One-step synthesis method of phenanthrene cyclic aromatic hydrocarbon derivative

Abstract

The invention belongs to the technical field of compound synthesis, and particularly relates to a one-step synthesis method of a phenanthrene cyclic aromatic hydrocarbon derivative, which comprises the following steps of: reacting 2-iodobiphenyl shown in a general formula (1) and alkyne shown in a general formula (2) in the presence of a transition metal Pd catalyst, a ligand, an alkaline substance and a solvent in a nitrogen atmosphere under the irradiation of visible light with the wavelength of 420-500nm to obtain the phenanthrene cyclic aromatic hydrocarbon derivative. The phenanthrene ring compound is generated. According to the reaction, aryl free radicals are generated through single electron transfer and then are subjected to free radical addition with alkyne, and then cyclization is carried out. A series of complex phenanthrene ring derivatives are synthesized under mild conditions. The reaction mode of the method for synthesizing the phenanthrene ring derivative is extremely rare.

Description

Technical Field

[0001] The invention belongs to the technical field of compound synthesis, and particularly relates to a one-step synthesis method of phenanthrene aromatic hydrocarbon derivatives. Background Art

[0002] As one of the most common polycyclic aromatic hydrocarbon structures, phenanthrene compounds are widely used in materials science and medicinal chemistry as basic structural elements and play a vital role (Traxler, JT; Krbechek, LO; Riter, RR; Wagner, RG; Huffmann, CW J Med. Chem. 1971, 14, 90-94; Banwell, MG; Bezos, A.; Burns, C.; Kruszelnicki, I.; Parish, CR; Su, S.; Sydnes, MO Bioorg. Med. Chem. Lett. 2006, 16, 181-185; Wei, L.; Brossi, A.; Kendall, R.; Bastow, KF; Morris-Natschk e, SL; Shi, Q.; Lee, K.-H. Bioorg. Med. Chem. 2006, 14, 6560-6569; Wilson, S.; Ruenitz, PCJ Pharm. Sci. 1993, 82, 571-574; Cannon, JG; Khonje, PR; Long, JPJ Med. Chem. 1975, 18, 110-112) It is worth noting that the molecular fragments of phenanthrene ring compounds are the core components of various OFET and OLED materials (Machado, AM; Munaro, M.; Martins, TD; Davila, LYA; ′Giro, R.; Caldas, MJ; Atvars, TDZ; Akcelrud, LC Macromolecules 2006, 39, 3398-3407; Liu, R.; Farinha, JPS; Winnik, MA Macromolecules 1999,32,3957-3963;Lewis,FD;Burch,ELJPhys.Chem.1996,100,4055-4063;Li,J.- C.; Hu, G.-F.; Wang, N.-N.; Hu, T.; Wen, Q.-D.; Lu, P.; Wang, Y.-GJOrg.Chem.2013,78 ,3001-3008; Mitsuhashi, R.; Suzuki, Y.; Yamanari, Y.; Mitamura, H.; Kambe, T.; Ikeda, N.; Okamoto, H.; Fujiwara, A.; Yamaji, M.; Kawasaki, N.; Maniwa, Y.; Kubozono, Y.Nature2010,464,76-79.Matsuo,Y.;Sato,Y.;Hashiguchi,M.;Matsuo,K.;.

[0003] Nakamura, E. Adv. Funct. Mater. 2009, 19, 2224-2229). The currently developed methods mainly have the problems of complicated synthesis steps, harsh reaction conditions and limited substrate structure. Summary of the invention

[0004] Due to the great limitations of the above-mentioned known synthesis methods and the harsh reaction conditions, it is urgent to develop a simple method with mild reaction conditions. In view of the shortcomings of the prior art, the present invention provides a one-step synthesis method for universal and mild phenanthrene aromatic derivatives.

[0005] In order to achieve the purpose of the present invention, the technical solution adopted is as follows:

[0006] The one-step synthesis method of phenanthrene aromatic hydrocarbon derivatives comprises the following steps: 2-iodobiphenyl as shown in general formula (1) and alkyne as shown in general formula (2) are used as a transition metal Pd catalyst, in the presence of a ligand, an alkaline substance and a solvent, in a nitrogen atmosphere, under the irradiation of visible light with a wavelength of 420 to 500 nm, to generate the phenanthrene compound as shown in general formula (3);

[0007]

[0008] R 1 is any one of hydrogen, alkyl (e.g., methyl, ethyl, propyl, isopropyl, butyl, isobutyl), halogen (e.g., fluorine, chlorine, bromine, iodine), phenyl, or substituted phenyl (e.g., methyl substituted phenyl, ethyl substituted phenyl, methoxy substituted phenyl, halogen substituted phenyl, etc.);

[0009] R 2 is hydrogen or halogen (e.g. fluorine, chlorine, bromine, iodine);

[0010] Ar is aryl or heteroaryl (e.g., thiophene, pyridine, naphthalene), R 3 is any one of hydrogen, alkyl (such as methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, etc.), methoxy, phenyl, naphthyl, formyl or cyano;

[0011] The Pd catalyst is any one of palladium acetate, tetrakis(triphenylphosphine)palladium, tris(dibenzylideneacetone)dipalladium, palladium trifluoroacetate, bis(triphenylphosphinophenyl)palladium dichloride, bis(diphenylphosphino)ferrocenepalladium dichloride, and palladium chloride; among them, palladium acetate and tris(dibenzylideneacetone)dipalladium are more efficient, and can react in one step under mild reaction conditions to efficiently obtain the phenanthrene ring compound;

[0012] The ligand is any one of 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene, bis(2-diphenylphosphinophenyl)ether, 4,6-bis(diphenylphosphino)phenoxazine, 1,1'-binaphthyl-2,2'-bis(diphenylphosphino)propane, 1,3-bis(diphenylphosphino)propane, 1,1'-bis(diphenylphosphino)ferrocene, and triphenylphosphine, among which bis(2-diphenylphosphinophenyl)ether and 1,1'-bis(diphenylphosphino)ferrocene are more efficient and can be reacted in one step under mild reaction conditions to efficiently obtain the phenanthrene ring compound;

[0013] The alkaline substance is any one of potassium carbonate, cesium carbonate, sodium tert-butoxide, potassium tert-butoxide, lithium tert-butoxide, and potassium phosphate, wherein potassium phosphate is preferred, which can react in one step under mild reaction conditions and efficiently obtain the phenanthrene ring compound;

[0014] The solvent is benzene or fluorobenzene, wherein benzene is preferred, and the phenanthrene ring compound can be efficiently obtained by one-step reaction under mild reaction conditions.

[0015] The above method of the present invention uses two simple raw materials, commercially available 2-iodobiphenyl and terminal alkyne, in a light-induced palladium catalytic system, and can realize free radical tandem cyclization to obtain a phenanthrene ring compound through a one-step reaction. The reaction produces an aryl radical by single electron transfer, and then undergoes free radical addition with alkyne, followed by ring closure (traditionally, terminal alkynes and aryl iodobenzenes mainly undergo sonogashira reactions, and then undergo ring closure under Lewis acid catalysis to obtain such products, and our strategy is to use a light-induced palladium catalyzed system to bypass the sonogashira reaction, and synthesize complex polycyclic aromatic hydrocarbons in one step, shortening the reaction steps). A series of complex phenanthrene ring derivatives are synthesized under mild conditions. The reaction mode of synthesizing phenanthrene ring derivatives by this method is extremely rare.

[0016] Furthermore, the ratio of the 2-iodobiphenyl to the ligand is 1:0.1 to 0.3 (molar ratio), more preferably 1:0.2;

[0017] Furthermore, the ratio of the 2-iodobiphenyl to the base is 1:1.5-3 ((molar ratio), more preferably 1:2;

[0018] Further, the equivalent of the 2-iodobiphenyl and the alkyne is 1:1-1:3.0 (molar ratio);

[0019] Furthermore, the initial concentration of 2-iodobiphenyl in the reaction system has little effect on the reaction yield and can be set to 20 g / L-30 g / L (solute concentration).

[0020] The wavelength of the light source is preferably 420-490 nm, and the reaction yield can reach 55-87%, more preferably 450-490 nm.

[0021] Furthermore, it also includes a purification step: concentration and purification (column chromatography) after the reaction is completed.

[0022] Preferably, the reaction is assisted with vigorous stirring.

[0023] The compound of general formula (3) is preferably the following specific compound:

[0024]

[0025] Compared with the prior art, the method of the present invention has achieved the following beneficial effects:

[0026] (1) The one-pot synthesis of complex polycyclic aromatic hydrocarbon molecular fragments is achieved through transition metal Pd catalysis. This specific reaction mode is extremely rare. There is currently no report on the synthesis of such molecules using this method.

[0027] (2) The method of the present invention is simple to operate and has excellent substrate universality. The synthesized series of phenanthrene ring molecules and their derivative active molecules play an important role in pharmaceutical chemistry, luminescent materials and superconducting materials. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] Figures 1 to 17 The compounds 3a to 3q prepared in Examples 1 to 17 are respectively 1 H NMR (400 MHz, CDCl 3 )and 13 C NMR (101 MHz, CDCl 3 ). DETAILED DESCRIPTION

[0029] In order to further understand the purpose, content and advantages of the present invention, the specific embodiments of the present invention are now described in detail as follows, but it is not limited to the following examples, and it is freely matched according to actual conditions. The endpoints and any values ​​of the scope disclosed in this article are not limited to the precise scope and value. For numerical ranges, between the endpoint values ​​of each scope, between the endpoint values ​​of each scope and a separate point value, and between separate point values, one or more new numerical ranges can be combined with each other, and these numerical ranges should be considered as specifically disclosed in this article.

[0030] The present invention is further described in detail below in conjunction with embodiments:

[0031] The one-step synthesis method of the phenanthrene aromatic derivative in the embodiment comprises the following steps: 2-iodobiphenyl as shown in the general formula (1) and alkyne as shown in the general formula (2) are reacted with a transition metal Pd catalyst, a ligand, an alkaline substance and a solvent, in a nitrogen atmosphere, and under irradiation with visible light of a wavelength of 420 to 500 nm to generate the phenanthrene compound as shown in the general formula (3);

[0032]

[0033] R 1 is any one of hydrogen, alkyl (e.g., methyl, ethyl, propyl, isopropyl, butyl, isobutyl), halogen (e.g., fluorine, chlorine, bromine, iodine), phenyl, or substituted phenyl (e.g., methyl substituted phenyl, ethyl substituted phenyl, methoxy substituted phenyl, halogen substituted phenyl, etc.); R 2 is hydrogen or halogen (e.g., fluorine, chlorine, bromine, iodine); Ar is aryl or heteroaryl (e.g., thiophene, pyridine, naphthalene), R 3 The alkyl group is any one of hydrogen, alkyl (such as methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, etc.), methoxy, phenyl, naphthyl, formyl or cyano; the Pd catalyst is any one of palladium acetate, tetrakis(triphenylphosphine)palladium, tris(dibenzylideneacetone)dipalladium, palladium trifluoroacetate, bis(triphenylphosphinophenyl)palladium dichloride, bis(diphenylphosphino)ferrocenepalladium dichloride and palladium chloride; palladium acetate and tris(dibenzylideneacetone)dipalladium are more efficient, and can be reacted in one step under mild reaction conditions to efficiently obtain the phenanthrene ring compound; the ligand is 4,5-bis(diphenylphosphino-9,9-dimethylxanthene, bis(2-diphenylphosphinophenyl)ether, 4,6-bis(diphenylphosphino)phenoxazine, 1,1 Any one of '-binaphthyl-2,2'-bisdiphenylphosphine, 1,3-bis(diphenylphosphino)propane, 1,1'-bis(diphenylphosphino)ferrocene, and triphenylphosphine, among which bis(2-diphenylphosphinophenyl)ether and 1,1'-bis(diphenylphosphino)ferrocene are more efficient, and can be reacted in one step under mild reaction conditions to efficiently obtain the phenanthrene ring compound; the alkaline substance is any one of potassium carbonate, cesium carbonate, sodium tert-butoxide, potassium tert-butoxide, lithium tert-butoxide, and potassium phosphate, among which potassium phosphate is preferred, and can be reacted in one step under mild reaction conditions to efficiently obtain the phenanthrene ring compound; the solvent is benzene or fluorobenzene, among which benzene is preferred, and can be reacted in one step under mild reaction conditions to efficiently obtain the phenanthrene ring compound.

[0034] More specific embodiments are as follows:

[0035] Example 1

[0036]

[0037] In a glove box, add 4.5 mg (0.02 mmol) of palladium acetate, 21.5 mg (0.04 mmol) of bis(2-diphenylphosphinophenyl) ether, 84.8 mg (0.40 mmol) of potassium phosphate, 56.0 mg (0.20 mmol) of compound 1a, 61.2 mg (0.6 mmol) of compound 2a to a 3 mL vial. Finally, add 2 mL of benzene. The mixture was stirred at room temperature for 20 hours under the irradiation of a 24 W blue LED lamp. After the reaction was completed, the mixture was washed with water and extracted with ethyl acetate, the organic phases were combined, dried over anhydrous sodium sulfate and concentrated under reduced pressure. The residue was separated by column chromatography to obtain the target compound 3a (product 41.7 mg, yield 82%).

[0038] The target product 3a obtained by the above synthesis method was tested by hydrogen and carbon nuclear magnetic resonance spectra, and the test results are as follows: 1 H NMR (400 MHz, CDCl 3 )δ8.81(d,J=8.4Hz,1H),8.75(d,J=8.0Hz,1H),7.94(ddd,J=14.0,8.0,1.2Hz,2H),7.72–7.62(m,4H),7.60–7.47(m,6H). 13 C NMR (101 MHz, CDCl 3 )δ140.8,138.7,131.5,131.1,130.6,130.0,129.9,128.6,128.3,127.5,127.3,126.9,126.8,126.6,126.5,126.4,122.9,122.5.

[0039] Example 2

[0040]

[0041] In a glove box, add 4.5 mg (0.02 mmol) of palladium acetate, 21.5 mg (0.04 mmol) of bis(2-diphenylphosphinophenyl) ether, 84.8 mg (0.40 mmol) of potassium phosphate, 56.0 mg (0.20 mmol) of compound 1a, 94.9 mg (0.6 mmol) of compound 2b to a 3 mL vial. Finally, add 2 mL of benzene. The mixture was stirred at room temperature for 20 hours under the irradiation of a 24 W blue LED lamp. After the reaction was completed, the mixture was washed with water and extracted with ethyl acetate, the organic phases were combined, dried over anhydrous sodium sulfate and concentrated under reduced pressure. The residue was separated by column chromatography to obtain the target compound 3b (product 39.9 mg, yield 64%).

[0042] The target product 3b obtained by the above synthesis method was tested by hydrogen and carbon nuclear magnetic resonance spectra, and the test results are as follows: 1 H NMR (400 MHz, CDCl 3 )δ8.80(d,J=8.4Hz,1H),8.74(d,J=8.0Hz,1H),8.00(dd,J=8.4,1.2Hz,1H),7.91(dd,J=7.6,1.6Hz,1H),7.71–7.61(m,4H),7.58–7.5 4(m,1H),7.49(d,J=8.0Hz,2H),7.36(d,J=8.0Hz,2H),2.78–2.74(m,2H),1.77–1.70(m,2H),1.52–1.43(m,2H),1.02(t,J=7.2Hz,3H). 13 CNMR(101MHz, CDCl3)δ142.0,138.7,137.9,131.6,131.2,130.6,129.88,129.86,129.8,128.6, 128.3,127.8,127.4,127.0,126.8,126.43,126.40,126.3,122.8,122.5,35.5,33.7,22.5,14.0.

[0043] Example 3

[0044]

[0045] In a glove box, add 4.5 mg (0.02 mmol) of palladium acetate, 21.5 mg (0.04 mmol) of bis(2-diphenylphosphinophenyl) ether, 84.8 mg (0.40 mmol) of potassium phosphate, 56.0 mg (0.20 mmol) of compound 1a, 94.9 mg (0.6 mmol) of compound 2c to a 3 mL vial. Finally, add 2 mL of benzene. The mixture was stirred at room temperature for 20 hours under 24 W blue LED light. After the reaction, the mixture was washed with water and extracted with ethyl acetate, the organic phases were combined, dried over anhydrous sodium sulfate and concentrated under reduced pressure. The residue was separated by column chromatography to obtain the target compound 3c (product 44.5 mg, yield 72%).

[0046] The target product 3c obtained by the above synthesis method was tested by hydrogen and carbon nuclear magnetic resonance spectra, and the test results are as follows: 1 H NMR (400 MHz, CDCl 3)δ8.79(d,J=8.4Hz,1H),8.73(d,J=8.0Hz,1H),8.00(d,J=8.0Hz,1H),7.89(d,J=8.0Hz,1H),7.70–7.60(m,4H),7.57–7.49(m,5H),1.43(s,9H). 13 CNMR (101MHz, CDCl 3 )δ150.2,138.7,137.7,131.6,131.2,130.6,129.9,129.8,129.7,128.6,127.8 ,127.5,127.0,126.8,126.44,126.41,126.36,125.2,122.8,122.5,34.6,31.5.

[0047] Example 4

[0048]

[0049] In a glove box, add 4.5 mg (0.02 mmol) of palladium acetate, 21.5 mg (0.04 mmol) of bis(2-diphenylphosphinophenyl) ether, 84.8 mg (0.40 mmol) of potassium phosphate, 56.0 mg (0.20 mmol) of compound 1a, 79.3 mg (0.6 mmol) of compound 2d to a 3 mL vial, and finally add 2 mL of benzene. The mixture was stirred at room temperature for 20 hours under 24 W blue LED light. After the reaction was completed, the mixture was washed with water and extracted with ethyl acetate, the organic phases were combined, dried over anhydrous sodium sulfate and concentrated under reduced pressure. The residue was separated by column chromatography to obtain the target compound 3d (product 45.3 mg, yield 80%).

[0050] The target product 3d obtained by the above synthesis method was tested by nuclear magnetic resonance hydrogen spectrum and carbon spectrum, and the test results are as follows: 1 H NMR (400 MHz, CDCl 3 )δ8.79(d,J=8.4Hz,1H),8.73(d,J=8.0Hz,1H),7.97(dd,J=8.4,1.2Hz,1H),7.90(dd,J=7.6,1.6Hz,1H), 7.70–7.60(m,4H),7.56(ddd,J=8.0,7.2,1.2Hz,1H),7.51–7.47(m,2H),7.09–7.05(m,2H),3.92(s,3H). 13 C NMR (101 MHz, CDCl 3)δ159.0,138.4,133.1,131.6,131.4,131.1,130.6,129.8,128.5,127.4,126.9,126.8,126.42,126.36,122.9,122.5,113.7,55.4.

[0051] Based on this embodiment, the following single variable experiment is also carried out:

[0052] Table 1 Catalyst selection as a single variable

[0053]

[0054] Table 2 Ligand selection as a single variable

[0055] Serial number Ligand Yield (%) 1 Bis(2-diphenylphosphinophenyl)ether 80 2 4,5-Bis(diphenylphosphino)-9,9-dimethylxanthene 39 3 4,6-Bis(diphenylphosphino)phenoxazine 57 4 1,1'-Binaphthyl-2,2'-bis(diphenylphosphine) 44 5 1,3-Bis(diphenylphosphino)propane 38 6 1,1'-Bis(diphenylphosphino)ferrocene 65 7 Triphenylphosphine 7 8 2,2'-Bipyridine 0

[0056] Table 3 Alkali Selection as a Single Variable

[0057]

[0058]

[0059] Table 4. Solvent selection as a single variable

[0060] Serial number Solvents Yield (%) 1 benzene 80 2 Tetrahydrofuran 4 3 1.4-Dioxane 14 4 Fluorobenzene 38

[0061] Table 5 Selection of light source as a single variable

[0062] Serial number Light source wavelength Yield (%) 1 450-490 80 2 420-430 58 3 520-530 15

[0063] Example 5

[0064]

[0065] In a glove box, add 4.5 mg (0.02 mmol) of palladium acetate, 21.5 mg (0.04 mmol) of bis(2-diphenylphosphinophenyl) ether, 84.8 mg (0.40 mmol) of potassium phosphate, 56.0 mg (0.20 mmol) of compound 1a, 69.7 mg (0.6 mmol) of compound 2e to a 3 mL vial, and finally add 2 mL of benzene. The mixture was stirred at room temperature for 20 hours under 24 W blue LED light. After the reaction was completed, the mixture was washed with water and extracted with ethyl acetate, the organic phases were combined, dried over anhydrous sodium sulfate and concentrated under reduced pressure. The residue was separated by column chromatography to obtain the target compound 3e (product 38.2 mg, yield 71%).

[0066] The target product 3e obtained by the above synthesis method was tested by hydrogen and carbon nuclear magnetic resonance spectra, and the test results are as follows: 1H NMR (400 MHz, CDCl 3 )δ8.80(d,J=8.4Hz,1H),8.77(d,J=8.0Hz,1H),7.91(d,J=8.8Hz,1H),7.73–7.63(m,4H),7.55–7.50(m,2H),7.44–7.35(m,4H),2.10(s,3H). 13 C NMR (101 MHz, CDCl 3 )δ140.2,138.4,137.0,131.6,131.3,130.33,130.29,130.0,129.9,128.6,1 27.7,127.1,126.82,126.76,126.6,126.5,126.4,125.7,122.8,122.5,20.1.

[0067] Example 6

[0068]

[0069] In a glove box, add 4.5 mg (0.02 mmol) of palladium acetate, 21.5 mg (0.04 mmol) of bis(2-diphenylphosphinophenyl) ether, 84.8 mg (0.40 mmol) of potassium phosphate, 56.0 mg (0.20 mmol) of compound 1a, 106.9 mg (0.6 mmol) of compound 2f to a 3 mL vial. Finally, add 2 mL of benzene. The mixture was stirred at room temperature for 20 hours under 24 W blue LED light. After the reaction, the mixture was washed with water and extracted with ethyl acetate, the organic phases were combined, dried over anhydrous sodium sulfate and concentrated under reduced pressure. The residue was separated by column chromatography to obtain the target compound 3f (product 41.6 mg, yield 63%).

[0070] The target product 3f obtained by the above synthesis method was tested by hydrogen and carbon nuclear magnetic resonance spectra, and the test results are as follows: 1 H NMR (400 MHz, CDCl 3 )δ8.81(d,J=8.4Hz,1H),8.75(d,J=8.0Hz,1H),8.02(d,J=8.0Hz,1H),7.92(d,J=7.6Hz,1H),7. 77–7.67(m,7H),7.65–7.62(m,3H),7.60–7.56(m,1H),7.51(t,J=7.6Hz,2H),7.43–7.38(m,1H). 13 C NMR (101 MHz, CDCl 3)δ140.8,140.2,139.7,138.3,131.5,131.0,130.6,130.5,129.9,128.9,128.7,1 27.5,127.4,127.1,127.0,126.89,126.86,126.6,126.54,126.49,122.9,122.5.

[0071] Example 7

[0072]

[0073] In a glove box, add 4.5 mg (0.02 mmol) of palladium acetate, 21.5 mg (0.04 mmol) of bis(2-diphenylphosphinophenyl) ether, 84.8 mg (0.40 mmol) of potassium phosphate, 56.0 mg (0.20 mmol) of compound 1a, 91.3 mg (0.6 mmol) of compound 2g to a 3 mL vial, and finally add 2 mL of benzene. The mixture was stirred at room temperature for 20 hours under the irradiation of a 24 W blue LED lamp. After the reaction was completed, the mixture was washed with water and extracted with ethyl acetate, the organic phases were combined, dried over anhydrous sodium sulfate and concentrated under reduced pressure. The residue was separated by column chromatography to obtain 3 g of the target compound (product 45.7 mg, yield 75%).

[0074] The target product 2g obtained by the above synthesis method was tested by nuclear magnetic resonance hydrogen spectrum and carbon spectrum, and the test results are as follows: 1 H NMR (400 MHz, CDCl 3 )δ8.82(d,J=8.4Hz,1H),8.77(d,J=8.0Hz,1H),8.05(s,1H),8.01–7.93(m,5H),7.81(s,1H),7.73–7.64(m,4H),7.60–7.53(m,3H). 13 C NMR (101 MHz, CDCl 3 )δ138.7,138.3,133.4,132.6,131.5,131.2,130.6,130.0,128.7,128.4,128.0,127. 84,127.76,127.6,127.0,126.9,126.6,126.54,126.49,126.3,126.1,122.9,122.5.

[0075] Example 8

[0076]

[0077] In a glove box, add 4.5 mg (0.02 mmol) of palladium acetate, 21.5 mg (0.04 mmol) of bis(2-diphenylphosphinophenyl) ether, 84.8 mg (0.40 mmol) of potassium phosphate, 56.0 mg (0.20 mmol) of compound 1a, 64.9 mg (0.6 mmol) of compound 2h to a 3 mL vial. Finally, add 2 mL of benzene. The mixture was stirred at room temperature for 20 hours under 24 W blue LED light. After the reaction was completed, the mixture was washed with water and extracted with ethyl acetate, the organic phases were combined, dried over anhydrous sodium sulfate and concentrated under reduced pressure. The residue was separated by column chromatography to obtain the target compound 3h (product 36.1 mg, yield 69%).

[0078] The target product 3h obtained by the above synthesis method was tested by hydrogen and carbon nuclear magnetic resonance spectra, and the test results are as follows: 1 H NMR (400 MHz, CDCl 3 )δ8.78(d,J=8.4Hz,1H),8.72(d,J=8.4Hz,1H),8.31–8.25(m,1H),7.91(dd,J=7.6,1.2Hz,1H),7.87(s,1H),7.73–7 .67(m,2H),7.65–7.60(m,2H),7.47(dd,J=5.2,1.2Hz,1H),7.32(dd,J=3.6,1.2Hz,1H),7.23(dd,J=5.2,3.6Hz,1H). 13 CNMR (101MHz, CDCl 3 )δ141.7,131.2,131.1,131.0,130.6,130.1,129.1,128.7,127.6,127.2,127.0,126.9,126.8,126.7,126.6,125.5,122.9,122.5.

[0079] Example 9

[0080]

[0081] In a glove box, add 4.5 mg (0.02 mmol) of palladium acetate, 21.5 mg (0.04 mmol) of bis(2-diphenylphosphinophenyl) ether, 84.8 mg (0.40 mmol) of potassium phosphate, 56.0 mg (0.20 mmol) of compound 1a, 61.9 mg (0.6 mmol) of compound 2i to a 3 mL vial. Finally, add 2 mL of benzene. The mixture was stirred at room temperature for 20 hours under 24 W blue LED light. After the reaction, the mixture was washed with water and extracted with ethyl acetate, the organic phases were combined, dried over anhydrous sodium sulfate and concentrated under reduced pressure. The residue was separated by column chromatography to obtain the target compound 3h (product 38.3 mg, yield 75%).

[0082] The target product 3i obtained by the above synthesis method was tested by hydrogen and carbon nuclear magnetic resonance spectra, and the test results are as follows: 1 H NMR (400 MHz, CDCl 3 )δ8.83(dd,J=2.4,0.8Hz,1H),8.80(d,J=8.4Hz,1H),8.75–8.72(m,2H),7.93–7.81(m,3H ),7.73–7.62(m,4H),7.57(ddd,J=8.0,7.2,1.2Hz,1H),7.46(ddd,J=7.8,4.8,0.8Hz,1H). 13 C NMR (101 MHz, CDCl 3 )δ150.6,148.7,137.4,136.4,134.9,131.2,130.7,130.6,130.2,128.7,128.3,127.1,127.0,126.79,126.76,126.2,123.1,123.1,122.6.

[0083] Example 10

[0084]

[0085] In a glove box, add 4.5 mg (0.02 mmol) of palladium acetate, 21.5 mg (0.04 mmol) of bis(2-diphenylphosphinophenyl) ether, 84.8 mg (0.40 mmol) of potassium phosphate, 56.0 mg (0.20 mmol) of compound 1a, 86.8 mg (0.6 mmol) of compound 2j to a 3 mL vial, and finally add 2 mL of benzene. The mixture was stirred at room temperature for 20 hours under 24 W blue LED light. After the reaction was completed, the mixture was washed with water and extracted with ethyl acetate, the organic phases were combined, dried over anhydrous sodium sulfate and concentrated under reduced pressure. The residue was separated by column chromatography to obtain the target compound 3j (product 36.8 mg, yield 62%).

[0086] The target product 3j obtained by the above synthesis method was tested by hydrogen and carbon nuclear magnetic resonance spectra, and the test results are as follows: 1 H NMR (400 MHz, CDCl 3 )δ8.80(d,J=8.4Hz,1H),8.74(d,J=8.0Hz,1H),8.12(d,J=8.4Hz,2H),7.91(d,J=7. 2Hz,1H),7.86(d,J=7.8Hz,1H),7.73–7.62(m,6H),7.58–7.54(m,1H),2.71(s,3H). 13 C NMR (101 MHz, CDCl 3 )δ197.9,145.8,137.6,136.1,131.3,130.6,130.5,130.3,130.1,128.8,128.4,127.7,127.01,126.98,126.7,126.5,123.0,122.6,26.8.

[0087] Embodiment 11

[0088]

[0089] In a glove box, add 4.5 mg (0.02 mmol) of palladium acetate, 21.5 mg (0.04 mmol) of bis(2-diphenylphosphinophenyl) ether, 84.8 mg (0.40 mmol) of potassium phosphate, 56.0 mg (0.20 mmol) of compound 1a, 76.3 mg (0.6 mmol) of compound 2k to a 3 mL vial. Finally, add 2 mL of benzene. The mixture was stirred at room temperature for 20 hours under 24 W blue LED light. After the reaction, the mixture was washed with water and extracted with ethyl acetate, the organic phases were combined, dried over anhydrous sodium sulfate and concentrated under reduced pressure. The residue was separated by column chromatography to obtain the target compound 3k (product 45.5 mg, yield 87%).

[0090] The target product 3k obtained by the above synthesis method was tested by nuclear magnetic resonance hydrogen spectrum and carbon spectrum, and the test results are as follows: 1 H NMR (400 MHz, CDCl 3 )δ8.80(d,J=8.4Hz,1H),8.74(d,J=8.0z Hz,1H),7.92–7.90(m,1H),7.83–7.77(m,3H),7.74–7.63(m,6H),7.57(ddd,J=8.0,7.2,1.2Hz,1H). 13CNMR (101MHz, CDCl 3 )δ145.7,136.8,132.2,131.1,130.8,130.7,130.23,130.16,128.8,12 7.9,127.2,127.1,126.87,126.86,126.2,123.1,122.6,118.9,111.3.

[0091] Example 12

[0092]

[0093] In a glove box, 4.5 mg (0.02 mmol) of palladium acetate, 21.5 mg (0.04 mmol) of bis(2-diphenylphosphinophenyl) ether, 84.8 mg (0.40 mmol) of potassium phosphate, 61.6 mg (0.20 mmol) of compound 1b, 61.2 mg (0.6 mmol) of compound 2a were added to a 3 mL vial. The mixture was stirred at room temperature for 20 hours under 24 W blue LED light. After the reaction was completed, the mixture was washed with water and extracted with ethyl acetate, the organic phases were combined, dried over anhydrous sodium sulfate and concentrated under reduced pressure. The residue was separated by column chromatography to obtain the target compound 31 (product 31.0 mg, yield 55%).

[0094] The target product 3l obtained by the above synthesis method was tested by hydrogen and carbon nuclear magnetic resonance spectra, and the test results are as follows: 1 H NMR (400 MHz, CDCl 3 )δ8.75(d,J=4.0Hz,1H),8.73(d,J=3.6Hz,1H),7.92(d,J=7.6Hz,1H),7.79(s,1H),7.72–7.6 7(m,2H),7.65–7.56(m,6H),7.53–7.50(m,1H),2.82(q,J=7.6Hz,2H),1.32(t,J=7.6Hz,3H). 13 CNMR (101MHz, CDCl 3 )δ142.6,140.9,138.6,131.2,130.03,129.97,128.7,128.6,128.3,127.6,127.2,127.0,126.5,126.4,125.3,122.9,122.3,29.0,15.7.

[0095] Example 13

[0096]

[0097] In a glove box, add 4.5 mg (0.02 mmol) of palladium acetate, 21.5 mg (0.04 mmol) of bis(2-diphenylphosphinophenyl) ether, 84.8 mg (0.40 mmol) of potassium phosphate, 62.9 mg (0.20 mmol) of compound 1c, 61.2 mg (0.6 mmol) of compound 2a to a 3 mL vial, and finally add 2 mL of benzene. The mixture was stirred at room temperature for 20 hours under the irradiation of a 24 W blue LED lamp. After the reaction was completed, the mixture was washed with water and extracted with ethyl acetate, the organic phases were combined, dried over anhydrous sodium sulfate and concentrated under reduced pressure. The residue was separated by column chromatography to obtain the target compound 3m (product 42.7 mg, yield 74%).

[0098] The target product 3m obtained by the above synthesis method was tested by nuclear magnetic resonance hydrogen spectrum and carbon spectrum, and the test results are as follows: 1 H NMR (400 MHz, CDCl 3 )δ8.69(d,J=8.8Hz,1H),8.66(d,J=8.0Hz,1H),7.91–7.89(m,2H),7.72–7.60(m,4H),7.57–7.48(m,5H). 13 CNMR (101MHz, CDCl 3 )δ140.0,137.8,132.6,132.3,131.4,129.9,129.5,128.9,128.8,128.7,128.5,127.6,127.1,127.0,126.9,126.0,124.5.

[0099] Embodiment 14

[0100]

[0101] In a glove box, 4.5 mg (0.02 mmol) of palladium acetate, 21.5 mg (0.04 mmol) of bis(2-diphenylphosphinophenyl) ether, 84.8 mg (0.40 mmol) of potassium phosphate, 66.0 mg (0.20 mmol) of compound 1d, 61.2 mg (0.6 mmol) of compound 2a were added to a 3 mL vial. The mixture was stirred at room temperature for 20 hours under the irradiation of a 24 W blue LED lamp. After the reaction was completed, the mixture was washed with water and extracted with ethyl acetate, the organic phases were combined, dried over anhydrous sodium sulfate and concentrated under reduced pressure. The residue was separated by column chromatography to obtain the target compound 3n (product 44.4 mg, yield 73%).

[0102] The target product 3n obtained by the above synthesis method was tested by nuclear magnetic resonance hydrogen spectrum and carbon spectrum, and the test results are as follows:1 H NMR (400 MHz, CDCl 3 )δ8.79(d,J=8.8Hz,2H),8.03(d,J=9.2Hz,1H),7.96(t,J=8.8Hz,2H),7.87–7.83(m,2H) ,7.72(t,J=7.6Hz,1H),7.66(t,J=7.2Hz,1H),7.51–7.46(m,6H),7.16(t,J=7.6Hz,1H). 13 C NMR (101 MHz, CDCl 3 )δ145.5,138.4,133.3,131.4,130.8,130.5,130.0,129.9,129.0,128.9,128.8, 128.3,128.1,128.0,127.4,126.9,126.72,126.66,125.7,124.5,123.1,121.2.

[0103] Embodiment 15

[0104]

[0105] In a glove box, 4.5 mg (0.02 mmol) of palladium acetate, 21.5 mg (0.04 mmol) of bis(2-diphenylphosphinophenyl) ether, 84.8 mg (0.40 mmol) of potassium phosphate, 56.2 mg (0.20 mmol) of compound 1e, 61.2 mg (0.6 mmol) of compound 2a were added to a 3 mL vial. The mixture was stirred at room temperature for 20 hours under 24 W blue LED light. After the reaction was completed, the mixture was washed with water and extracted with ethyl acetate, the organic phases were combined, dried over anhydrous sodium sulfate and concentrated under reduced pressure. The residue was separated by column chromatography to obtain the target compound 3o (product 38.8 mg, yield 75%).

[0106] The target product 3o obtained by the above synthesis method was tested by nuclear magnetic resonance hydrogen spectrum and carbon spectrum, and the test results are as follows: 1 H NMR (400 MHz, CDCl 3 )δ9.29(s,1H),8.78(d,J=5.6Hz,1H),8.72–8.70(m,1H),8.49(d,J=5.6Hz,1H),7.95–7.93(m,1H),7.77–7.71(m,3H),7.59–7.48(m,5H). 13 C NMR (101 MHz, CDCl 3)δ150.5,145.0,138.9,137.7,135.2,133.0,130.0,128.9,128.8,128.7,128.5,128.0,127.9,127.1,125.9,123.0,116.0.

[0107] Example 16

[0108]

[0109] In a glove box, 4.5 mg (0.02 mmol) of palladium acetate, 21.5 mg (0.04 mmol) of bis(2-diphenylphosphinophenyl) ether, 84.8 mg (0.40 mmol) of potassium phosphate, 62.9 mg (0.20 mmol) of compound 1f, 61.2 mg (0.6 mmol) of compound 2a were added to a 3 mL vial. The mixture was stirred at room temperature for 20 hours under 24 W blue LED light. After the reaction was completed, the mixture was washed with water and extracted with ethyl acetate, the organic phases were combined, dried over anhydrous sodium sulfate and concentrated under reduced pressure. The residue was separated by column chromatography to obtain the target compound 3p (product 37.0 mg, yield 74%).

[0110] The target product 3q obtained by the above synthesis method was tested by hydrogen and carbon nuclear magnetic resonance spectra, and the test results are as follows: 1 H NMR (400 MHz, CDCl 3 )δ8.68(d,J=6.8Hz,2H),7.94(d,J=8.4Hz,1H),7.82(d,J=8.4Hz,1H),7.69(t,J=7.6Hz,1H),7.65(s,1H),7.59–7.44(m,7H). 13 C NMR (101 MHz, CDCl 3 )δ140.4,139.1,132.5,131.3,131.0,130.7,130.0,129.9,129.8,129.6, 128.3,128.0,127.5,127.3,127.1,127.0,126.74,126.72,122.9,122.2.

[0111] Embodiment 17

[0112]

[0113] In a glove box, 4.5 mg (0.02 mmol) of palladium acetate, 21.5 mg (0.04 mmol) of bis(2-diphenylphosphinophenyl) ether, 84.8 mg (0.40 mmol) of potassium phosphate, 71.2 mg (0.20 mmol) of compound 1g, 61.2 mg (0.6 mmol) of compound 2a were added to a 3 mL vial. The mixture was stirred at room temperature for 20 hours under 24 W blue LED light. After the reaction was completed, the mixture was washed with water and extracted with ethyl acetate, the organic phases were combined, dried over anhydrous sodium sulfate and concentrated under reduced pressure. The residue was separated by column chromatography to obtain the target compound 3q (product 56.8 mg, yield 86%).

[0114] The target product 3q obtained by the above synthesis method was tested by hydrogen and carbon nuclear magnetic resonance spectra, and the test results are as follows: 1 H NMR (400 MHz, CDCl 3 )δ8.85(d,J=8.4Hz,1H),8.75(d,J=8.0Hz,1H),8.17(s,1H),7.93(t,J=8.0Hz,2H),7.74–7.68(m, 2H),7.63(dd,J=12.4,7.2Hz,5H),7.55(t,J=7.2Hz,2H),7.48–7.44(m,3H),7.36(t,J=7.6Hz,1H). 13 C NMR (101 MHz, CDCl 3 )δ141.0,140.7,139.1,138.9,131.6,131.4,130.0,129.79,129.75,128.8,128.7 ,128.4,128.0,127.42,127.37,127.3,126.9,126.7,125.7,125.0,123.5,122.6.

[0115] Based on Example 17, when only the ratio of the 2-iodobiphenyl to the ligand is adjusted to 1:0.1-0.3 (molar ratio), and / or the ratio of the 2-iodobiphenyl to the base is 1:1.5-3 (molar ratio), and / or the equivalent of 2-iodobiphenyl to the alkyne is 1:1-1:3.0 (molar ratio), the product yield ranges from 80% to 86%.

[0116] The above is only a preferred specific implementation of the present invention, but the protection scope of the present invention is not limited thereto. Any technician familiar with the technical field within the technical scope disclosed by the present invention, according to the technical solution and its concept of the present invention, shall be covered within the protection scope of the present invention. It should be noted that the embodiments of the present invention and the features in the embodiments can be combined with each other without conflict.

Claims

1. A one-step synthesis method of phenanthrene aromatic derivatives, characterized in that: The method comprises the following steps: using 2-iodobiphenyl as shown in the general formula (1) and alkyne as shown in the general formula (2), using a transition metal Pd catalyst, a ligand, an alkaline substance and a solvent, in a nitrogen atmosphere, and under the irradiation of visible light with a wavelength of 420 to 500 nm, to generate the phenanthrene ring compound as shown in the general formula (3); R 1 Any one of hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, halogen, phenyl, methyl substituted phenyl, ethyl substituted phenyl, methoxy substituted phenyl, and halogen substituted phenyl; R 2 is hydrogen or halogen; Ar is aryl, thiophene, pyridine or naphthalene, R 3 Any one of hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, methoxy, phenyl, naphthyl, formyl or cyano; The Pd catalyst is any one of palladium acetate, tetrakis(triphenylphosphine)palladium, tris(dibenzylideneacetone)dipalladium, palladium trifluoroacetate, bis(triphenylphosphinophenyl)palladium dichloride, bis(diphenylphosphino)ferrocenepalladium dichloride, and palladium chloride; The ligand is any one of 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene, bis(2-diphenylphosphinophenyl)ether, 4,6-bis(diphenylphosphino)phenoxazine, 1,1'-binaphthyl-2,2'-bis(diphenylphosphino)propane, 1,1'-bis(diphenylphosphino)ferrocene, and triphenylphosphine; The alkaline substance is any one of potassium carbonate, cesium carbonate, sodium tert-butoxide, potassium tert-butoxide, lithium tert-butoxide, and potassium phosphate; The solvent is benzene or fluorobenzene; The molar ratio of the 2-iodobiphenyl to the ligand is 1:0.1-0.3; The molar ratio of 2-iodobiphenyl to the base is 1:1.5-3; The molar ratio of the 2-iodobiphenyl to the alkyne is 1:1-1:3.

0.

2. The one-step synthesis method of phenanthrene aromatic derivatives according to claim 1, characterized in that: The molar ratio of 2-iodobiphenyl to the ligand is 1:0.

2.

3. The one-step synthesis method of phenanthrene aromatic derivatives according to claim 1, characterized in that: The molar ratio of the 2-iodobiphenyl to the base is 1:

2.

4. The one-step synthesis method of phenanthrene aromatic derivatives according to claim 1, characterized in that: The wavelength of the light source is 420-490nm.

5. The one-step synthesis method of phenanthrene aromatic derivatives according to claim 1, characterized in that: The wavelength of the light source is 450-490nm.

6. The one-step synthesis method of phenanthrene aromatic derivatives according to claim 1, characterized in that: The step of purification is also included: concentration after the reaction is completed and purification by column chromatography.

7. The one-step synthesis method of phenanthrene aromatic derivatives according to claim 1, characterized in that: The compound of general formula (3) is the following specific compound:

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