阅读说明：本技术 一种铱光催化合成9-乙酰氧基-9,10-二氢菲类化合物的方法 (Method for synthesizing 9-acetoxyl-9, 10-dihydrophenanthrene compound by virtue of iridium photocatalysis ) 是由 刘运奎 郑立孟 周丙伟 于 2019-08-27 设计创作，主要内容包括：一种铱光催化合成9-乙酰氧基-9,10-二氢菲类化合物的方法,所述方法为：将底物(I)、光敏剂、碱性物质、溶剂混合,在蓝色LED光照、温度15～40℃、惰性气体保护的条件下反应20～36h,之后反应液经后处理,得到9-乙酰氧基-9,10-二氢菲类化合物(II)；本发明安全环保,不产生废气,操作危险性低；底物适应性好,各种取代基都可以实现环化；反应条件温和；同时,该反应具有一定的创新性,原子经济性高,采用光催化的方式来替代传统加热的模式,减少了能耗,更加符合现代绿色化学的理念；(A method for synthesizing 9-acetoxyl-9, 10-dihydrophenanthrene compounds by iridium photocatalysis comprises the following steps: mixing a substrate (I), a photosensitizer, an alkaline substance and a solvent, and keeping inert gas at the temperature of 15-40 ℃ under the illumination of a blue LEDReacting for 20-36 h under the protection condition, and then carrying out post-treatment on the reaction solution to obtain a 9-acetoxyl-9, 10-dihydrophenanthrene compound (II); 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 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;)

1. A method for synthesizing 9-acetoxyl-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-acetoxyl-9, 10-dihydrophenanthrene compound (II);

the ratio of the amounts of the substrate (I), the photosensitizer and the alkaline substance is 1: 0.01-0.05: 1-2;

the photosensitizer is Ir (bpy)₃、Ir(bpy)₂(dtbpy)PF₆、Ir(dF(CF₃)ppy)₂(dtbbpy)PF₆One or a mixture of more than two of the above 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 or chlorine;

R²is hydrogen, fluorine, chlorine or methyl.

2. The method for synthesizing a 9-acetoxy-9, 10-dihydrophenanthrene compound according to claim 1, wherein the ratio of the amounts of the substrate (I), the photosensitizer, and the basic substance is 1: 0.02: 1.5.

3. the method for synthesizing 9-acetoxy-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 a 9-acetoxy-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 eluent containing target product, evaporating solvent and drying to obtain 9-acetoxyl-9, 10-dihydrophenanthrene compound (II).

(I) technical field

The invention relates to a method for synthesizing 9-acetoxyl-9, 10-dihydrophenanthrene compounds by iridium photocatalysis.

(II) background of the invention

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. In addition, substituted dihydrophenanthrenes have one or two chiral centers and can be designed to synthesize a series of chiral ligands. For example, in 2002, a series of chiral ligands derived from 9, 10-dihydrophenanthrene-9, 10-diol have been reported to be designed, synthesized and applied to asymmetric catalysis (Chin. J. Synth. chem.,2002,10,95-97), so that the dihydrophenanthrene compounds have a great application prospect in the aspect of chiral ligands. The 9-acetoxyl-9, 10-dihydrophenanthrene reported by the invention can be further oxidized to obtain a 9-acetoxyl phenanthrene compound, and the phenanthrene compound is also an important medical intermediate and chemical raw material. Furthermore, 9-acetoxyl-9, 10-dihydrophenanthrene can be hydrolyzed to obtain 9-hydroxy-9, 10-dihydrophenanthrene, and the compound has a chiral center and can be applied to chiral ligands (scheme 1).

With intensive research on photocatalysis in recent years, more and more photosensitizers are developed and put into production life, wherein the metal complex corresponding to the most widely used precious metal iridium is adopted, and currently, methods for synthesizing dihydrophenanthrene compounds are more, for example, 2011, Daniela et al (org.lett.,2011,13,12) report that 2-phenethyliodobenzene is taken as a substrate, potassium tert-butoxide is taken as a base, pyridine is taken as a solvent, and the dihydrophenanthrene compounds are synthesized by adopting a free radical addition cyclization mode at a high temperature of 160 ℃, but the synthesis mode has great limitation, needs to be carried out at a high temperature, and meanwhile, the adoption of the solvent with high toxicity, namely pyridine, has great influence on the environment and is not beneficial to industrial production. The synthesis reports of the dihydrophenanthrene compounds are relatively more, but the reports of the relevant documents for synthesizing the 9-substituted dihydrophenanthrene compounds are obviously less, while the 9-acetoxyl-9, 10-dihydrophenanthrene is synthesized by heating and reacting 9-hydroxy-9, 10-dihydrophenanthrene and acetic anhydride which are used as substrates and pyridine which is used as a solvent in the traditional method, and the method also adopts an unfriendly solvent pyridine, and simultaneously needs to prepare the 9-hydroxy-9, 10-dihydrophenanthrene in advance, so that the raw materials are relatively not easily obtained. Therefore, it is necessary to find a more environmentally friendly method which is closer to the theme of the green chemistry era.

With the intensive research on photocatalysis in recent years, more and more photosensitizers are developed and applied to production and life of people, wherein the metal complex corresponding to the most widely applied noble metal Ir is shown to have higher catalytic activity and longer excited state retention time through research tests in various aspects. The invention combines the high reactivity of the iridium photosensitizer, uses a 2-phenyl-alpha-acetoxyl-styrene compound which is relatively easy to synthesize as a substrate, uses tetrahydrofuran which is relatively less toxic as a solvent, and uses common K₂CO₃The target product 9-acetoxyl-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 era theme of current green chemical development.

Disclosure of the invention

Aiming at the defects of the prior art, the invention provides a universal, simple and efficient method for synthesizing 9-acetoxyl-9, 10-dihydrophenanthrene compounds.

The technical scheme of the invention is as follows:

a method for synthesizing 9-acetoxyl-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-acetoxyl-9, 10-dihydrophenanthrene compound (II);

the ratio of the amounts of the substrate (I), the photosensitizer and the alkaline substance is 1: 0.01-0.05: 1-2, preferably 1: 0.02: 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 Ir (bpy)₃、Ir(bpy)₂(dtbpy)PF₆、Ir(dF(CF₃)ppy)₂(dtbbpy)PF₆One or a mixture of more than two of the above 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 and drying to obtain 9-acetoxyl-9, 10-dihydrophenanthrene compound (II);

the reaction formula is as follows:

in the formula (I) or the formula (II),

R¹is hydrogen or chlorine;

R²is hydrogen, fluorine, chlorine or methyl;

the structural formula of the photosensitizer is as follows:

specifically, the 9-acetoxy-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

9,10-dihydrophenanthren-9-ylacetate

Mixing alpha-acetoxy-2-phenylstyrene (0.3mmol, 0.0714g), photosensitizer Ir (bpy)₃(0.006mmol, 0.0039g), potassium carbonate (0.45mmol, 0.0621g) were added to a 15mL lock tube3mL of tetrahydrofuran was added as a solvent to the reaction tube. 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 93% yield.

Characterization data:¹H NMR(500MHz,CDCl₃)δ7.86(t,J＝5.5Hz,2H),7.50(d,J＝7.5Hz,1H),7.48-7.45(m,1H),7.39-7.37(m,1H),7.36-7.33(m,1H),7.32-7.29(m,1H),6.09(t,J＝5Hz,1H),3.23-3.16(m,2H),2.00(s,3H).¹³C NMR(125MHz,CDCl₃)δ170.82,135.94,134.50,134.32,134.22,133.211,131.11,128.37,127.87,127.14,127.01,126.83,126.65,70.27,35.89,21.28.

example 2

9,10-dihydrophenanthren-9-ylacetate

Mixing alpha-acetoxy-2-phenylstyrene (0.3mmol, 0.0714g), Ir (bpy)₂(dtbpy)PF₆(0.006mmol, 0.0055g) and potassium carbonate (0.45mmol, 0.0621g) were charged into 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 57% yield.

Characterization data:¹H NMR(500MHz,CDCl₃)δ7.86(t,J＝5.5Hz,2H),7.50(d,J＝7.5Hz,1H),7.48-7.45(m,1H),7.39-7.37(m,1H),7.36-7.33(m,1H),7.32-7.29(m,1H),6.09(t,J＝5Hz,1H),3.23-3.16(m,2H),2.00(s,3H).¹³C NMR(125MHz,CDCl₃)δ170.82,135.94,134.50,134.32,134.22,133.211,131.11,128.37,127.87,127.14,127.01,126.83,126.65,70.27,35.89,21.28.

example 3

9,10-dihydrophenanthren-9-ylacetate

Alpha-acetoxy-2-phenylstyrene (0.3mmol, 0.0714g), Ir (dF (CF)₃)ppy)₂(dtbbpy)PF₆(0.006mmol, 0.0067g), potassium carbonate (0.45mmol, 0.0621g) were charged into a 15mL closed tube 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)δ7.86(t,J＝5.5Hz,2H),7.50(d,J＝7.5Hz,1H),7.48-7.45(m,1H),7.39-7.37(m,1H),7.36-7.33(m,1H),7.32-7.29(m,1H),6.09(t,J＝5Hz,1H),3.23-3.16(m,2H),2.00(s,3H).¹³C NMR(125MHz,CDCl₃)δ170.82,135.94,134.50,134.32,134.22,133.211,131.11,128.37,127.87,127.14,127.01,126.83,126.65,70.27,35.89,21.28.

example 4

6-chloro-9,10-dihydrophenanthren-9-ylacetate

Mixing alpha-acetoxy-2-phenyl-4-chlorostyrene (0.3mmol, 0.0816g), photosensitizer Ir (bpy)₃(0.003mmol, 0.002g) and potassium carbonate (0.45mmol, 0.0621g) were charged into a 15mL sealed reaction tube, and 3mL of tetrahydrofuran was added as a solvent. Then, the mixture is reacted for 24 hours under the condition of 25 ℃ and nitrogen atmosphere under the irradiation of 15w Blue LED, and then the reaction is carried outAfter 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 an eluent). The material was a yellow liquid in 87% yield.

Characterization data:¹H NMR(500MHz,CDCl₃)δ7.82(d,J＝2Hz,1H),7.79(d,J＝7.5Hz,1H),7.44(d,J＝8.5Hz,1H),7.38(td,J₁＝7.5Hz,J₂＝1Hz,1H),7.33(td,J₁＝7.5Hz,J₂＝1.5Hz,1H),7.31-7.28(m,2H),6.04(t,J＝4.5Hz,1H),3.17(d,J＝4.5Hz,2H),1.99(s,3H).¹³C NMR(125MHz,CDCl₃)δ170.62,135.92,135.30,132.98,132.02,131.82,130.01,129.22,128.61,127.56,127.54,124.09,123.70,69.13,34.28,21.24.

example 5

6-chloro-9,10-dihydrophenanthren-9-ylacetate

Mixing alpha-acetoxy-2-phenyl-4-chlorostyrene (0.3mmol, 0.0816g), photosensitizer Ir (bpy)₃(0.015mmol, 0.0098g) and potassium carbonate (0.45mmol, 0.0621g) 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 91% yield.

Characterization data:¹H NMR(500MHz,CDCl₃)δ7.82(d,J＝2Hz,1H),7.79(d,J＝7.5Hz,1H),7.44(d,J＝8.5Hz,1H),7.38(td,J₁＝7.5Hz,J₂＝1Hz,1H),7.33(td,J₁＝7.5Hz,J₂＝1.5Hz,1H),7.31-7.28(m,2H),6.04(t,J＝4.5Hz,1H),3.17(d,J＝4.5Hz,2H),1.99(s,3H).¹³C NMR(125MHz,CDCl₃)δ170.62,135.92,135.30,132.98,132.02,131.82,130.01,129.22,128.61,127.56,127.54,124.09,123.70,69.13,34.28,21.24.

example 6

6-chloro-9,10-dihydrophenanthren-9-ylacetate

Mixing alpha-acetoxy-2-phenyl-4-chlorostyrene (0.3mmol, 0.0816g), photosensitizer Ir (bpy)₃(0.006mmol, 0.0039g) and potassium carbonate (0.45mmol, 0.0621g) were charged into a 15mL tube-sealed reaction tube, and 3mL of acetonitrile was further 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 66% yield.

Characterization data:¹H NMR(500MHz,CDCl₃)δ7.82(d,J＝2Hz,1H),7.79(d,J＝7.5Hz,1H),7.44(d,J＝8.5Hz,1H),7.38(td,J₁＝7.5Hz,J₂＝1Hz,1H),7.33(td,J₁＝7.5Hz,J₂＝1.5Hz,1H),7.31-7.28(m,2H),6.04(t,J＝4.5Hz,1H),3.17(d,J＝4.5Hz,2H),1.99(s,3H).¹³C NMR(125MHz,CDCl₃)δ170.62,135.92,135.30,132.98,132.02,131.82,130.01,129.22,128.61,127.56,127.54,124.09,123.70,69.13,34.28,21.24.

example 7

4-methyl-9,10-dihydrophenanthren-9-ylacetate

Mixing alpha-acetoxy-2- (2-methyl-phenyl) styrene (0.3mmol, 0.0756g), photosensitizer Ir (bpy)₃(0.006mmol, 0.0039g) and potassium carbonate (0.45mmol, 0.0621g) were charged into a 15mL tube-sealed reaction tube, and3mL of 1, 4-dioxane 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 83% yield.

Characterization data:¹H NMR(500MHz,CDCl₃)δ7.77-7.75(m,1H),7.50-7.48(m,1H),7.43(td,J₁＝7.5Hz,J₂＝1.5Hz,1H),7.33(td,J₁＝7.5Hz,J₂＝1.5Hz,1H),7.24(d,J＝7.5Hz,1H),7.19(t,J＝7.5Hz,1H),7.14(d,J＝6.5Hz,1H),5.95(t,J＝5.5Hz,1H),3.08(d,J＝5.5Hz,2H),2.68(s,3H),2.04(s,3H).¹³C NMR(125MHz,CDCl₃)δ170.84,135.98,134.53,134.38,134.36,133.23,131.17,128.43,127.91,127.19,127.02,126.88,126.68,70.33,35.92,23.07,21.32

example 8

4-methyl-9,10-dihydrophenanthren-9-ylacetate

Mixing alpha-acetoxy-2- (2-methyl-phenyl) styrene (0.3mmol, 0.0756g), photosensitizer Ir (bpy)₃(0.006mmol, 0.0039g) and potassium phosphate (0.45mmol, 0.0954g) were put into 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 86% yield.

Characterization data:¹H NMR(500MHz,CDCl₃)δ7.77-7.75(m,1H),7.50-7.48(m,1H),7.43(td,J₁＝7.5Hz,J₂＝1.5Hz,1H),7.33(td,J₁＝7.5Hz,J₂＝1.5Hz,1H),7.24(d,J＝7.5Hz,1H),7.19(t,J＝7.5Hz,1H),7.14(d,J＝6.5Hz,1H),5.95(t,J＝5.5Hz,1H),3.08(d,J＝5.5Hz,2H),2.68(s,3H),2.04(s,3H).¹³C NMR(125MHz,CDCl₃)δ170.84,135.98,134.53,134.38,134.36,133.23,131.17,128.43,127.91,127.19,127.02,126.88,126.68,70.33,35.92,23.07,21.32

example 9

4-methyl-9,10-dihydrophenanthren-9-ylacetate

Mixing alpha-acetoxy-2- (2-methyl-phenyl) styrene (0.3mmol, 0.0756g), photosensitizer Ir (bpy)₃(0.006mmol, 0.0039g) and sodium carbonate (0.45mmol, 0.0477g) were put into 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 77% yield.

Characterization data:¹H NMR(500MHz,CDCl₃)δ7.77-7.75(m,1H),7.50-7.48(m,1H),7.43(td,J₁＝7.5Hz,J₂＝1.5Hz,1H),7.33(td,J₁＝7.5Hz,J₂＝1.5Hz,1H),7.24(d,J＝7.5Hz,1H),7.19(t,J＝7.5Hz,1H),7.14(d,J＝6.5Hz,1H),5.95(t,J＝5.5Hz,1H),3.08(d,J＝5.5Hz,2H),2.68(s,3H),2.04(s,3H).¹³C NMR(125MHz,CDCl₃)δ170.84,135.98,134.53,134.38,134.36,133.23,131.17,128.43,127.91,127.19,127.02,126.88,126.68,70.33,35.92,23.07,21.32

example 10

2-chloro-9,10-dihydrophenanthren-9-ylacetate

Mixing alpha-acetoxy-2- (4-chlorophenyl) styrene (0.3mmol, 0.0816g), photosensitizer Ir (bpy)₃(0.006mmol, 0.0039g) and potassium carbonate (0.3mmol, 0.0414g) were put into 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 65% yield.

Characterization data:¹H NMR(500MHz,CDCl₃)δ7.82(d,J＝2Hz,1H),7.79(d,J＝7.5Hz,1H),7.44(d,J＝8.5Hz,1H),7.38(td,J₁＝7.5Hz,J₂＝1Hz,1H),7.33(td,J1＝7.5Hz,J₂＝1.5Hz,1H),7.31-7.28(m,2H),6.04(t,J＝4.5Hz,1H),3.17(d,J＝4.5Hz,2H),1.99(s,3H).¹³C NMR(125MHz,CDCl₃)δ170.62,135.92,135.30,132.98,132.02,131.82,130.01,129.22,128.61,127.56,127.54,124.09,123.70,69.13,34.28,21.24.

example 11

2-chloro-9,10-dihydrophenanthren-9-ylacetate

Mixing alpha-acetoxy-2- (4-chlorophenyl) styrene (0.3mmol, 0.0816g), photosensitizer Ir (bpy)₃(0.006mmol, 0.0039g) and potassium carbonate (0.6mmol, 0.0828g) were charged into 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 89% yield.

Characterization data:¹H NMR(500MHz,CDCl₃)δ7.82(d,J＝2Hz,1H),7.79(d,J＝7.5Hz,1H),7.44(d,J＝8.5Hz,1H),7.38(td,J₁＝7.5Hz,J₂＝1Hz,1H),7.33(td,J1＝7.5Hz,J₂＝1.5Hz,1H),7.31-7.28(m,2H),6.04(t,J＝4.5Hz,1H),3.17(d,J＝4.5Hz,2H),1.99(s,3H).¹³C NMR(125MHz,CDCl₃)δ170.62,135.92,135.30,132.98,132.02,131.82,130.01,129.22,128.61,127.56,127.54,124.09,123.70,69.13,34.28,21.24.

example 12

2-chloro-9,10-dihydrophenanthren-9-ylacetate

Mixing alpha-acetoxy-2- (4-chlorophenyl) styrene (0.3mmol, 0.0816g), photosensitizer Ir (bpy)₃(0.006mmol, 0.0039g) and potassium carbonate (0.45mmol, 0.0621g) were charged into 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 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 87% yield.

Characterization data:¹H NMR(500MHz,CDCl₃)δ7.82(d,J＝2Hz,1H),7.79(d,J＝7.5Hz,1H),7.44(d,J＝8.5Hz,1H),7.38(td,J₁＝7.5Hz,J₂＝1Hz,1H),7.33(td,J1＝7.5Hz,J₂＝1.5Hz,1H),7.31-7.28(m,2H),6.04(t,J＝4.5Hz,1H),3.17(d,J＝4.5Hz,2H),1.99(s,3H).¹³C NMR(125MHz,CDCl₃)δ170.62,135.92,135.30,132.98,132.02,131.82,130.01,129.22,128.61,127.56,127.54,124.09,123.70,69.13,34.28,21.24.

example 13

4-fluoro-9,10-dihydrophenanthren-9-ylacetate

Mixing alpha-acetoxy-2- (2-fluorophenyl) styrene (0.3mmol, 0.0768g), photosensitizer Ir (bpy)₃(0.006mmol, 0.0039g) and potassium carbonate (0.45mmol, 0.0621g) were charged into 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 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 83% yield.

Characterization data:¹H NMR(500MHz,CDCl₃)δ8.17(d,J＝8Hz,1H),7.51(d,J＝7.5Hz,1H),7.48-7.45(m,1H),7.36(td,J₁＝7.5Hz，J₂＝1Hz,1H),7.26-7.22(m,1H),7.11-7.07(m,2H),6.02(t,J＝4.5Hz,1H),3.21-3.12(m,2H),2.00(s,3H).¹³C NMR(125MHz,CDCl₃)δ170.68,161.38,159.38,136.03(J＝3.75Hz),134.01,130.48(J＝3.75Hz),129.20,128.64(J＝10Hz),128.34,128.21,127.99,124.76(J＝2.5Hz),121.34(J＝10Hz),115.36(J＝23.75Hz),69.79,34.74(J＝2.5Hz),21.26.

example 14

4-fluoro-9,10-dihydrophenanthren-9-ylacetate

Mixing alpha-acetoxy-2- (2-fluorophenyl) styrene (0.3mmol, 0.0768g), photosensitizer Ir (bpy)₃(0.006mmol, 0.0039g) and potassium carbonate (0.45mmol, 0.0621g) were charged into a 15mL tube-sealed reaction tube, and 3mL of tetrahydrofuran was added as a solvent. Then, reacting for 20h 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 the product shown in the structural formulaPure product (petroleum ether/ethyl acetate 20:1 as eluent). The material was a yellow liquid in 88% yield.

Characterization data:¹H NMR(500MHz,CDCl₃)δ8.17(d,J＝8Hz,1H),7.51(d,J＝7.5Hz,1H),7.48-7.45(m,1H),7.36(td,J₁＝7.5Hz，J₂＝1Hz,1H),7.26-7.22(m,1H),7.11-7.07(m,2H),6.02(t,J＝4.5Hz,1H),3.21-3.12(m,2H),2.00(s,3H).¹³C NMR(125MHz,CDCl₃)δ170.68,161.38,159.38,136.03(J＝3.75Hz),134.01,130.48(J＝3.75Hz),129.20,128.64(J＝10Hz),128.34,128.21,127.99,124.76(J＝2.5Hz),121.34(J＝10Hz),115.36(J＝23.75Hz),69.79,34.74(J＝2.5Hz),21.26.

example 15

4-fluoro-9,10-dihydrophenanthren-9-ylacetate

Mixing alpha-acetoxy-2- (2-fluorophenyl) styrene (0.3mmol, 0.0768g), photosensitizer Ir (bpy)₃(0.006mmol, 0.0039g) and potassium carbonate (0.45mmol, 0.0621g) were charged into 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 92% yield.

Characterization data:¹H NMR(500MHz,CDCl₃)δ8.17(d,J＝8Hz,1H),7.51(d,J＝7.5Hz,1H),7.48-7.45(m,1H),7.36(td,J₁＝7.5Hz，J₂＝1Hz,1H),7.26-7.22(m,1H),7.11-7.07(m,2H),6.02(t,J＝4.5Hz,1H),3.21-3.12(m,2H),2.00(s,3H).¹³C NMR(125MHz,CDCl₃)δ170.68,161.38,159.38,136.03(J＝3.75Hz),134.01,130.48(J＝3.75Hz),129.20,128.64(J＝10Hz),128.34,128.21,127.99,124.76(J＝2.5Hz),121.34(J＝10Hz),115.36(J＝23.75Hz),69.79,34.74(J＝2.5Hz),21.26.

meanwhile, the product synthesized by the invention can be used for the following purposes in industry, and can be used for synthesizing 9, 10-dihydrophenanthrene compounds and phenanthrene compounds, as shown in the following:

dissolving the synthesized compound 9-acetoxyl-9, 10-dihydrophenanthrene compound (0.3mmol) in 5ml of dichloromethane, adding 3.5g of silica gel, reacting for 30 minutes at 110 ℃, eluting with dichloromethane after the reaction is finished, and spin-drying to obtain the target product phenanthrene compound.

Synthesis of specific substances such as:

dissolving the compound 9-acetoxyl-9, 10-dihydrophenanthrene (0.3mmol, 0.0714g) in 5ml dichloromethane, adding 3.5g silica gel, reacting at 110 ℃ for 30 minutes, eluting with dichloromethane after the reaction is finished, and spin-drying to obtain the target product phenanthrene, wherein the yield is 92%.

6-chloro-9-acetoxyl-9, 10-dihydrophenanthrene (0.3mmol, 0.0816g) is dissolved in 5ml dichloromethane, 3.5g silica gel is added, the reaction is carried out for 30 minutes at 110 ℃, and after the reaction is finished, the target product 3-chlorophenanthrene is obtained by eluting with dichloromethane and spin-drying, wherein the yield is 90%.

4-methyl-9-acetoxyl-9, 10-dihydrophenanthrene (0.3mmol, 0.0756g) is dissolved in 5ml dichloromethane, 3.5g silica gel is added, the reaction is carried out for 30 minutes at 110 ℃, and after the reaction is finished, the target product 4-methylphenanthrene is obtained by eluting with dichloromethane and spin-drying, wherein the yield is 93%.

Dissolving 2-chloro-9-acetoxyl-9, 10-dihydrophenanthrene (0.3mmol, 0.0816g) in 5ml dichloromethane, adding 3.5g silica gel, reacting for 30 minutes at 110 ℃, eluting with dichloromethane after the reaction is finished, and spin-drying to obtain the target product 2-chlorophenanthrene with the yield of 91%.

Dissolving 4-fluoro-9-acetoxyl-9, 10-dihydrophenanthrene (0.3mmol, 0.0816g) in 5ml dichloromethane, adding 3.5g silica gel, reacting for 30 minutes at 110 ℃, eluting with dichloromethane after the reaction is finished, and spin-drying to obtain the target product 4-fluorophenanthrene, wherein the yield is 90%.