealed reaction tube, and 3mL of tetrahydrofuran was added as a solvent. And then, reacting for 20 hours under the condition of 25 ℃ and nitrogen atmosphere under the irradiation of 15w Blue LED, adding two-spoon column chromatography silica gel (100-200 meshes) into the reaction liquid after the reaction is finished, removing the solvent through reduced pressure distillation, and separating by column chromatography to obtain a pure product (petroleum ether/ethyl acetate-20: 1 is used as an eluent) shown in the structural formula. The material was a yellow liquid in 69% yield.
Characterization data:1H NMR(500MHz,CDCl3)δ7.90(d,J＝7.5Hz,1H),7.86(d,J＝8.5Hz,1H),7.68-7.66(m,2H),7.59(dd,J1＝8Hz,J2＝1.5Hz,1H),7.51-7.46(m,4H),7.41-7.33(m,3H),3.66-3.61(m,1H),3.36(dd,J1＝16Hz,J2＝6.5Hz,1H),3.29(dd,J1＝16Hz,J2＝8.5Hz,1H)
13C NMR(126MHz,CDCl3)δ140.85,140.49,134.93,133.47,132.47,130.36,129.25,129.21,128.82,127.68,127.48,126.97,126.80(q,J＝280Hz),126.92,126.17,124.19,124.01,42.49(q,J＝27Hz),28.68(q,J＝2.5Hz).
example 14
Alpha-trifluoromethyl-2- (4-phenyl) styrene (0.3mmol, 0.0972g), photosensitizer (III) (0.015mmol, 0.0167g), potassium phosphate (0.45mmol, 0.0954g) were added to a 15mL tube-sealed reaction tube, and 3mL of tetrahydrofuran was added as a solvent. And then, reacting for 36h under the condition of 25 ℃ and nitrogen atmosphere under the irradiation of 15w Blue LED, adding two-spoon column chromatography silica gel (100-200 meshes) into the reaction liquid after the reaction is finished, removing the solvent through reduced pressure distillation, and separating by column chromatography to obtain a pure product (petroleum ether/ethyl acetate-20: 1 is used as an eluent) shown in the structural formula. The material was a yellow liquid in 77% yield.
Characterization data:1H NMR(500MHz,CDCl3)δ7.90(d,J＝7.5Hz,1H),7.86(d,J＝8.5Hz,1H),7.68-7.66(m,2H),7.59(dd,J1＝8Hz,J2＝1.5Hz,1H),7.51-7.46(m,4H),7.41-7.33(m,3H),3.66-3.61(m,1H),3.36(dd,J1＝16Hz,J2＝6.5Hz,1H),3.29(dd,J1＝16Hz,J2＝8.5Hz,1H)13C NMR(126MHz,CDCl3)δ140.85,140.49,134.93,133.47,132.47,130.36,129.25,129.21,128.82,127.68,127.48,126.97,126.80(q,J＝280Hz),126.92,126.17,124.19,124.01,42.49(q,J＝27Hz),28.68(q,J＝2.5Hz).
meanwhile, the 9-trifluoromethyl-9, 10-dihydrophenanthrene compound synthesized by the present invention has the following applications (scheme 2 shown below).
Synthesis of specific substances such as:
dissolving the synthesized 9-trifluoromethyl-9, 10-dihydrophenanthrene compound (0.3mmol) in 3ml of tetrahydrofuran, adding DDQ (0.45mmol,0.102g), stirring at room temperature for 1 hour, adding two-spoon column chromatography silica gel (100-200 meshes) into the reaction liquid after the reaction is finished, removing the solvent through reduced pressure distillation, and separating through column chromatography to obtain a pure product (petroleum ether/ethyl acetate 20:1 is used as an eluent) shown in the structural formula. Obtaining the target product 9-trifluoromethyl phenanthrene compound.
Dissolving 9-trifluoromethyl-9, 10-dihydrophenanthrene (0.3mmol, 0.0744g) in 3ml of tetrahydrofuran, adding DDQ (0.45mmol,0.102g), stirring at room temperature for 1 hour, adding two-spoon column chromatography silica gel (100-200 meshes) into the reaction liquid after the reaction is finished, removing the solvent by reduced pressure distillation, and separating by column chromatography to obtain a pure product (petroleum ether/ethyl acetate 20:1 is used as an eluent) shown in the structural formula. Obtaining the target product 9-trifluoromethyl phenanthrene.
6-methyl-9-trifluoromethyl-9, 10-dihydrophenanthrene (0.3mmol, 0.0786g) is dissolved in 3ml tetrahydrofuran, then DDQ (0.45mmol,0.102g) is added, stirring is carried out for 1 hour under the condition of room temperature, after the reaction is finished, two-spoon column chromatography silica gel (100-200 meshes) is added into the reaction liquid, the solvent is removed by reduced pressure distillation, and then the product pure product shown in the structural formula is obtained by column chromatography separation (petroleum ether/ethyl acetate ═ 20:1 is used as eluent). Obtaining the target product 6-methyl-9-trifluoromethyl phenanthrene.
Dissolving 4-methyl-7-chloro-9-trifluoromethyl-9, 10-dihydrophenanthrene (0.3mmol, 0.0888g) in 3ml of tetrahydrofuran, adding DDQ (0.45mmol,0.102g), stirring at room temperature for 1 hour, adding two-spoon column chromatography silica gel (100-200 meshes) into the reaction liquid after the reaction is finished, removing the solvent by reduced pressure distillation, and separating by column chromatography to obtain a pure product shown in the structural formula (petroleum ether/ethyl acetate 20:1 is used as an eluent). The target product 4-methyl-7-chlorine-9-trifluoromethyl phenanthrene is obtained.
6-methoxy-9-trifluoromethyl-9, 10-dihydrophenanthrene (0.3mmol, 0.0834g) is dissolved in 3ml tetrahydrofuran, DDQ (0.45mmol,0.102g) is added, stirring is carried out for 1 hour at room temperature, after the reaction is finished, two-spoon column chromatography silica gel (100-200 meshes) is added into the reaction liquid, the solvent is removed by reduced pressure distillation, and the product pure product shown in the structural formula is obtained by column chromatography separation (petroleum ether/ethyl acetate ═ 20:1 is used as eluent). Obtaining the target product 6-methoxy-9-trifluoromethyl phenanthrene.
Claims (4)
1. A method for synthesizing 9-trifluoromethyl-9, 10-dihydrophenanthrene compounds is characterized by comprising the following steps:
mixing a substrate (I), a photosensitizer, an alkaline substance and a solvent, reacting for 20-36 h under the conditions of illumination of a blue LED, temperature of 15-40 ℃ and protection of inert gas, and then carrying out aftertreatment on a reaction solution to obtain a 9-trifluoromethyl-9, 10-dihydrophenanthrene compound (II);
the ratio of the amounts of the substrate (I), the photosensitizer and the alkaline substance is 1: 0.01-0.1: 1-2;
the photosensitizer is one or a mixture of two of a formula (III) and a formula (IV) in any proportion;
the alkaline substance is one or a mixture of more than two of potassium phosphate, potassium carbonate and sodium carbonate in any proportion;
the solvent is one or a mixed solvent of more than two of acetonitrile, tetrahydrofuran and 1, 4-dioxane in any proportion;
the reaction formula is as follows:
in the formula (I) or the formula (II),
R1is hydrogen, chlorine, methyl or methoxy;
R2is hydrogen, methyl or phenyl.
2. The method for synthesizing 9-trifluoromethyl-9, 10-dihydrophenanthrene compound according to claim 1, wherein the ratio of the amounts of the substrate (I), photosensitizer, and basic substance is 1: 0.05: 1.5.
3. the method for synthesizing 9-trifluoromethyl-9, 10-dihydrophenanthrene compound according to claim 1, wherein the volume of the solvent is 10 to 20mL/mmol based on the amount of the substance of the substrate (I).
4. The method for synthesizing 9-trifluoromethyl-9, 10-dihydrophenanthrene compound according to claim 1, wherein the post-treatment method is: after the reaction is finished, adding column chromatography silica gel into the reaction liquid, evaporating the solvent under reduced pressure, and performing column chromatography separation, wherein the volume ratio of petroleum ether to ethyl acetate is 20:1 as eluent, collecting the eluent containing the target product, evaporating the solvent to obtain the 9-trifluoromethyl-9, 10-dihydrophenanthrene compound (II).
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