A phenanthridine compound and its synthesis method

Abstract

This article relates to a method for preparing phenanthridine. The invention involves converting biphenyl isonitriles into polysubstituted phenanthridines and their derivatives under photocatalysis and blue light in an argon atmosphere, yielding molecules with stable structures and excellent chemical properties. The synthetic method utilizes inexpensive and readily available raw materials; the reaction requires only a photocatalyst, additives, and blue light, thus saving raw materials and reducing reaction costs. The entire reaction system is simple, the reaction conditions are mild, the required equipment is minimal, the experimental operation is straightforward, and the yield is moderate to high.

Description

Technical Field

[0001] This invention relates to a phenanthridine compound and its synthesis method, belonging to the field of organic synthesis. Background Technology

[0002] Phenyridine and its derivatives are important organic nitrogen-containing heterocyclic compounds. Phenyridine forms the backbone of fluorescent dyes that intercalate into and bind to DNA, allowing the relative positions of nucleic acids to be identified on the gel after nucleic acid electrophoresis, such as the nucleic acid dyes ethidium bromide and propidium iodide. Phenyridine plays a significant role in pharmaceuticals and medicinal chemistry, and its core backbone appears in various drugs, such as Trispheridine, Decarine, and Asiatcumine A.

[0003] Summary of the Invention

[0004] Therefore, in order to overcome the deficiencies of the prior art, the present invention provides phenanthridine and its derivatives with stable molecular structure and excellent chemical properties.

[0005] The technical solution adopted by this invention to solve its technical problem is as follows: This invention provides phenanthridine and its derivatives, whose general formula is Formula I:

[0006]

[0007] in

[0008] R1 is selected from:

[0009] Hydrogen atom, halogen group, alkyl group, methoxy group, cyano group.

[0010] R2 is selected from:

[0011] Hydrogen atom, halogen group, alkyl group, methoxy group, cyano group, phenoxy group, phenyl group, ester group, trifluoromethyl group, methylthio group, benzodiazole subunit.

[0012] This invention also provides a method for synthesizing phenanthridine and its derivatives, under photocatalysis and blue light irradiation, comprising the following steps:

[0013] (I) Add biphenyl isonitrile compounds, additives, catalysts, and organic solvents into the reaction vessel;

[0014] (II) Mix the reactants thoroughly and carry out the reaction under blue light irradiation and heating under argon protection;

[0015] (III) Purify to obtain the product.

[0016] Preferably, in the method of the present invention, the biphenyl isonitrile compound has the general formula II:

[0017]

[0018] in

[0019] R1 is selected from:

[0020] Hydrogen atom, halogen group, alkyl group, methoxy group, cyano group.

[0021] R2 is selected from:

[0022] Hydrogen atom, halogen group, alkyl group, methoxy group, cyano group, phenoxy group, phenyl group, ester group, trifluoromethyl group, methylthio group, benzodiazole subunit.

[0023] Preferably, in the method of the present invention, the additive is selected from: triphenylphosphine, tricyclohexylphosphine, and tris(4-methoxyphenyl)phosphine.

[0024] Preferably, in the method of the present invention, the photocatalyst is one of: Ir(ppy)3, Ir(dFCF3ppy)2(dtbbpy)PF6, 4CzIPN, Rose Bengal, Ru(bpy)3·6H2O, and Eosin Y.

[0025] Preferably, in the method of the present invention, the organic solvent is one of DCM, MeCN, MeOH, DCE, Acetone, 1,4-Dioxane, PhCl, and DMF.

[0026] Preferably, in the method of the present invention, the atmosphere of the reaction vessel is: argon atmosphere; the molar ratio of biphenyl isonitrile compound to photocatalyst to additive is 1.0:0.01-0.05:0.2-0.6; the reaction temperature is 50℃-65℃; and the reaction time is 24h-36h.

[0027] The beneficial effects of this invention compared to the prior art are as follows:

[0028] (I) This invention provides a technical solution for converting biphenyl isonitriles into phenanthridine and its derivatives under photocatalysis and blue light irradiation in an argon atmosphere. It employs a one-pot, direct, and selective synthesis of the target product with a moderate to high yield, overcoming the significant waste of human, financial, and material resources associated with existing multi-step synthesis methods, and saving substantial research and development time and production cycles. (II) This technical solution for converting biphenyl isonitriles into phenanthridine and its derivatives under photocatalysis and blue light irradiation in an argon atmosphere features a simple reaction system, mild reaction conditions, wide availability of raw materials, high product utilization value, and promising market commercialization prospects. (III) This technical solution for converting biphenyl isonitriles into phenanthridine and its derivatives under photocatalysis and blue light irradiation in an argon atmosphere is scientifically sound, rationally designed, easy to operate, requires fewer reaction steps, and necessitates less equipment. The phenanthridine derivatives and their synthesis method of this invention can be used in multiple fields such as dyes, pharmaceuticals, and materials; it is particularly suitable for the research and development of efficient and selective one-pot synthesis of phenanthridine compounds. Attached Figure Description

[0029] To demonstrate the product of this invention, the present invention provides hydrogen NMR and carbon NMR spectra of some embodiments.

[0030] Figure 1a and 1b NMR spectrum of the product in Example 2.

[0031] Figure 2a and 2b NMR spectrum of the product in Example 3.

[0032] Figure 3a and 3b NMR spectrum of the product in Example 10.

[0033] Where a is the proton spectrum and b is the carbon spectrum.

[0034] Figure 4 This is the chemical reaction principle equation of this application. Detailed Implementation

[0035] The present invention will now be described in further detail with reference to the accompanying drawings. These drawings are simplified schematic diagrams, illustrating only the basic structure of the invention, and therefore only show the components relevant to the invention.

[0036]

[0037] Examples 1-15

[0038] Step 1: Add the biphenyl isonitrile compound (see Table 1 for specific substances) to the reaction vessel, and add the additive (see Table 1 for specific substances), photocatalyst (see Table 1 for specific substances), and organic solvent (see Table 1 for specific substances) to the reaction vessel respectively.

[0039] Step 2: Irradiate the reaction vessel under blue light, and allow the biphenyl isonitrile compounds to react in the solvent for the time specified in Table 1; it should be noted that argon is selected as the protective atmosphere for this reaction.

[0040] Step 3: Purification step.

[0041] Table 1: Molar ratios and reaction times of biphenyl isonitrile compounds, photocatalysts, additives, and organic solvents (biphenyl isonitrile compounds, photocatalysts, and additives) in Examples 1-15.

[0042]

[0043]

[0044] *Molar ratio of biphenyl isonitrile compounds, photocatalysts, and additives.

[0045] The conversion rate of the substances in the reaction vessel after step 3 was detected and nuclear magnetic resonance was performed. The results of some embodiments are as follows:

[0046] The NMR data of the product from Example 2 are as follows:

[0047] 1H NMR(400MHz,Chloroform-d)δ9.02(s,1H),8.29(d,J=8.2Hz,1H),8.12(d,J=8.2Hz,1H),7.79 (d,J=1.7Hz,1H),7.66(t,J=7.5Hz,1H),7.58(t,J=7.6Hz,1H),7.24(s,1H),6.10(s,2H); 13C NMR(101MHz,Chloroform-d)δ151.66,151.27,148.01,130.02,129.91,127.86,126.54,124.12,122.89,121.87,105.29,101.81,99.74.

[0048] The NMR data of the product in Example 3 are as follows:

[0049] 1H NMR(400MHz,Chloroform-d)δ9.24(s,1H),8.49(dd,J=5.1,2.8Hz,2H),8.10(q,J=2.4Hz,1H),8 .04(d,J=7.9Hz,1H),7.89–7.84(m,1H),7.73(t,J=7.5Hz,1H),7.67(dd,J=8.7,2.2Hz,1H); 13C NMR(101MHz,Chloroform-d)δ153.69,142.80,132.97,131.54,131.48,131.25,128.78,128.13,126.41,125.14,121.86,121.83.

[0050] The NMR data of the product of Example 10 are as follows:

[0051] 1H 13C NMR(101MHz,Chloroform-d)δ153.29,144.06,137.41,132.70,130.30,129.96,128.13,128.04,126.90,126.45,124.10,121.96,121.65,21.45.

[0052] Table 2. Conversion rates and products of reactions in Examples 1-15

[0053]

[0054]

[0055] Based on the above-described preferred embodiments of the present invention, and through the foregoing description, those skilled in the art can make various changes and modifications without departing from the inventive concept. The technical scope of this invention is not limited to the contents of the specification, but must be determined according to the scope of the claims.

Claims

1. A method of synthesizing phenanthridine and its derivatives, characterized by, Under the irradiation of blue light and the photocatalyst, the method comprises the following steps: (I) adding a biphenyl isonitrile compound, an additive, a photocatalyst and an organic solvent into a reaction container; (II) mixing the reactants, and performing a reaction under the irradiation of blue light and heating in an argon atmosphere; (III) purifying to obtain a product; The chemical formula of the phenanthridine and the derivative is: The photocatalyst is Ru(bpy)3·6H2O; The additive is triphenylphosphine; The organic solvent is 1,4-dioxane; The biphenyl isonitrile compound is 5-chloro-2-isocyanyl-1,1'-biphenyl; The atmosphere of the reaction container is an argon atmosphere; the molar ratio of the biphenyl isonitrile compound, the photocatalyst and the additive is 1.0:0.03:0.6; the reaction temperature is 50 DEG C; and the reaction time is 24 hours.

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