A method for the photoinduced catalytic synthesis of 1-phenylseleno-N-benzyl-2-naphthylamine compounds
By using N-benzyl-2-naphthalene amine and diphenyldiselene as substrates and metal iodide as catalysts under visible light, it directly constructs C-H bonds to form C-Se bonds, solving the problem of synthesis of ortho-aromatic selenonaphthalene compounds in the prior art, and providing an efficient and green synthesis method.
Patent Information
- Application Number
- CN202310138115.6
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2023-02-20
- Publication Date
- 2025-07-08
- Estimated Expiration
- 2043-02-20
AI Technical Summary
The prior art is difficult to efficiently and greenly synthesize ortho-aromatic selenonaphthylamine compounds, especially when transition metals, high temperatures and photosensitizers are not used, and the synthesis conditions do not have good functional group tolerance.
N-benzyl-2-naphthylamine and diphenyldiselene are used as substrates, metal iodide or ammonium iodide as catalysts, and C-H bonds are directly constructed under air or oxygen atmosphere through visible light induction, and oxygen is used as an oxidant to avoid the construction of carbon halogen bonds.
The efficient synthesis of 1-phenylselenium-N-benzyl-2-naphthylamine compound under mild conditions is achieved, with high atomic economy and good functional group compatibility, and is suitable for actual industrial production.
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Abstract
Description
Technical Field
[0001] The present invention belongs to the field of compound synthesis, and particularly relates to a method for photoinduced catalytic synthesis of 1-phenylseleno-N-benzyl-2-naphthylamine compounds. Background Art
[0002] Naphthyl skeleton-containing compounds can not only serve as important intermediates for the synthesis of drug molecules and functional materials, but also organic small molecules containing this structure widely exist in drug molecular structures. For example, the drug molecule propranolol containing a naphthyl skeleton is one of the best-selling antihypertensive drugs in the world, and naproxen is a non-steroidal anti-inflammatory drug (Eur. J. Org. Chem., 2017, 2017, 4740). In order to develop new drugs or improve the activity of drugs, functionalization of the naphthyl skeleton has become a research hotspot. It has been found that arylselenonaphthalenes have good biological activities (Synlett 2021, 32(09), 940), and ortho-arylselenoarylamine compounds are not only important reaction precursors for the synthesis of benzoselenazoles and benzoselenazines, but also their skeleton structures widely exist in drug molecular structures. Therefore, developing green and efficient synthesis methods for ortho-arylseleno-naphthylamine compounds has important research significance.
[0003] The present invention develops a method for the visible light-induced catalytic synthesis of 1-phenylseleno-N-benzyl-2-naphthylamine compounds using N-benzyl-2-naphthylamine and diphenyldiselenide as substrates and metal iodide or ammonium iodide as a catalyst. This method directly reacts with C-H bonds to construct C-Se bonds, without the addition of transition metals, without high temperature, and without the need to additionally add photosensitizers. Using oxygen as a green oxidant, the reaction conditions are mild, the functional group tolerance is excellent, and it has good application prospects, providing an efficient and green synthesis method for the synthesis of ortho-arylseleno-naphthylamine compounds. Summary of the Invention
[0004] The purpose of the present invention is to provide a method for photoinduced catalytic synthesis of 1-phenylseleno-N-benzyl-2-naphthylamine compounds in view of the disadvantages and deficiencies of the prior art. The present invention develops a method for the visible light-induced catalytic synthesis of ortho-arylseleno-naphthylamine compounds using N-benzyl-2-naphthylamine and diphenyldiselenide as substrates and metal iodide or ammonium iodide as a catalyst. This method avoids constructing C-Se bonds through carbon-halogen bonds, but directly uses C-H bonds to construct C-Se bonds, without transition metals, without high temperature, and without the need to additionally add photosensitizers. Using oxygen as a green oxidant, the reaction conditions are mild, the functional group tolerance is excellent, and it has good application prospects, providing an efficient and green synthesis method for the synthesis of ortho-arylseleno-naphthylamine compounds.
[0005] The purpose of the present invention is achieved through the following technical solutions.
[0006] A method for photocatalytic synthesis of 1-phenylseleno-N-benzyl-2-naphthylamine compound, comprising the following steps:
[0007] In a reaction tube, add N-benzyl-2-naphthylamine, diphenyldiselenide, catalyst metal iodide or ammonium iodide, and a solvent. Under an air or oxygen atmosphere, irradiate the reaction tube with visible light at 25~80 °C for reaction. After the reaction is completed, through separation and purification, the o-arylselenenylnaphthylamine compound is obtained.
[0008] Furthermore, the chemical reaction equation in the synthesis process is as follows:
[0009]
[0010] Furthermore, the catalyst is sodium iodide, potassium iodide or ammonium iodide, preferably sodium iodide.
[0011] Furthermore, the oxidant is oxygen.
[0012] Furthermore, the atmosphere is air or oxygen.
[0013] Furthermore, the solvent is acetonitrile, dichloromethane, tetrahydrofuran, ethanol, or methanol, preferably acetonitrile.
[0014] Furthermore, the visible light is 2~10 W violet light, 2~10 W blue light, or 2~10 W green light, preferably 6 W blue light.
[0015] Furthermore, the operation of separation and purification is: add the reaction solution into ethyl acetate, wash and extract twice with saturated NaCl solution, take the upper organic phase solution, dry it with anhydrous magnesium sulfate, filter, concentrate under reduced pressure, and then separate and purify by column chromatography to obtain the o-arylselenenylnaphthylamine compounds.
[0016] Furthermore, the molar ratio of the compound represented by structural formula I to the compound represented by structural formula II is 1:0.5~3, preferably 1:0.55.
[0017] Furthermore, the molar ratio of the catalyst to the compound represented by formula I is 0.05~0.30:1, preferably 0.1:1.
[0018] Furthermore, the stirring reaction duration is 13~39 hours.
[0019] Furthermore, the reaction temperature is 25~80 °C, preferably 60 °C.
[0020] The present invention uses oxygen as an oxidant, metal iodide or ammonium iodide as a catalyst, and under the induction of visible light, uses N-benzyl-2-naphthylamine and diphenyl diselenide as substrates to construct a C-Se bond at the C-H bond at the 1-position of N-benzyl-2-naphthylamine to synthesize 1-phenylseleno-N-benzyl-2-naphthylamine compounds, providing an efficient and green synthesis method for the synthesis of ortho-arylselenonaphthylamine compounds.
[0021] Compared with the existing technologies, the present invention has the following advantages and beneficial effects:
[0022] The present invention constructs a C-Se bond using the C-H bond at the 1-position of N-benzyl-2-naphthylamine, avoiding the use of halogen-containing substrates as reaction precursors, and all diphenyl diselenide is used to participate in the reaction, having the advantage of high atom economy;
[0023] The present invention does not require transition metals, high temperatures, or additional photosensitizers, uses oxygen as a green oxidant, has simple reaction conditions, easily available raw materials, and good functional group compatibility, and thus is expected to be applied to actual industrial production for better application. Specific Embodiments
[0024] The following further describes the technical solutions of the present invention in detail with specific embodiments, but the protection scope and implementation manners of the present invention are not limited thereto. Examples
[0025] In a reaction tube, N-benzyl-2-naphthylamine (0.2 mmol), diphenyl diselenide (0.11 mmol), sodium iodide (0.02 mmol), acetonitrile (2.0 mL), and a magnetic stir bar were successively added, and the reaction was carried out under 6W blue light irradiation at 60 °C in an air atmosphere for 39 hours. After cooling to room temperature, the reaction solution was added to ethyl acetate, washed and extracted twice with saturated NaCl solution, the upper organic phase solution was taken, dried with anhydrous magnesium sulfate, filtered, concentrated under reduced pressure, and then purified by column chromatography to obtain the target product with a yield of 53%. The NMR data of the obtained target product are as follows:
[0026] 1 H NMR (500 MHz, CDCL3) δ 8.33 (d, J J = 8.5 Hz, 1H), 7.75 (d, J J = 9.0 Hz,1H), 7.67 (d, J J = 8.0 Hz, 1H), 7.41 (t, J J = 7.5 Hz, 1H), 7.25-7.18 (m, 7H), 7.13(s, 4H), 7.04 (d,J = 9.0 Hz, 1H), 6.04 (s, 1H), 4.52 (s, 2H); 13 C NMR (126 MHz, CDCl3) δ 148.47, 139.20, 137.11, 131.94, 131.84, 129.24, 128.74, 128.62, 128.35, 127.71, 127.68, 127.13, 126.93, 126.56, 125.90, 122.10, 113.63, 105.82, 47.92。
[0027] Based on the above data, the structure of the target product is speculated as follows:
[0028] 。
Claims
1. A method for the photocatalytic synthesis of 1-phenylseleno-N-benzyl-2-naphthylamine compounds, characterized in that, It comprises the following steps: ； Add N-benzyl-2-naphthylamine shown by formula I, diphenyldiselenide shown by formula II, a catalyst and a solvent into a reaction tube, and under an oxygen or air atmosphere, irradiate the reaction tube with visible light at 25-80 °C for reaction. After the reaction is completed, 1-phenylseleno-N-benzyl-2-naphthylamine compound shown by formula III is obtained through separation and purification; Wherein, the catalyst is sodium iodide, potassium iodide or ammonium iodide; The oxidant is oxygen; The solvent is acetonitrile, dichloromethane, tetrahydrofuran, ethanol or methanol; The visible light is violet light, blue light or green light.
2. The method according to claim 1, wherein The operation of the separation and purification is: add the reaction solution into ethyl acetate, wash and extract twice with saturated NaCl solution, take the upper organic phase solution, dry it with anhydrous magnesium sulfate, filter, concentrate under reduced pressure, and then separate and purify by column chromatography to obtain the 1-phenylseleno-N-benzyl-2-naphthylamine compound.
3. The method according to claim 1, characterized in that, The molar ratio of the compound shown by the structural formula I to the compound shown by the structural formula II is 1:0.5-3.
4. The method according to claim 1, wherein The molar ratio of the catalyst to the compound shown by formula I is 0.05-0.30:
1.
5. The method according to claim 1, characterized in that, The power of the visible light is 2-10 W.
6. The method according to claim 1, characterized in that, The reaction duration is 13-39 hours.
7. The method according to claim 1, wherein The reaction temperature is 25-80 °C.
8. The method according to claim 1, characterized in that The reaction atmosphere is air or oxygen.
Citation Information
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