A method for photoinduced catalytic synthesis of diaryl sulfide amine compounds

Abstract

The present invention belongs to the field of compound synthesis, and specifically relates to a method for photoinduced catalytic synthesis of diaryl sulfide amine compounds. The synthesis method is: adding aromatic amine, aromatic persulfur mystery, catalyst metal iodide or ammonium iodide, and solvent to a reaction tube, and irradiating the reaction tube with visible light at 25~80°C in an air or oxygen atmosphere to react, and after the reaction is completed, diaryl sulfide amine compounds are obtained by post-processing. The present invention directly constructs a C-S bond by C-H bond reaction, does not require the addition of transition metals, does not require high temperature, and does not require the additional addition of photosensitizers. It uses oxygen in the air as a green oxidant, and can react under the catalytic action of visible light-induced iodide. The reaction conditions are mild and the functional group tolerance is excellent. It has a good application prospect and provides an efficient and green synthesis method for the synthesis of diaryl sulfide amine compounds.

Description

Technical Field

[0001] The invention belongs to the field of compound synthesis, and in particular relates to a method for synthesizing diaryl sulfide amine compounds by light-induced catalysis. Background Art

[0002] Diaryl sulfide amine compounds can not only be used as important intermediates for the synthesis of drug molecules and functional materials, but also small organic molecules containing this structure are widely present in the molecular structure of drugs. For example, the antipsychotic phenothiazine and the drug vortioxetine for the treatment of depression both contain this structure (Synlett 2021, 32(09), 940). Therefore, it is of certain significance to study the synthesis method of diaryl sulfide amine compounds.

[0003] The present invention develops a method for synthesizing diaryl sulfide amine compounds using aromatic amine and aromatic persulfide as substrates and catalyzed by metal iodide or ammonium iodide induced by visible light. The method directly reacts the CH bond to construct the CS bond, does not require the addition of transition metals, does not require high temperature, and does not require the additional addition of photosensitizers. It uses oxygen as a green oxidant, has mild reaction conditions, and has excellent functional group tolerance. It has good application prospects and provides an efficient and green synthesis method for the synthesis of diaryl sulfide amine compounds. Summary of the invention

[0004] The purpose of the present invention is to provide a method for photo-induced catalytic synthesis of diaryl sulfide amine compounds in view of the shortcomings and deficiencies of the prior art. The present invention develops a method for synthesizing diaryl sulfide amine compounds by visible light induced catalytic reaction using aromatic amines and aromatic persulfides as substrates and metal iodides or ammonium iodide as catalysts. The method avoids constructing a CS bond through a carbon-halogen bond, but directly uses a CH bond to construct a CS bond, does not require transition metals, does not require high temperatures, and does not require additional photosensitizers. It uses oxygen as a green oxidant, has mild reaction conditions, and has excellent functional group tolerance. It has good application prospects and provides an efficient and green synthesis method for the synthesis of diaryl sulfide amine compounds.

[0005] The purpose of the present invention is achieved through the following technical solutions.

[0006] A method for photoinduced catalytic synthesis of diaryl sulfide amine compounds comprises the following steps:

[0007] In a reaction tube, aromatic amine, aromatic persulfur, catalyst metal iodide or ammonium iodide, and solvent are added, and the reaction tube is irradiated with visible light at 25-80° C. in an air or oxygen atmosphere to react. After the reaction is completed, the diaryl sulfide amine compound is obtained by separation and purification.

[0008] Further, the chemical reaction equation of the synthesis process is as follows:

[0009]

[0010] In the formula, Ar is 2-naphthyl, 6-bromo-2-naphthyl, 3,4,5-trimethylphenyl, 3,4-trimethoxyphenyl, or 3,4,5-trimethoxyphenyl; R 1 is methyl, benzyl, phenyl, 2-acetoxymethyl, or allyl; R 2 is phenyl, p-chlorophenyl, p-hydroxyphenyl, p-aminophenyl, 4-pyridyl, or 2-benzothiazolyl;

[0011] Further, the general formula I is 2-naphthylamine, N-methyl-2-naphthylamine, N-phenyl-2-naphthylamine, 2-(naphthalene-2-amino)methyl acetate, N-allyl-2-naphthylamine, N-benzyl-6-bromo-2-naphthylamine, N-benzyl-3,4,5-trimethylaniline, N-benzyl-3,4-dimethoxyaniline, N-benzyl-3,4,5-trimethoxyaniline, or N-benzyl-2-naphthylamine; the general formula II is 2,2',4,4'-tetramethyl diphenyl disulfide, diphenyl disulfide, 4,4'-dichlorodiphenyl disulfide, 4,4'-dihydroxydiphenyl disulfide, 4,4'-diaminodiphenyl disulfide, 4,4'-bipyridyl disulfide, or 2,2'-dibenzothiazole disulfide.

[0012] Furthermore, the catalyst is sodium iodide, potassium iodide or ammonium iodide, preferably sodium iodide.

[0013] Furthermore, the oxidant is oxygen.

[0014] Furthermore, the atmosphere is air or oxygen.

[0015] Furthermore, the solvent is acetonitrile, dichloromethane, tetrahydrofuran, ethanol, or methanol, preferably acetonitrile.

[0016] Furthermore, the visible light is 2-10W violet light, 2-10W blue light, or 2-10W green light, preferably 6W blue light.

[0017] Furthermore, the separation and purification operation is as follows: adding the reaction solution to ethyl acetate, washing and extracting twice with a saturated NaCl solution, taking the upper organic phase solution, drying it with anhydrous magnesium sulfate, filtering it, concentrating it under reduced pressure, and then separating and purifying it by column chromatography to obtain the diaryl sulfide amine compound.

[0018] Furthermore, the molar ratio of the compound of structural formula I to the compound of structural formula II is 1:0.5-3, preferably 1:0.55.

[0019] Furthermore, the molar ratio of the catalyst to the compound of formula I is 0.05 to 0.30:1, preferably 0.1:1.

[0020] Furthermore, the stirring reaction time is 13 to 39 hours.

[0021] Furthermore, the reaction temperature is 25-80°C, preferably 60°C.

[0022] The invention uses oxygen as an oxidant, metal iodide or ammonium iodide as a catalyst, aromatic amines and aromatic persulfides as substrates under the induction of visible light, and synthesizes diaryl sulfide amine compounds by constructing CS bonds from ortho-CH bonds in the aromatic amines, thereby providing an efficient and green synthesis method for the synthesis of diaryl sulfide amine compounds.

[0023] Compared with the existing technology, the present invention has the following advantages and beneficial effects:

[0024] The present invention utilizes the ortho-CH bond in the aromatic amine to construct the CS bond, thus avoiding the use of a halogen-containing substrate as a reaction precursor, and all the aromatic persulfur is used to participate in the reaction, which has the advantage of high atom economy.

[0025] The present invention does not require transition metals, high temperatures, or additional photosensitizers, but uses oxygen as a green oxidant, has simple reaction conditions, readily available raw materials, and good functional group compatibility. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 and Figure 2 They are respectively the hydrogen spectrum and carbon spectrum of the target product obtained in Example 1.

[0027] Figure 3 and Figure 4 They are respectively the hydrogen spectrum and carbon spectrum of the target product obtained in Example 2.

[0028] Figure 5 and Figure 6 They are respectively the hydrogen spectrum and carbon spectrum of the target product obtained in Example 3.

[0029] Figure 7 and Figure 8 They are respectively the hydrogen spectrum and carbon spectrum of the target product obtained in Example 4.

[0030] Fig. 9 and Fig.10 They are respectively the hydrogen spectrum and carbon spectrum of the target product obtained in Example 5.

[0031] Fig.11 and Fig.12 They are respectively the hydrogen spectrum and carbon spectrum of the target product obtained in Example 6.

[0032] Fig.13 and Fig.14 They are respectively the hydrogen spectrum and carbon spectrum of the target product obtained in Example 7.

[0033] Fig.15 and Fig.16 They are respectively the hydrogen spectrum and carbon spectrum of the target product obtained in Example 8.

[0034] Fig.17 and Fig.18 They are respectively the hydrogen spectrum and carbon spectrum of the target product obtained in Example 9.

[0035] Fig.19 and Fig. 20 They are respectively the hydrogen spectrum and carbon spectrum of the target product obtained in Example 10.

[0036] Fig.21 and Fig. 22 They are respectively the hydrogen spectrum and carbon spectrum of the target product obtained in Example 11.

[0037] Fig.23 and Fig.24 They are respectively the hydrogen spectrum and carbon spectrum of the target product obtained in Example 12.

[0038] Fig.25 and Fig.26 They are respectively the hydrogen spectrum and carbon spectrum of the target product obtained in Example 13.

[0039] Fig. 27 and Fig.28 They are respectively the hydrogen spectrum and carbon spectrum of the target product obtained in Example 14.

[0040] Fig.29 and Fig.30 They are respectively the hydrogen spectrum and carbon spectrum of the target product obtained in Example 15. Specific implementation methods

[0041] The technical solution of the present invention is further described in detail below in conjunction with specific embodiments and drawings, but the protection scope and implementation methods of the present invention are not limited thereto. Example 1

[0042] 2-naphthylamine (0.2 mmol), 2,2',4,4'-tetramethyl diphenyl disulfide (0.11mmol), sodium iodide (0.02 mmol), acetonitrile (2.0 mL) and a magnetic stirrer were added to the reaction tube in sequence, and the mixture was reacted for 20 hours under 6W blue light irradiation at 60 °C in an air atmosphere, cooled to room temperature, and the reaction solution was added to ethyl acetate, washed and extracted twice with saturated NaCl solution, and the upper organic phase solution was taken, dried with anhydrous magnesium sulfate, filtered, concentrated under reduced pressure, and then separated and purified by column chromatography to obtain the target product with a yield of 43%. The hydrogen spectrum and carbon spectrum of the obtained target product are shown as follows: Figure 1 and Figure 2 The NMR data are shown below:

[0043] 1 H NMR (500 MHz, CDCl 3 ) δ 8.20 (d, J = 8.0 Hz, 1H), 7.75 (d, J = 9.0Hz, 1H), 7.71 (d, J = 8.0 Hz, 1H), 7.40 (t, J = 8.0 Hz, 1H), 7.25 (t, J = 7.0Hz, 1H), 7.04 (d, J = 9.0 Hz, 1H), 6.99 (s, 1H), 6.66 (d, J = 8.0 Hz, 1H),6.34 (d, J = 8.0 Hz, 1H), 4.67 (s, 2H), 2.51 (s, 3H), 2.20 (s, 3H); 13 C NMR (126 MHz, CDCl 3 ) δ .82, 134.39, 132.02, 131.59, 131.10,128.51, 128.34, 127.72, 127.29, 124.47, 124.32, 122.56, 117.66, 104.57,20.70, 19.96.

[0044] The structure of the target product is inferred from the above data as follows:

[0045] . Example 2

[0046] N-methyl-2-naphthylamine (0.2 mmol), 2,2',4,4'-tetramethyldiphenyl disulfide (0.11 mmol), sodium iodide (0.02 mmol), acetonitrile (2.0 mL) and a magnetic stirrer were added to the reaction tube in sequence. The mixture was reacted for 13 hours under 6W blue light irradiation at 60 °C in an air atmosphere. The mixture was cooled to room temperature, and the reaction solution was added to ethyl acetate. The mixture was washed and extracted twice with a saturated NaCl solution. The upper organic phase solution was taken, dried over anhydrous magnesium sulfate, filtered, concentrated under reduced pressure, and then separated and purified by column chromatography to obtain the target product with a yield of 79%.

[0047] The hydrogen spectrum and carbon spectrum of the obtained target product are as follows: Figure 3 and Figure 4 The NMR data are shown below:

[0048] 1 H NMR (500 MHz, CDCl 3 ) δ 8.17 (d, J = 9.0 Hz, 1H), 7.89 (d, J = 9.0Hz, 1H), 7.74 (d, J = 8.0 Hz, 1H), 7.42-7.39 (m, 1H), 7.23 (t, J = 7.5 Hz,1H), 7.18 (d, J = 9.0 Hz, 1H), 7.00 (s, 1H), 6.65 (d, J = 8.0 Hz, 1H), 6.25(d, J = 8.0 Hz, 1H), 2.97 (s, 3H), 2.52 (s, 3H), 2.21 (s, 3H); 13 C NMR (126MHz, CDCl 3 ) δ .88, 127.76, 127.28, 124.27, 124.14, 122.25, 113.35, 104.32, 31.22, 20.68,19.93.

[0049] The structure of the target product is inferred from the above data as follows:

[0050] . Example 3

[0051] N-phenyl-2-naphthylamine (0.2 mmol), 2,2',4,4'-tetramethyldiphenyl disulfide (0.11 mmol), sodium iodide (0.02 mmol), acetonitrile (2.0 mL) and a magnetic stirrer were added to the reaction tube in sequence. The mixture was reacted for 39 hours under 6W blue light irradiation at 60 °C in an air atmosphere. The mixture was cooled to room temperature, and the reaction solution was added to ethyl acetate. The mixture was washed and extracted twice with a saturated NaCl solution. The upper organic phase solution was taken, dried over anhydrous magnesium sulfate, filtered, concentrated under reduced pressure, and then separated and purified by column chromatography to obtain the target product with a yield of 61%.

[0052] The hydrogen spectrum and carbon spectrum of the obtained target product are as follows: Figure 5 and Figure 6 The NMR data are shown below:

[0053] 1 H NMR (500 MHz, CDCl 3 ) δ 8.26 (d, J = 8.5 Hz, 1H), 7.82 (d, J = 9.0Hz, 1H), 7.77 (d, J = 8.0 Hz, 1H), 7.58 (d, J = 8.5 Hz, 1H), 7.45 (t, J = 7.5Hz, 1H), 7.35-7.30 (m, 3H), 7.19 (d, J = 7.5 Hz, 2H), 7.08 (t, J = 7.5 Hz,1H), 7.03 (s, 1H), 6.71 (d, J = 8.0 Hz, 1H), 6.42 (d, J = 8.0 Hz, 1H), 2.56(s, 3H), 2.23 (s, 3H); 13 C NMR (126 MHz, CDCl 3 ) δ.81, 124.56, 123.19, 123.16, 121.42, 116.43, 107.85, 20.67, 19.98.

[0054] The structure of the target product is inferred from the above data as follows:

[0055] . Example 4

[0056] Methyl 2-(naphthalene-2-amino)acetate (0.2 mmol), 2,2',4,4'-tetramethyldiphenyl disulfide (0.11 mmol), sodium iodide (0.02 mmol), acetonitrile (2.0 mL) and a magnetic stirrer were added to the reaction tube in sequence, and the mixture was reacted for 25 hours under 6W blue light irradiation at 60 °C in an air atmosphere. The mixture was cooled to room temperature, and the reaction solution was added to ethyl acetate, washed and extracted twice with saturated NaCl solution. The upper organic phase solution was taken, dried over anhydrous magnesium sulfate, filtered, concentrated under reduced pressure, and then separated and purified by column chromatography to obtain the target product with a yield of 61%.

[0057] The hydrogen spectrum and carbon spectrum of the obtained target product are as follows: Figure 7 and Figure 8 The NMR data are shown below:

[0058] 1 H NMR (500 MHz, CDCl 3 ) δ 8.13 (d, J = 8.0 Hz, 1H), 7.74 (d, J = 9.0Hz, 1H), 7.62 (d, J = 7.5 Hz, 1H), 7.32 (t, J = 8.0 Hz, 1H), 7.15 (t, J = 7.5Hz, 1H), 6.90 (s, 1H), 6.86 (d, J = 9.0 Hz, 1H), 6.55 (d, J = 8.0 Hz, 1H),6.24 (d, J= 8.0 Hz, 1H), 5.96 (s, 1H), 3.96 (d, J = 5.5 Hz, 2H), 3.62 (s, 3H), 2.46 (s, 3H), 2.10 (s, 3H); 13 C NMR (126 MHz, CDCl 3 ) δ 8, 171.05, 148.23,136.87, 135.08, 134.46, 132.10, 132.00, 131.08, 128.41, 127.87, 127.26,124.79, 124.53, 122.52, 117.68, 113.09, 105.60, 52.27, 45.69, 20.74, 20.06.

[0059] The structure of the target product is inferred from the above data as follows:

[0060] . Example 5

[0061] N-allyl-2-naphthylamine (0.2 mmol), 2,2',4,4'-tetramethyldiphenyl disulfide (0.11 mmol), sodium iodide (0.02 mmol), acetonitrile (2.0 mL) and a magnetic stirrer were added to the reaction tube in sequence. The mixture was reacted for 39 hours under 6W blue light irradiation at 60 °C in an air atmosphere. The mixture was cooled to room temperature, and the reaction solution was added to ethyl acetate. The mixture was washed and extracted twice with a saturated NaCl solution. The upper organic phase solution was taken, dried over anhydrous magnesium sulfate, filtered, concentrated under reduced pressure, and then separated and purified by column chromatography to obtain the target product with a yield of 58%.

[0062] The hydrogen spectrum, carbon spectrum and fluorine spectrum of the obtained target product are as follows: Fig. 9 and Fig.10 The NMR data are shown below:

[0063] 1 H NMR (500 MHz, CDCl 3 ) δ 8.17 (d, J = 8.5 Hz, 1H), 7.82 (d, J = 9.0Hz, 1H), 7.71 (d, J = 8.0 Hz, 1H), 7.38 (t, J= 7.5 Hz, 1H), 7.23-7.19 (m,1H), 7.08 (d, J = 9.0 Hz, 1H), 6.99 (s, 1H), 6.65 (d, J = 8.0 Hz, 1H), 6.30(d, J = 8.0 Hz, 1H), 5.92-5.85 (m, 1H), 5.70 (s, 1H), 5.19 (d, J = 17.0 Hz,1H), 5.11 (d, J = 10.0 Hz, 1H), 3.93 (d, J = 4.0 Hz, 2H), 2.52 (s, 3H), 2.20(s, 3H); 13 C NMR (126 MHz, CDCl 3 ) δ .04, 113.72, 103.74, 46.03, 20.73, 20.00.

[0064] The structure of the target product is inferred from the above data as follows:

[0065] . Example 6

[0066] N-benzyl-6-bromo-2-naphthylamine (0.2 mmol), 2,2',4,4'-tetramethyldiphenyl disulfide (0.11 mmol), sodium iodide (0.02 mmol), acetonitrile (2.0 mL) and a magnetic stirrer were added to the reaction tube in sequence. The mixture was reacted for 15 hours under 6W blue light irradiation at 60°C in an air atmosphere. The mixture was cooled to room temperature, and the reaction solution was added to ethyl acetate. The mixture was washed and extracted twice with saturated NaCl solution. The upper organic phase solution was taken, dried over anhydrous magnesium sulfate, filtered, concentrated under reduced pressure, and then separated and purified by column chromatography to obtain the target product with a yield of 70%.

[0067] The hydrogen spectrum and carbon spectrum of the obtained target product are as follows: Fig.11 and Fig.12 The NMR data are shown below:

[0068] 1 H NMR (500 MHz, CDCl 3 ) δ 7.97 (d, J = 9.0 Hz, 1H), 7.71 (d, J = 1.5Hz, 1H), 7.53 (d, J = 9.0 Hz, 1H), 7.33 (dd, J = 9.0 Hz, J = 1.5 Hz, 1H),7.18-7.10 (m, 5H), 6.93 (d, J = 9.5 Hz, 1H), 6.90 (s, 1H), 6.59 (d, J = 8.0Hz, 1H), 6.22 (d, J = 8.0 Hz, 1H), 5.89 (s, 1H), 4.39 (d, J = 4.5 Hz, 2H), 2.39 (s, 3H), 2.13 (s, 3H); 13 C NMR (126 MHz, CDCl 3 ) δ .76, 128.70,127.37, 127.26, 126.87, 126.29, 124.61, 115.56, 114.65, 104.48, 47.61, 20.76, 20.00.

[0069] The structure of the target product is inferred from the above data as follows:

[0070] . Example 7

[0071] N-benzyl-3,4,5-trimethylaniline (0.2 mmol), 2,2',4,4'-tetramethyldiphenyl disulfide (0.11 mmol), sodium iodide (0.02 mmol), acetonitrile (2.0 mL) and a magnetic stirrer were added to the reaction tube in sequence. The mixture was reacted for 13 hours under 6W blue light irradiation at 60 °C in an air atmosphere. The mixture was cooled to room temperature, and the reaction solution was added to ethyl acetate. The mixture was washed and extracted twice with a saturated NaCl solution. The upper organic phase solution was taken, dried over anhydrous magnesium sulfate, filtered, concentrated under reduced pressure, and then separated and purified by column chromatography to obtain the target product with a yield of 78%.

[0072] The hydrogen spectrum and carbon spectrum of the obtained target product are as follows: Fig.13 and Fig.14 The NMR data are shown below:

[0073] 1 H NMR (500 MHz, CDCl 3 ) δ 7.26-7.23 (m, 2H), 7.21-7.18 (m, 3H), 6.96(s, 1H), 6.78 (d, J = 7.5 Hz, 1H), 6.45 (d, J = 8.0 Hz, 1H), 6.38 (s, 1H), 5.45 (s, 1H), 4.32 (s, 2H), 2.40 (s, 3H), 2.37 (s, 3H), 2.24 (s, 3H), 2.23(s, 3H), 2.12 (s, 3H); 13 C NMR (126 MHz, CDCl 3 ) δ 8.80, 142.45, 139.71,139.26, 134.73, 134.18, 132.70, 131.00, 128.49, 127.25, 127.03, 126.89,124.26, 124.21, 111.34, 110.46, 47.94, 21.63, 20.79, 19.91, 18.60, 15.87.

[0074] The structure of the target product is inferred from the above data as follows:

[0075] . Example 8

[0076] N-benzyl-3,4-dimethoxyaniline (0.2 mmol), 2,2',4,4'-tetramethyldiphenyl disulfide (0.11 mmol), sodium iodide (0.02 mmol), acetonitrile (2.0 mL) and a magnetic stirrer were added to the reaction tube in sequence. The mixture was reacted for 14 hours under 6W blue light irradiation at 60 °C in an air atmosphere. The mixture was cooled to room temperature, and the reaction solution was added to ethyl acetate. The mixture was washed and extracted twice with a saturated NaCl solution. The upper organic phase solution was taken, dried over anhydrous magnesium sulfate, filtered, concentrated under reduced pressure, and then separated and purified by column chromatography to obtain the target product with a yield of 67%.

[0077] The hydrogen spectrum and carbon spectrum of the obtained target product are as follows: Fig.15 and Fig.16 The NMR data are shown below:

[0078] 1 H NMR (500 MHz, CDCl 3 ) δ 7.28-7.24 (m, 2H), 7.23-7.20 (m, 3H), 7.00(s, 1H), 6.97 (s, 1H), 6.84 (d, J = 8.0 Hz, 1H), 6.59 (d, J = 8.0 Hz, 1H), 6.24 (s, 1H), 5.12 (s, 1H), 4.34 (s, 2H), 3.77 (s, 3H), 3.76 (s, 3H), 2.37(s, 3H), 2.26 (s, 3H); 13 C NMR (126 MHz, CDCl 3 ) δ 8, 125.26, 121.18, 103.22, 96.55, 56.78, 55.72, 48.47, 20.74, 19.83.

[0079] The structure of the target product is inferred from the above data as follows:

[0080] . Example 9

[0081] N-benzyl-3,4,5-trimethoxyaniline (0.2 mmol), 2,2',4,4'-tetramethyldiphenyl disulfide (0.11 mmol), sodium iodide (0.02 mmol), acetonitrile (2.0 mL) and a magnetic stirrer were added to the reaction tube in sequence. The mixture was reacted for 12 hours under 6W blue light irradiation at 60 °C in an air atmosphere. The mixture was cooled to room temperature, and the reaction solution was added to ethyl acetate. The mixture was washed and extracted twice with a saturated NaCl solution. The upper organic phase solution was taken, dried over anhydrous magnesium sulfate, filtered, concentrated under reduced pressure, and then separated and purified by column chromatography to obtain the target product with a yield of 80%.

[0082] The hydrogen spectrum and carbon spectrum of the obtained target product are as follows: Fig.17 and Fig.18 The NMR data are shown below:

[0083] 1 H NMR (500 MHz, CDCl 3 ) δ 7.28-7.19 (m, 5H), 6.95(s, 1H), 6.82 (d, J =8.0 Hz, 1H), 6.58 (d, J = 8.0 Hz, 1H), 5.98 (s, 1H), 5.46 (s, 1H), 4.32 (s,2H), 3.78 (s, 6H), 3.74 (s, 3H), 2.41 (s, 3H), 2.25 (s, 3H); 13 C NMR (126 MHz, CDCl 3 ) δ 08, 126.99, 124.72, 98.96, 91.12, 61.43, 61.15,55.64, 48.12, 20.69, 19.82.

[0084] The structure of the target product is inferred from the above data as follows:

[0085] . Example 10

[0086] In a reaction tube, N-benzyl-2-naphthylamine (0.2 mmol), diphenyl disulfide (0.11 mmol), sodium iodide (0.02 mmol), acetonitrile (2.0 mL) and a magnetic stir bar were added successively. The reaction was carried out under 6W blue light irradiation at 60 °C in an air atmosphere for 20 hours. After cooling to room temperature, the reaction solution was added to ethyl acetate and 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 separated and purified by column chromatography to obtain the target product with a yield of 55%.

[0087] The hydrogen NMR spectrum and carbon NMR spectrum of the obtained target product are shown in Fig.19 and Fig. 20 respectively, and the NMR data are as follows:

[0088] 1 H NMR (500 MHz, CDCl 3 ) δ 8.27 (d, J = 8.5 Hz, 1H), 7.75 (d, J = 9.0Hz, 1H), 7.68 (d, J = 8.0 Hz, 1H), 7.41 (t, J = 8.0 Hz, 1H), 7.26 - 7.19 (m,6H), 7.15 (t, J = 8.0 Hz, 2H), 7.08 - 7.01 (m, 4H), 6.04 (s, 1H), 4.50 (s, 2H); 13 C NMR (126 MHz, CDCl 3 ) δ 148.96, 139.16, 136.88, 136.86, 132.08, 129.02,128.67, 128.43, 127.82, 127.65, 127.20, 126.92, 125.99, 125.14, 124.20,122.21, 113.74, 104.29, 47.64。

[0089] Based on the above data, the structure of the target product is speculated as follows:

[0090] 。 Example 11

[0091] N-benzyl-2-naphthylamine (0.2 mmol), 4,4'-dichlorodiphenyl disulfide (0.11 mmol), sodium iodide (0.02 mmol), acetonitrile (2.0 mL) and a magnetic stirrer were added to the reaction tube in sequence. The mixture was reacted for 13 hours under 6W blue light irradiation at 60 °C in an air atmosphere. The mixture was cooled to room temperature, and the reaction solution was added to ethyl acetate. The mixture was washed and extracted twice with a saturated NaCl solution. The upper organic phase solution was taken, dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The target product was separated and purified by column chromatography with a yield of 89%.

[0092] The hydrogen spectrum and carbon spectrum of the obtained target product are as follows: Fig.21 and Fig. 22 The NMR data are shown below:

[0093] 1 H NMR (500 MHz, CDCl 3 ) δ 8.21 (d, J = 8.5 Hz, 1H), 7.77 (d, J = 9.0Hz, 1H), 7.69 (d, J = 8.0 Hz, 1H), 7.42 (t, J = 7.5 Hz, 1H), 7.29-7.20 (m,6H), 7.11 (d, J = 8.5 Hz, 2H), 7.05 (d, J = 9.0 Hz, 1H), 6.92 (d, J = 8.5 Hz,2H), 6.00 (s, 1H), 4.52 (s, 2H); 13 C NMR (126 MHz, CDCl 3 ) δ 33, 113.75, 103.80, 47.65, 128.71, 128.49, 127.96, 127.65, 127.29, 127.22, 126.92, 123.91, 122.33, 113.75, 103.80, 47.65.

[0094] The structure of the target product is inferred from the above data as follows:

[0095] . Example 12

[0096] N-benzyl-2-naphthylamine (0.2 mmol), 4,4'-dihydroxydiphenyl disulfide (0.11 mmol), sodium iodide (0.02 mmol), acetonitrile (2.0 mL) and a magnetic stirrer were added to the reaction tube in sequence. The mixture was reacted for 13 hours under 6W blue light irradiation at 60 °C in an air atmosphere. The mixture was cooled to room temperature, and the reaction solution was added to ethyl acetate. The mixture was washed and extracted twice with a saturated NaCl solution. The upper organic phase solution was taken, dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The target product was separated and purified by column chromatography with a yield of 81%.

[0097] The hydrogen spectrum and carbon spectrum of the obtained target product are as follows: Fig.23 and Fig.24 The NMR data are shown below:

[0098] 1 H NMR (500 MHz, CDCl 3 ) δ 8.31 (d, J = 8.5 Hz, 1H), 7.71 (d, J = 9.0Hz, 1H), 7.65 (d, J =8.0 Hz, 1H), 7.41 (t, J = 7.5 Hz, 1H), 7.26-7.18 (m,7H), 7.01 (d, J = 9.0 Hz, 1H), 6.91 (d, J = 8.5 Hz, 2H), 6.59 (d, J = 8.5 Hz,2H), 6.04 (s, 1H), 4.48 (s, 2H); 13 C NMR (126 MHz, CDCl 3 ) δ 8, 116.27, 116.08, 106.04, 47.77.

[0099] The structure of the target product is inferred from the above data as follows:

[0100] . Example 13

[0101] N-benzyl-2-naphthylamine (0.2 mmol), 4,4'-diaminodiphenyl disulfide (0.11 mmol), sodium iodide (0.02 mmol), acetonitrile (2.0 mL) and a magnetic stirrer were added to the reaction tube in sequence. The mixture was reacted for 16 hours under 6W blue light irradiation at 60 °C in an air atmosphere. The mixture was cooled to room temperature, and the reaction solution was added to ethyl acetate. The mixture was washed and extracted twice with a saturated NaCl solution. The upper organic phase solution was taken, dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The target product was separated and purified by column chromatography with a yield of 72%.

[0102] The hydrogen spectrum and carbon spectrum of the obtained target product are as follows: Fig.25 and Fig.26 The NMR data are shown below:

[0103] 1 H NMR (500 MHz, CDCl 3 ) δ 8.36 (d, J = 8.5 Hz, 1H), 7.69 (d, J = 9.0Hz, 1H), 7.64 (d, J = 8.0 Hz, 1H), 7.40 (t, J = 7.5 Hz, 1H), 7.25-7.18 (m,6H), 6.99 (d, J = 9.0 Hz, 1H), 6.90-6.88 (m, 2H), 6.45 (d, J = 8.5 Hz, 2H), 6.08 (s, 1H), 4.47 (s, 2H), 3.46 (s, 2H); 13 C NMR (126 MHz, CDCl 3 ) δ 8.89, 124.59, 124.32, 121.92, 115.92, 113.62, 106.57, 47.63.

[0104] The structure of the target product is inferred from the above data as follows:

[0105] . Embodiment 14

[0106] N-benzyl-2-naphthylamine (0.2 mmol), 4,4'-bipyridyl disulfide (0.11 mmol), sodium iodide (0.02 mmol), acetonitrile (2.0 mL) and a magnetic stirrer were added to the reaction tube in sequence. The mixture was reacted for 29 hours under 6W blue light irradiation at 60 °C in an air atmosphere. The mixture was cooled to room temperature, and the reaction solution was added to ethyl acetate. The mixture was washed and extracted twice with a saturated NaCl solution. The upper organic phase solution was taken, dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The target product was separated and purified by column chromatography with a yield of 62%.

[0107] The hydrogen spectrum and carbon spectrum of the obtained target product are as follows: Fig. 27 and Fig.28 The NMR data are shown below:

[0108] 1 H NMR (500 MHz, CDCl 3 ) δ 8.27 (d, J = 5.5 Hz, 2H), 8.11 (d, J = 8.5Hz, 1H), 7.81 (d, J = 9.0 Hz, 1H), 7.70 (d, J = 8.0 Hz, 1H), 7.42 (t, J =7.5Hz, 1H), 7.29-7.20 (m, 6H), 7.07 (d, J = 9.0 Hz, 1H), 6.87 (d, J = 6.0 Hz,2H), 5.85 (s, 1H), 4.51 (d, J = 5.0 Hz, 2H); 13 C NMR (126 MHz, CDCl 3 ) δ 8, 123.46, 122.46, 120.40, 113.68, 100.87, 47.61.

[0109] The structure of the target product is inferred from the above data as follows:

[0110] . Embodiment 15

[0111] N-benzyl-2-naphthylamine (0.2 mmol), 2,2'-dibenzothiazole disulfide (0.11 mmol), sodium iodide (0.02 mmol), acetonitrile (2.0 mL) and a magnetic stirrer were added to the reaction tube in sequence. The mixture was reacted for 11 hours under 6W blue light irradiation at 60 °C in an air atmosphere. The mixture was cooled to room temperature, and the reaction solution was added to ethyl acetate. The mixture was washed and extracted twice with a saturated NaCl solution. The upper organic phase solution was taken, dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The target product was separated and purified by column chromatography with a yield of 64%.

[0112] The hydrogen spectrum and carbon spectrum of the obtained target product are as follows: Fig.29 and Fig.30 The NMR data are shown below:

[0113] 1 H NMR (500 MHz, CDCl 3 ) δ 8.28 (d, J = 8.5 Hz, 1H), 7.86 (d, J = 8.5Hz, 1H), 7.81 (d, J = 9.0 Hz, 1H), 7.69 (d, J = 8.0 Hz, 1H), 7.49 (d, J = 8.0Hz, 1H), 7.44 (t, J = 7.5 Hz, 1H), 7.35 (t, J = 7.5 Hz, 1H), 7.25-7.16 (m,7H), 7.04 (d, J = 9.0 Hz, 1H), 6.05 (s, 1H), 4.51 (d, J = 6.0 Hz, 2H); 13 C NMR (126 MHz, CDCl 3 ) δ 47.54, 121.54, 120.77, 113.75, 102.38, 47.56.

[0114] The structure of the target product is inferred from the above data as follows:

[0115] .

Claims

1. A method for photoinduced catalytic synthesis of diaryl sulfide amine compounds, It is characterized in that The following steps are involved: ； An aromatic amine compound represented by Formula I, an aromatic persulfide represented by Formula II, a catalyst and a solvent are added to a reaction tube, and the reaction tube is irradiated with visible light at 25-80° C. under an oxygen or air atmosphere with oxygen as an oxidant to react. After the reaction is completed, a diaryl sulfide amine compound represented by Formula III is obtained through separation and purification; Wherein, in the formula III, Ar is 3,4,5-trimethylphenyl or 3,4,5-trimethoxyphenyl; R 1 is benzyl; R 2 is 2,4-dimethylphenyl; The compound of formula I is N-benzyl-3,4,5-trimethylaniline or N-benzyl-3,4,5-trimethoxyaniline; The compound of formula II is 2,2',4,4'-tetramethyl diphenyl disulfide; The catalyst is sodium iodide; the oxidant is oxygen; the solvent is acetonitrile; the visible light is blue light; the molar ratio of the catalyst to the compound represented by formula I is 0.05-0.30:1; and the visible light power is 2-10W.

2. The synthesis method according to claim 1, It is characterized in that The separation and purification operation is as follows: adding the reaction solution into ethyl acetate, washing and extracting twice with a saturated NaCl solution, taking the upper organic phase solution, drying it with anhydrous magnesium sulfate, filtering it, concentrating it under reduced pressure, and then separating and purifying it by column chromatography to obtain the diaryl sulfide amine compound.

3. The synthesis method according to claim 1, It is characterized in that The molar ratio of the compound represented by formula I to the compound represented by formula II is 1:0.5-3.

4. The synthesis method according to claim 1, It is characterized in that The reaction time is 13 to 39 hours.

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