A method for synthesizing 6-arylphenanthridine compounds

Abstract

This invention discloses a method for synthesizing 6-arylphenanthrene diphenyl compounds. The method involves a dehydrazine radical tandem addition-cyclization reaction of 2-isocyanuric biphenyl and arylhydrazine under air atmosphere and blue visible light irradiation, catalyzed by a molybdenum sulfide / N-hydroxyphthalimide synergistic catalytic system, to generate 6-arylphenanthrene diphenyl compounds. This method has the advantages of readily available raw materials, simple operation, mild reaction conditions, high reaction selectivity and yield, and excellent substrate functional group compatibility.

Description

Technical Field

[0001] This invention relates to a method for synthesizing 6-arylphenanthrene diphenyl ether compounds, and particularly to a method using arylhydrazine as the aryl source and molybdenum sulfide as a semiconductor heterogeneous photocatalyst. N Using 2-hydroxyphthalimide as a homogeneous small organic molecule co-catalyst, a method is developed to generate 6-arylphenanthrene diphenyl compounds by a dehydrazine radical tandem addition-cyclization reaction of arylhydrazine and 2-isocyanate biphenyl derivatives under air atmosphere and blue visible light irradiation. This method belongs to the field of organic synthesis technology. Background Technology

[0002] Phenyridine compounds are commonly used pharmacophores in drug research. Derivatives of this parent structure possess a variety of physiological and pharmacological activities and are widely used as anticancer, antitumor, and antibacterial drugs, representing a class of potential multi-purpose lead compounds with broad development and application prospects. In fact, the functional groups modified on the phenyridine parent structure influence the drug and biological activities of the molecule, not just the quinoxalinone parent structure itself. Therefore, the modification of the phenyridine parent structure with different substituents and the study of its structure-activity relationship have gradually become a research hotspot.

[0003] 6-Arylphenanthridine and its derivatives possess a wide range of biological and pharmacological activities. Therefore, numerous synthetic methods for these compounds have been established in recent years. However, almost all methods proposed to date are limited to homogeneous synthesis, and homogeneous reaction catalysts are difficult to recover and reuse, for example (Yan Gao, Yi Jing, Lixin Li, Jie Zhang, Xuenian Chen, Yan-Na Ma, Synthesis of Phenanthridines through Iodine-SupportedIntramolecular C–H Amination and Oxidation under Visible Light, J. Org.Chem., 2020, 85(19): 12187-12198); (Hidenori Okamura, Momoka Iida, YuiKaneyama, Fumi Nagatsugi, o-Nitrobenzyl Oxime Ethers Enable PhotoinducedCyclization Reaction to Provide Phenanthridines under Aqueous Conditions, Org. Lett., 2023, 25(3): 466-470, etc.). There are no reports on heterogeneous catalytic synthesis of 6-arylphenanthridines. Summary of the Invention

[0004] To address the shortcomings of existing methods for synthesizing phenanthridine compounds, the present invention aims to provide a method for synthesizing 6-arylphenanthridine compounds, using arylhydrazine as the aryl source and molybdenum sulfide as a semiconductor heterogeneous photocatalyst. N -Hydroxyphthalimide serves as a homogeneous small organic molecule co-catalyst. Under air atmosphere and blue visible light irradiation, arylhydrazine undergoes a dehydrazine radical tandem addition-cyclization reaction with 2-isocyanate biphenyl derivatives to generate 6-arylphenanthridine compounds. This method features readily available raw materials, simple operation, mild reaction conditions, high reaction selectivity and yield, and excellent substrate functional group compatibility, providing intermediate raw materials for the synthesis of phenanthridine compounds.

[0005] This invention provides a method for synthesizing 6-arylphenanthrene diphenyl compounds, wherein 2-isocyanate biphenyl and arylhydrazine are reacted in an atmosphere of air and under blue visible light irradiation in a molybdenum disulfide / N Under the catalytic action of a hydroxyphthalimide-co-catalyzed system, a dehydrazine radical tandem addition-cyclization reaction occurs to generate a 6-arylphenanthridine compound; the arylhydrazine has the structure of Formula 1:

[0006]

[0007] Formula 1

[0008] The 6-arylphenanthridine compound has the structure of Formula 2:

[0009]

[0010] Formula 2

[0011] in,

[0012] Ar is phenyl, substituted phenyl, naphthyl or substituted naphthyl;

[0013] The substituted phenyl group has at least C1 to C2 on its benzene ring. 10 Alkyl, C1~C 10 One of the following substituents: alkoxy, halogen substituent, trifluoromethyl, benzyl, or phenyl;

[0014] The substituted naphthyl benzene ring contains at least C1 to C2. 10 Alkyl, C1~C 10 One of the following substituents: alkoxy, halogen substituent, trifluoromethyl, benzyl, or phenyl.

[0015] In the 6-arylphenanthrene diamine compound of the present invention, Ar is a substituent introduced by an arylhydrazine substrate. Different substituents will produce different electronic effects and steric hindrance effects, which will have a certain impact on the yield of the target product 6-arylphenanthrene diamine compound. However, in general, within the selectable range of Ar, by optimizing the reaction conditions, the yield of the target product is between 84% and 94%, which is a relatively ideal yield.

[0016] Ar represents an aryl group, specifically a phenyl, a substituted phenyl, a naphthyl, or a substituted naphthyl group. Substituted phenyl groups are derivatives of phenyl, and substituted naphthyl groups are derivatives of naphthyl. They contain conventional small-molecule substituents on their benzene rings. The number of substituents can be one or more, typically one to two, and their positions are not limited. Specifically, the substituents on the benzene ring can be selected from C1 to C2. 10 Alkyl groups (such as straight-chain alkyl groups like methyl, ethyl, propyl, octyl, etc.; alkyl groups with 3 or more carbon atoms also include isomers, such as branched alkyl groups, specifically isobutyl, isooctyl, etc.), C1~C 10 Alkoxy groups (including straight-chain alkoxy groups and branched alkoxy groups, such as methoxy, ethoxy, hexoxy, isobutoxy, etc.), halogen substituents (such as fluorine substituents, chlorine substituents, bromine substituents or iodine substituents), trifluoromethyl, benzyl or phenyl.

[0017] As a preferred embodiment, the molar ratio of 2-isocyanate biphenyl to arylhydrazine is 1:1 to 2. The theoretical reaction molar ratio of 2-isocyanate biphenyl to arylhydrazine is 1:1. Appropriately increasing the molar amount of arylhydrazine is beneficial to obtaining a higher yield of the target product. The molar ratio of 2-isocyanate biphenyl to arylhydrazine is further preferably 1:1.5 to 2.

[0018] As a preferred embodiment, the molybdenum disulfide to 2-isocyanuric biphenyl ratio is 5-20 mg:0.2 mmol. Within the preferred dosage range, increasing the amount of molybdenum disulfide significantly improves the yield of the target product. However, the yield reaches its maximum when the molybdenum disulfide to 2-isocyanuric biphenyl ratio is 10 mg:0.2 mmol, and further increasing the molybdenum disulfide content does not significantly increase the yield. A further preferred molybdenum disulfide to 2-isocyanuric biphenyl ratio is 10-15 mg:0.2 mmol.

[0019] As a preferred solution, the N The amount of 2-hydroxyphthalimide (NHPI) used is 5 to 15% of the molar amount of 2-isocyanate biphenyl. N -Hydroxyphthalimide, within the preferred dosage range, as N Increasing the amount of β-hydroxyphthalimide can significantly improve the yield of the target product, but NThe yield of the target product reaches its maximum when the amount of 2-hydroxyphthalimide is 10% of the molar amount of 2-isocyanopropyl biphenyl, and further increases in concentration result in a lower yield. N The yield increase of the target product was not significant with -hydroxyphthalimide. N The amount of -hydroxyphthalimide is further preferably 10 to 15% of the molar amount of 2-isocyanate biphenyl.

[0020] As a preferred embodiment, the wavelength of the blue visible light is 450~460nm.

[0021] As a preferred embodiment, the blue visible light is provided by a 5W to 10W LED light source. While the blue visible light has a relatively small impact on the reaction, a high yield of the target product can be ensured at the preferred blue visible light wavelength and power.

[0022] As a preferred embodiment, the reaction uses ethyl acetate as the reaction medium. The reaction solvent should be selected to simultaneously dissolve organic substrates such as 2-isocyanate biphenyl and arylhydrazine, and to have good dispersibility for inorganic compounds such as molybdenum disulfide. Ethyl acetate has a clear advantage in this regard.

[0023] As a preferred embodiment, the conditions for the dehydrazine radical tandem addition-cyclization reaction are: 8-20 hours at room temperature.

[0024] The route for the dehydrazine radical tandem addition-cyclization reaction of the 2-isocyanate biphenyl derivative and arylhydrazine of the present invention is as follows:

[0025]

[0026] This invention also proposes a reasonable reaction mechanism:

[0027]

[0028] Under blue visible light irradiation, MoS2 absorbs photons to generate photogenerated holes and photoelectrons. The photoelectrons reduce oxygen molecules in the air to generate superoxide radical anions, which combine with hydrogen ions to form superoxide radicals. N -Hydroxyphthalimide is oxidized by photogenerated holes to... N The 1-hydroxyphthalimide radical oxidizes phenylhydrazine (2) to generate a phenyl radical, nitrogen gas, and hydrogen ions. The phenyl radical selectively attacks the isonitrile group of 2-isocyanate biphenyl (1) to generate a carbon-centered radical intermediate (A), which undergoes an intramolecular cycloaddition reaction to give an aryl radical intermediate (B). Finally, under the action of superoxide radicals, intermediate B undergoes dehydrogenation aromatization to generate the target product 6-phenylphenanthrene (3) and hydrogen peroxide byproduct. The hydrogen peroxide byproduct rapidly decomposes into water and oxygen molecules.

[0029] Compared with the prior art, the technical solution of the present invention brings the following beneficial technical effects:

[0030] 1) This invention uses MoS2 and N The semi-heterogeneous photocatalytic reaction system constructed with hydroxyphthalimide combines the advantages of homogeneous semiconductor photocatalysis and heterogeneous organic catalysis. The semiconductor catalyst MoS2 is easily recovered and recycled. N -Hydroxyphthalimide diffuses organic synthesis reactions from the semiconductor solid / liquid interface to the homogeneous phase, significantly improving reaction efficiency.

[0031] 2) This invention does not use homogeneous transition metal catalysts, making it safe, environmentally friendly, and low-cost. The semiconductor catalyst MoS2 can be reused.

[0032] 3) This invention uses air as the oxidation source and does not use other peroxides, persulfates or other oxidants, making it green and environmentally friendly. The byproduct is water.

[0033] 4) This invention uses a visible light source, has mild reaction conditions, high efficiency, and is easy to promote and use. Attached Figure Description

[0034] Figure 1 The 1H NMR spectrum of 6-phenylphenanthridine;

[0035] Figure 2 The image shows the carbon NMR spectrum of 6-phenylphenanthridine. Detailed Implementation

[0036] The following specific embodiments are intended to further illustrate the content of the present invention, rather than to limit the scope of protection of the claims of the present invention.

[0037] Unless otherwise specified, all chemical reagents used in the following examples were commercially available and used without further purification. Thin-layer chromatography (TLC) was performed using 0.25 mm silica gel glass plates. The chromatographic column was packed with 200-300 mesh silica gel. Recording was performed at 500 MHz. 1 1H NMR spectrum, recorded at 125 MHz 13 19F NMR spectra were recorded at 471 MHz using a Bruker Avance 500 spectrometer. The undeuterated residual solvent was used as an internal control. (1 ¹H NMR: CDCl 37.26 ppm, 13 CNMR (CDCl 377.0 ppm) was used to determine the chemical shift, which is expressed in ppm and J value in Hz. HRMS was performed on an ESI-TOF spectrometer.

[0038] Compared with the control group of examples, the reaction conditions were optimized using the following specific reactions as standard reactions:

[0039]

[0040] The specific operating steps are as follows: Add 2-isocyanuric biphenyl (0.2 mmol), phenylhydrazine (0.3 mmol), and MoS2 (10 mg) to a 10.0 mL quartz reaction tube. N -Hydroxyphthalimide (0.02 mmol) and ethyl acetate (3 mL) were used in a quartz reaction tube exposed to air at room temperature for about 12 hours under 6W blue (455 nm) LED illumination. The reaction was monitored by thin-layer chromatography and the yield was analyzed by gas chromatography-mass spectrometry after the reaction was completed.

[0041] Table 1 Optimization of Reaction Conditions ab

[0042] Entry Different from standard conditions Yield (%) 1 none 97 2 <![CDATA[Replacement of MoS2 with g-C3N4]]> 36 3 <![CDATA[CdS replaces MoS2]]> 41 4 <![CDATA[Replacement of MoS2 with MoO3]]> No response 5 <![CDATA[Replacement of MoS2 with ZnS]]> No response 6 <![CDATA[MoS 2 (5 mg) Replacement for MoS 2 (10 mg) 84 7 <![CDATA[MoS 2 (15 mg) Alternative to MoS 2 (10 mg) 97 8 <![CDATA[Do not use MoS2]]> No response 9 NaI replaces NHP 57 11 TEMPO replaces NHPI 36 12 <![CDATA[Replacement of NHPI with NPh3]]> 50 13 Do not use NHPI 58 14 <![CDATA[O2 replacement for Air]]> 97 15 <![CDATA[N2 replaces Air]]> No response 16 No lighting No response

[0043] a Standard reaction conditions: 2-isocyanobiphenyl (0.2 mmol), phenylhydrazine (0.3 mmol), MoS2 (15 mg), NHPI (10% mol), ethyl acetate (3 mL), 455 nm Blue LED (6 W), air, room temperature.

[0044] b Estimated by GC-MS.

[0045] The experimental groups 1-5 in the table above investigated the effects of different catalysts on the dehydrazine radical tandem addition-cyclization reaction between 2-isocyanobiphenyl and phenylhydrazine. The experimental data show that photocatalysts such as MoS2, g-C3N4 and CdS can catalyze the reaction smoothly. However, the catalytic effects of g-C3N4 and CdS are much lower than those of MoS2. Using MoS2 can achieve the ideal yield of the target product.

[0046] The experimental groups 1 and 6-8 in the table above investigated the effect of different molybdenum disulfide dosages on the dehydrazine radical tandem addition-cyclization reaction between 2-isocyanobiphenyl and phenylhydrazine. The experimental data show that within the preferred dosage range, the reaction hardly proceeds without molybdenum disulfide. However, increasing the dosage of molybdenum disulfide can significantly improve the yield of the target product. But when the dosage of molybdenum disulfide reaches a certain level, the yield of the target product can reach its maximum value, and further increasing the dosage of molybdenum disulfide does not significantly increase the yield of the target product.

[0047] The table above shows experimental groups 1 and 9-13, which investigated the effects of different co-catalysts on the dehydrazine radical tandem addition-cyclization reaction between 2-isocyanobiphenyl and phenylhydrazine. The experimental data show that NaI, TEMPO, and NPh3, as co-catalysts, did not significantly promote the reaction; in particular, TEMPO and NPh3 exhibited inhibitory effects, significantly worsening the reaction upon their addition. In contrast, NHPI, as a co-catalyst, significantly promoted the reaction, substantially increasing the yield of the target product compared to a single molybdenum disulfide catalytic system. Furthermore, a significant synergistic catalytic effect between molybdenum disulfide and NHPI was observed. While molybdenum disulfide alone produced relatively poor catalytic performance, NHPI alone showed no catalytic effect. This indicates that the combination of molybdenum disulfide as the main catalyst and NHPI as the co-catalyst results in a synergistic catalytic effect greater than the sum of its parts (1+1>2).

[0048] The experimental groups 1 and 14-16 in the table above investigated the effects of light, reaction atmosphere and other conditions on the dehydrazine radical tandem addition-cyclization reaction between 2-isocyanobiphenyl and phenylhydrazine. The experimental data show that oxygen and light are necessary conditions for the reaction.

[0049] Examples 1-8

[0050] Examples 1-8 below all react according to the following reaction equations:

[0051]

[0052] The specific operating steps are as follows: 2-isocyanobiphenyl (0.2 mmol), arylhydrazine (0.3 mmol), MoS2 (10 mg), NHPI (0.02 mmol) and ethyl acetate (3 mL) were added to a 10.0 mL quartz reaction tube. Under 6 W blue (455 nm) LED irradiation, the quartz reaction tube was exposed to air at room temperature and stirred. The reaction progress was monitored by thin-layer chromatography. After the reaction was completed, the insoluble matter was removed by filtration, the filtrate was evaporated under reduced pressure, and purified by silica gel column chromatography to obtain the corresponding 6-arylphenanthrene diphenyl compound.

[0053] Example 1

[0054]

[0055] 6-phenylphenanthridine, yield 94%.

[0056] 1 H NMR (500 MHz, DMSO) δ 8.95 (d, J = 8.2 Hz, 1H), 8.86 (d,J = 8.1Hz, 1H), 8.12 (d, J = 8.1 Hz, 1H), 8.04 (d, J = 8.2 Hz, 1H), 8.01 - 7.95 (m,1H), 7.85–7.76 (m, 1H), 7.78–7.69 (m, 4H), 7.60 (d, J = 7.0 Hz, 3H); 13 C NMR(126 MHz, DMSO) δ 160.5, 143.2, 139.3, 132.9, 131.1, 129.8, 129.7, 129.2,128.8, 128.4, 128.2, 127.9, 127.3, 124.4, 123.3, 122.9, 122.8. Example

[0057] 6-(p-tolyl)phenanthridine, yield 92%.

[0058]

[0059] 1 H NMR (500 MHz, CDCl3) δ 8.70 (d, J = 8.2 Hz, 1H), 8.61 (d, J = 8.2Hz, 1H), 8.26 (d, J = 8.2 Hz, 1H), 8.16 (d, J = 8.2 Hz, 1H), 7.86 (t, J = 7.6Hz, 1H), 7.76 (t, J = 7.8 Hz, 1H), 7.71 - 7.65 (m, 2H), 7.67 - 7.58 (m, 2H),7.38 (d, J = 7.7 Hz, 2H), 2.49 (s, 3H);

[0060] 13C NMR (126 MHz, CDCl3) δ 161.5, 143.9, 138.7, 136.8, 133.6, 130.6,130.3, 129.8, 129.3, 129.2, 128.8, 127.2, 126.8, 122.2, 121.8, 21.6. Example

[0061] 6-(4-methoxyphenyl)phenanthridine, yield 89%.

[0062]

[0063] 1 H NMR (500 MHz, CDCl3) δ 8.74 (d, J = 8.3 Hz, 1H), 8.68–8.62 (m, 1H), 8.30–8.25 (m, 1H), 8.21 (d, J = 8.3 Hz, 1H), 7.93–7.86 (m, 1H), 7.82–7.74 (m,2H), 7.76–7.69 (m, 2H), 7.69–7.63 (m, 1H), 7.14 (d, J = 8.7 Hz, 2H), 3.96 (s, 3H);

[0064] 13 C NMR (126 MHz, CDCl3) δ 160.9, 160.2, 143.9, 133.5, 132.3, 131.2,130.5, 130.3, 129.0, 128.8, 127.1, 126.8, 125.4, 123.6, 122.2, 121.9, 113.9,55.5. Example

[0065] 6-(4-fluorophenyl)phenanthridine, yield 91%.

[0066]

[0067] 1 H NMR (500 MHz, CDCl3) δ 8.72 (d, J = 8.3 Hz, 1H), 8.63 (d, J= 8.2Hz, 1H), 8.24 (d, J = 8.1 Hz, 1H), 8.08 (d, J = 8.3 Hz, 1H), 7.88 (t, J = 7.7Hz, 1H), 7.81–7.67 (m, 4H), 7.64 (t, J = 7.6 Hz, 1H), 7.27 (d, J = 17.0 Hz,2H);

[0068] 13 C NMR (126 MHz, CDCl3) δ 164.2, 162.2, 160.2, 143.7, 135.8, 133.5,131.7, ۱۳۱.۶, ۱۳۰.۷, ۱۳۰.۳, ۱۲۹.۰, ۱۲۸.۷, ۱۲۷.۳, ۱۲۷.۱, ۱۲۵.۲, ۱۲۳.۸, ۱۲۲.۳,۱۲۲.۰, ۱۱۵.۶, ۱۱۵.۴. Example

[0069] 6-(4-chlorophenyl)phenanthridine, yield 93%.

[0070]

[0071] 1 H NMR (500 MHz, CDCl3) δ 8.73 (d, J = 8.3 Hz, 1H), 8.64 (d, J = 8.1Hz, 1H), 8.24 (d, J = ۷.۷ Hz, 1H), 8.08 (d, J = 8.2 Hz, 1H), 7.92–7.86 (m,1H), 7.81–7.68 (m, 4H), 7.68–7.61 (m, 1H), 7.56 (d, J = 8.2 Hz, 2H);

[0072] 13 It should be noted that in the translation of the "C NMR" part, the Chinese characters in the original text seem to be incorrect. I have translated them according to the correct content in the English text. If there are specific requirements for this part, please let me know.C NMR (126 MHz, CDCl3) δ 160.0, 143.7, 138.2, 134.9, 133.5, 131.2,130.7, 130.4, 129.0, 128.7, 128.5, 127.3, 127.2, 125.0, 123.8, 122.4, 122.0. Example

[0073] 6-(4-bromophenyl)phenanthridine, yield 90%.

[0074]

[0075] 1H NMR (500 MHz, CDCl 3 ) δ 8.73 (d, J = 8.3 Hz, 1H), 8.64 (d, J = 8.1Hz, 1H), 8.24 (d, J = 8.1 Hz, 1H), 8.07 (d, J = 8.2 Hz, 1H), 7.89 (t, J = 7.6Hz, 1H), 7.78 (t, J = 7.5 Hz, 1H), 7.75–7.69 (m, 3H), 7.68–7.62 (m, 3H);

[0076] 13C NMR (126 MHz, CDCl3) δ 160.0, 143.7, 138.7, 133.5, 131.7, 131.4,130.7, 130.4, 129.0, 128.5, 127.3, 127.2, 125.0, 123.8, 123.2, 122.4, 122.0. Example

[0077] 6-(4-(trifluoromethyl)phenyl)phenanthridine, yield 87%.

[0078]

[0079] 1 H NMR (500 MHz, CDCl3) δ 8.74 (d, J = 8.3 Hz, 1H), 8.64 (d, J = 8.1Hz, 1H), 8.24 (d, J = 8.1 Hz, 1H), 8.02 (d,J = 8.3 Hz, 1H), 7.93–7.87 (m,1H), 7.89–7.82 (m, 4H), 7.82–7.76 (m, 1H), 7.76–7.70 (m, 1H), 7.65 (t, J =7.7 Hz, 1H); 13 C NMR (126 MHz, CDCl3) δ 159.7, 143.7, 143.4, 133.5, 131.3,131.2, 131.0, 130.9, 130.7, 130.5, 130.4, 130.2, 129.5, 129.1, 128.3, 127.4,125.5, 125.5, 125.5, 125.4, 125.3, 124.9, 123.9, 123.1, 122.4, 122.0; 19 F NMR(471 MHz, CDCl3) δ -62.57. Example

[0080] 6-(naphthalen-1-yl)phenanthridine, yield 84%.

[0081]

[0082] 1 H NMR (500 MHz, CDCl3) δ 8.75 (d, J = 8.3 Hz, 1H), 8.70 (d, J = 8.1Hz, 1H), 8.28 (d, J = 7.9 Hz, 1H), 8.06–8.00 (m, 1H), 7.97 (d, J = 8.3 Hz,1H), 7.89–7.72 (m, 2H), 7.69–7.62 (m, 3H), 7.52–7.46 (m, 1H), 7.44 (d, J =8.5 Hz, 1H), 7.34–7.27 (m, 1H); 13C NMR (126 MHz, CDCl3) δ 161.1, 143.9,137.2, 133.7, 133.1, 132.3, 130.8, 130.5, 129.1, 128.9, 128.3, 127.4, 127.3,127.2, 126.6, 126.4, 126.1, 126.0, 125.4, 124.0, 122.1. Example

[0083] 2-Isocyanobiphenyl (0.2 mmol), phenylhydrazine (0.3 mmol), MoS2 (10 mg), NHPI (0.02 mmol), and ethyl acetate (3 mL) were added to a 10.0 mL quartz reaction tube. Under 6 W blue (455 nm) LED illumination, the quartz reaction tube was exposed to air at room temperature and stirred for about 12 hours. The reaction progress was monitored by thin-layer chromatography. After the reaction was completed, the filtrate was filtered to separate MoS2, which was then directly used for the next batch of reactions. The new reaction was carried out according to the above operation. The yield of 6-phenylphenanthrene was analyzed by gas chromatography-mass spectrometry of the filtrate. After 4 cycles, the catalytic efficiency of MoS2 remained at a high level, which is beneficial to reducing the cost of catalyst use.

[0084] .

Claims

1. A method for synthesizing a 6-arylphenanthrene diphenyl ether compound, characterized in that: Under air atmosphere and blue visible light irradiation conditions, 2-isocyanobiphenyl and arylhydrazine in molybdenum disulfide and N Under the catalytic action of a hydroxyphthalimide co-catalytic system, a dehydrazine radical tandem addition-cyclization reaction occurs to generate a 6-arylphenanthridine compound; The arylhydrazine has the structure of Formula 1: ； Formula 1 The 6-arylphenanthridine compound has the structure of Formula 2: ； Formula 2 in, Ar is phenyl, substituted phenyl, naphthyl or substituted naphthyl; The substituents on the benzene ring of the substituted phenyl group are C1~C1. 10 Alkyl, C1~C 10 alkoxy, halogen substituents, trifluoromethyl, benzyl or phenyl; The substituents on the benzene ring of the substituted naphthyl group are C1~C1. 10 Alkyl, C1~C 10 The alkoxy, halogen substituent, trifluoromethyl, benzyl or phenyl groups.

2. The method for synthesizing a 6-arylphenanthrene diphenyl compound according to claim 1, characterized in that: The molar ratio of 2-isocyanate biphenyl to arylhydrazine is 1:1~2.

3. The method for synthesizing a 6-arylphenanthrene diphenyl compound according to claim 1, characterized in that: The ratio of molybdenum disulfide to 2-isocyanuric biphenyl is 5~20 mg : 0.2 mmol.

4. The method for synthesizing a 6-arylphenanthrene diphenyl compound according to claim 1, characterized in that: The N The amount of 2-hydroxyphthalimide used is 5 to 15% of the molar amount of 2-isocyanate biphenyl.

5. A method for synthesizing a 6-arylphenanthrene dimethyl compound according to claim 1, 2, 3 or 4, characterized in that: The wavelength of the blue visible light is 450~460nm.

6. The method for synthesizing a 6-arylphenanthrene diphenyl compound according to claim 5, characterized in that: The blue visible light is provided by a 5W~10W LED light source.

7. The method for synthesizing a 6-arylphenanthrene diphenyl compound according to claim 1, characterized in that: The reaction uses ethyl acetate as the reaction medium.

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