A dithiophosphoryl-substituted azine compound and a method for synthesizing the same

Abstract

This invention discloses a dithiophosphoryl-substituted azine compound and its synthetic method, belonging to the field of organic synthesis technology. The synthetic method uses azine compounds, phosphorus pentasulfide, and alcohols as substrates. In a membrane-free electrolytic cell, using tetrabutylammonium bisulfate as the electrolyte and acetonitrile as the solvent, a three-component dehydrogenation coupling reaction is achieved by constant current electrolysis at room temperature. No metal catalyst or external chemical oxidant is required. Inexpensive phosphorus pentasulfide serves as both the sulfur and phosphorus source. By controlling the electrolysis time, mono- or bis-dithiophosphoryl-substituted azine compounds can be selectively prepared with moderate to excellent product yields. Mechanistic studies show that the reaction proceeds via a free radical-mediated pathway. This method is mild, simple to operate, and has a wide range of applicable substrates, meeting the requirements of green chemistry and providing a new route for the efficient synthesis of functionalized phenoxazine derivatives.

Description

Technical Field

[0001] This invention belongs to the field of organic synthesis technology, specifically relating to a dithiophosphoryl-substituted azircon compound and its synthesis method. Background Technology

[0002] Organic dithiophosphorus compounds are an important class of sulfur- and phosphorus-containing heterocyclic functional compounds with wide applications in organic synthesis, medicinal chemistry, agrochemicals and functional materials. Their molecular skeletons often exhibit a variety of biological activities such as antibacterial, anticancer, antiviral and enzyme inhibition, and they are also important structural units of optoelectronic functional materials.

[0003] Phenothiazines and phenoxazines, as typical nitrogen-sulfur and nitrogen-oxygen heterocyclic anthracene derivatives, possess rigid large π-conjugated skeletons, excellent hole transport properties, and unique non-planar butterfly conformations, effectively suppressing intermolecular π-π stacking. They are widely used in optoelectronic fields such as dye-sensitized solar cells, organic light-emitting diodes, and organic semiconductor polymers. Currently, functionalization modifications of phenothiazines and phenoxazines mostly focus on the direct conversion of NH bonds. Efficient synthetic methods for selectively constructing CS bonds from CH bonds still have many limitations. Existing technologies often rely on metal catalysts and stoichiometric oxidants, resulting in harsh reaction conditions, poor atom economy, and high environmental impact, which does not meet the requirements of green chemistry synthesis. Summary of the Invention

[0004] To address the numerous shortcomings of existing technologies, namely their reliance on metal catalysts and stoichiometric oxidants, harsh reaction conditions, poor atom economy, and severe environmental pollution, as well as the difficulty in controlling product selectivity and the challenges of large-scale synthesis, this invention aims to provide a metal-free and oxidant-free electrochemical synthesis method. This method enables the efficient and controllable preparation of mono- and di-substituted dithiophosphoryl-substituted azine compounds, meeting the requirements of green chemical synthesis and overcoming the shortcomings of existing technologies.

[0005] This invention discloses a method for synthesizing dithiophosphoryl-substituted azine compounds:

[0006] A azine compound, phosphorus pentasulfide, and alcohol compound were uniformly mixed in an electrolyte, and then a direct current was passed through the electrolyte until the reaction was completed. The dithiophosphoryl-substituted azine compound was then obtained by separation.

[0007] The azine compounds are phenoxazine compounds or phenothiazine compounds;

[0008] The electrolyte is an acetonitrile solution containing tetrabutylammonium hydrogen sulfate;

[0009] The molar ratio of the azine compound, phosphorus pentasulfide, and alcohol compound is 0.4:0.4:10.0.

[0010] Wherein, the phenoxazine compound is a phenoxazine;

[0011] The phenothiazine compound is one of phenothiazine, halophenothiazine, or alkyl-substituted phenothiazine;

[0012] The alcohol compound is one of C1-C6 aliphatic straight-chain alcohols, cyclopropanol, cyclobutanol, cyclopentanol, phenethyl alcohol, and p-methoxyphenol.

[0013] The DC current intensity is 6 mA - 12 mA.

[0014] The concentration of tetrabutylammonium hydrogen sulfate in the electrolyte is 50 mmol / L.

[0015] The DC power supply time is 75 min to 25 h.

[0016] The present invention also provides a dithiophosphoryl-substituted azircon compound, which is prepared by the above method, wherein the dithiophosphoryl-substituted azircon compound is at least one of a dithiophosphoryl monosubstituted azircon compound or a dithiophosphoryl disubstituted azircon compound.

[0017] The synthesis method of this invention requires no inert gas protection or high / low temperature control during the reaction process, and is simple and easy to operate. After the reaction, the target product is obtained by solvent removal under reduced pressure and purification by column chromatography. The product yield is in the range of 23%-94%, showing potential for large-scale preparation. Mechanistic studies confirm that the reaction proceeds via a free radical-mediated pathway, where phosphorus pentasulfide reacts with an alcohol in situ to form a dithiophosphate intermediate, which is then anolyzed to form a sulfur free radical, which then selectively couples with the substrate to obtain the target product.

[0018] This invention eliminates the need for metal catalysts and external chemical oxidants, using electrons as a clean oxidizing agent. The only byproduct is hydrogen, making it green, environmentally friendly, and highly atom-economical, perfectly aligning with the concept of sustainable chemical development. The reaction conditions are mild, allowing for efficient operation at room temperature. The equipment is versatile and easy to operate, significantly reducing the synthesis threshold and energy consumption. The substrates are widely applicable, suitable for various fatty alcohols, cyclic alcohols, aromatic alcohols, and substituted phenothiazine derivatives, demonstrating strong substrate compatibility. The product substitution mode can be precisely controlled by the electrolysis time, and both single and double substituted products can be obtained efficiently with excellent selectivity. The raw materials are inexpensive and readily available, and the dual-source utilization of phosphorus pentasulfide further reduces costs. It has both laboratory preparation and industrial application value, providing a new technical route for the green and efficient synthesis of functionalized nitrogen-oxygen / nitrogen-sulfur heterocyclic compounds.

[0019] These dithiophosphoryl-substituted azine compounds have potential applications in organic synthesis, medicinal chemistry, agrochemicals, and functional materials. Attached Figure Description

[0020] Figure 1 This is a mechanism diagram of the synthesis method of Embodiment 1 of the present invention. Detailed Implementation

[0021] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0022] Example 1

[0023] Phenyrazine 1a (0.4 mmol), ethanol 2a (EtOH, 10.0 mmol), and phosphorus pentasulfide (P4S) were added. 10 A mixture of 0.4 mmol of tetrabutylammonium bisulfate (n-Bu4NHSO4) and 8.0 mL of acetonitrile was added to a diaphragm-free electrolytic cell, where the tetrabutylammonium bisulfate served as the electrolyte and the acetonitrile as the solvent. The electrolytic cell was equipped with two 1.0 × 1.0 cm² platinum electrodes. The reaction mixture was stirred thoroughly and electrolyzed at a constant current of 6 mA for 90 minutes at room temperature. The reaction equation is shown below:

[0024]

[0025] After the reaction was complete, the reaction solvent was removed under reduced pressure using a rotary evaporator. 10 mL of water was added to the remaining system, and the mixture was extracted three times with 10 mL of ethyl acetate each time. The combined organic phases were dried over anhydrous sodium sulfate and then concentrated under reduced pressure to remove the extraction solvent. The concentrated residue was purified by column chromatography to obtain dithiophosphoryl-substituted azine compound 3a, with a separation yield of 82%.

[0026] The structural characterization data of the prepared dithiophosphoryl-substituted azine compounds are as follows:

[0027]

[0028] 1H NMR (400 MHz, DMSO-d6) δ 8.57 (s, 1H), 6.88 – 6.85 (m, 1H), 6.76 –6.72 (m, 1H), 6.69 (t, J = 2.0 Hz, 1H), 6.63 – 6.57 (m, 2H), 6.47 – 6.43 (m,2H), 4.18 – 4.08 (m, 4H), 1.24 (t, J = 7.2 Hz, 6H). 13 C NMR (100 MHz, DMSO-d6)δ 143.37, 143.35, 142.9, 134.75, 134.72, 131.97, 131.92, 131.7, 124.7,121.53, 121.50, 116.5, 116.4, 115.6, 114.1, 114.0, 64.35, 64.30, 16.09,16.01. 31 P NMR (162 MHz, DMSO-d6) δ 87.4. HRMS (ESI) m / z calcd for C 16 H 18 NO3PS2[M+Na] + 390.0358, found 390.0351.

[0029] The mechanism of the synthesis method is as follows: Figure 1 First, phosphorus pentasulfide reacts with ethanol (2a) to generate O,O-diethyldithiophosphoric acid (intermediate I) in situ. Subsequently, intermediate I undergoes an anodic oxidation reaction to generate the corresponding sulfur radical (intermediate II), which can further undergo a dimerization reaction to obtain a disulfide intermediate (intermediate III). The sulfur radical then reacts with phenoxazine to generate the target monosubstituted product 3a.

[0030] Example 2

[0031] The difference from Example 1 is that the reaction substrate was methanol, the reaction was electrolyzed for 105 min, purified by silica gel column chromatography, and the eluent was petroleum ether / ethyl acetate (volume ratio 3:1) to obtain a green oily substance; the yield was 89.5 mg, the yield was 66%, and the product was O,O-dimethyl-S-(10H-phenoxazine-3-yl)dithiophosphate (3b).

[0032] The structural characterization data of the O,O-dimethyl-S-(10H-phenoxazine-3-yl)dithiophosphate compound prepared in Example 2 are as follows:

[0033]

[0034] 1 H NMR (400 MHz, DMSO-d6) δ 8.58 (s, 1H), 6.90 – 6.87 (m, 1H), 6.76 –6.72 (m, 1H), 6.70 (t, J = 2.0 Hz, 1H), 6.63 – 6.58 (m, 2H), 6.47 – 6.43 (m,2H), 3.75 (d, J = 15.6 Hz, 6H). 13 C NMR (100 MHz, DMSO-d6) δ 143.42, 143.40,142.9, 134.86, 134.83, 131.9, 131.8, 131.7, 124.7, 121.5, 121.35, 121.31,116.29, 116.21, 115.6, 114.2, 114.1, 114.0, 54.56, 54.51. 31 P NMR (162 MHz, DMSO-d6) δ 92.6. HRMS (ESI) m / z calcd for C 14 H 14 NO3PS2 [M+Na] + 362.0045, found362.0047.

[0035] Example 3

[0036] The difference from Example 1 is that the reaction substrate was n-propanol, electrolyzed for 75 min, purified by silica gel column chromatography, and the eluent was petroleum ether / ethyl acetate (volume ratio 6:1), yielding a yellow-green solid; the yield was 75.85 mg, with a yield of 48%, and the product was S-(10H-phenoxazine-3-yl)-O,O-dipropyl dithiophosphate (3c).

[0037] The structural characterization data of the S-(10H-phenoxazine-3-yl)-O,O-dipropyl dithiophosphate compound prepared in Example 3 are as follows:

[0038]

[0039] 1H NMR (400 MHz, DMSO-d6) δ 8.54 (s, 1H), 6.89 - 6.85 (m, 1H), 6.75 –6.71 (m, 1H), 6.69 (t, J = 2.0 Hz, 1H), 6.61 – 6.56 (m, 2H), 6.45 (t, J = 7.6Hz, 2H), 4.08 - 3.97 (m, 4H), 1.66 - 1.57 (m, 4H), 0.87 (t, J = 7.2 Hz, 6H). 13 C NMR (100 MHz, DMSO-d6) δ 143.37, 143.34, 142.9, 134.7, 134.6, 131.89,131.85, 131.7, 124.7, 121.55, 121.51, 121.4, 116.5, 116.4, 115.6, 114.05,114.01, 69.6, 69.5, 23.3, 23.2, 10.4. 31 P NMR (162 MHz, DMSO-d6) δ 87.7. HRMS(ESI) m / z calcd for C 18 H 22 NO3PS2 [M+Na] + 418.0671, found 418.0673.

[0040] Example 4

[0041] The difference from Example 1 is that the reaction substrate was n-butanol, electrolyzed for 95 min, purified by silica gel column chromatography, and the eluent was petroleum ether / ethyl acetate (volume ratio 12:1) to obtain a yellow oily substance; the yield was 86.4 mg, with a yield of 50%, and the product obtained was O,O-dibutyl-S-(10H-phenoxazine-3-yl)dithiophosphate (3d).

[0042] The structural characterization data of the O,O-dibutyl-S-(10H-phenoxazine-3-yl)dithiophosphate compound prepared in Example 4 are as follows:

[0043]

[0044] 1H NMR (400 MHz, DMSO-d6) δ 8.55 (s, 1H), 6.88 – 6.85 (m, 1H), 6.76 –6.72 (m, 1H), 6.69 (t, J = 2.0 Hz, 1H), 6.61 – 6.58 (m, 2H), 6.45 (t, J = 8.0Hz, 2H), 4.12 - 4.01 (m, 4H), 1.61 - 1.54 (m, 4H), 1.35 - 1.26 (m, 4H), 0.86(t, J = 7.2 Hz, 6H). 13 C NMR (100 MHz, DMSO-d6) δ 143.36, 143.34, 142.9,134.75, 134.72, 131.8, 131.7, 124.7, 121.58, 121.54, 121.50, 116.5, 116.4,115.6, 114.06, 114.02, 113.9, 67.8, 67.7, 31.8, 31.7, 18.7, 13.9. 31 P NMR (162MHz, DMSO-d6) δ 92.4. HRMS (ESI) m / z calcd for C 20 H 26 NO3PS2 [M+Na] + 446.0984, found 446.0983.

[0045] Example 5

[0046] The difference from Example 1 is that the reaction substrate was n-pentanol, the reaction was electrolyzed for 80 min, purified by silica gel column chromatography, and the eluent was petroleum ether / ethyl acetate (volume ratio 12:1) to obtain a yellow oily substance; the yield was 108.3 mg, the yield was 60%, and the product was O,O-dipentyl-S-(10H-phenoxazine-3-yl)dithiophosphate (3e).

[0047] The structural characterization data of the O,O-dipentyl-S-(10H-phenoxazine-3-yl)dithiophosphate compound prepared in Example 5 are as follows:

[0048]

[0049] 1H NMR (400 MHz, DMSO-d6) δ 8.54 (s, 1H), 6.87 – 6.83 (m, 1H), 6.75 –6.70 (m, 1H), 6.68 (s, 1H), 6.60 – 6.57 (m, 2H), 6.44 (t, J = 8.4 Hz, 2H), 4.11 – 3.99 (m, 4H), 1.62 – 1.55 (m, 4H), 1.28 – 1.20 (m, 8H), 0.84 (t, J =6.8 Hz, 6H). 13 C NMR (100 MHz, DMSO-d6) δ 143.37, 143.35, 142.9, 134.73,134.70, 131.78, 131.73, 131.6, 124.6, 121.48, 121.43, 116.5, 116.4, 115.5,114.0, 113.96, 113.94, 68.1, 68.0, 29.58, 29.50, 27.7, 22.2, 14.3. 31 P NMR (162 MHz, DMSO-d6) δ 87.4. HRMS (ESI) m / z calcd for C 22 H 30 NO3PS2 [M+H] + 452.1477, found 452.1479.

[0050] Example 6

[0051] The difference from Example 1 is that the reaction substrate was n-hexanol, electrolyzed for 100 min, purified by silica gel column chromatography, and the eluent was petroleum ether / ethyl acetate (volume ratio 12:1) to obtain a yellow oily substance; the yield was 120.8 mg, the yield was 63%, and the product was O,O-dihexyl-S-(10H-phenoxazine-3-yl)dithiophosphate (3f).

[0052] The structural characterization data of the O,O-dihexyl-S-(10H-phenoxazine-3-yl)dithiophosphate compound prepared in Example 6 are as follows:

[0053]

[0054] 1H NMR (400 MHz, DMSO-d6) δ 8.54 (s, 1H), 6.86 – 6.83 (m, 1H), 6.74 – 6.70 (m, 1H), 6.67 (s, 1H), 6.59 – 6.54 (m, 2H), 6.45 – 6.40 (m, 2H), 4.10 –3.98 (m, 4H), 1.60 – 1.54 (m, 4H), 1.29 – 1.14 (m, 12H), 0.81 (t, J = 7.2 Hz, 6H). 13 C NMR (100 MHz, DMSO-d6) δ 143.38, 143.35, 142.9, 134.7, 134.6, 131.7,131.66, 131.61, 124.6, 121.4, 121.3, 116.5, 116.4, 115.5, 113.99, 113.92,113.8, 68.1, 68.0, 31.3, 29.8, 29.7, 25.3, 22.5, 14.3. 31 P NMR (162 MHz, DMSO-d6) δ 87.3. HRMS (ESI) m / z calcd for C 24 H 34 NO3PS2 [M+H] + 480.1790, found480.1790.

[0055] Example 7

[0056] The difference from Example 1 is that the reaction substrate was isopropanol, electrolyzed for 100 min, purified by silica gel column chromatography, and the eluent was petroleum ether / ethyl acetate (volume ratio 6:1), yielding a yellow oily substance; the yield was 77.4 mg, with a yield of 49%, and the product was O,O-diisopropyl-S-(10H-phenoxazine-3-yl)dithiophosphate (3 g).

[0057] The structural characterization data of the O,O-diisopropyl-S-(10H-phenoxazine-3-yl)dithiophosphate compound prepared in Example 7 are as follows:

[0058]

[0059] 1H NMR (400 MHz, DMSO-d6) δ 8.54 (s, 1H), 6.89 – 6.86 (m, 1H), 6.76 –6.72 (m, 1H), 6.69 (t, J = 2.0 Hz, 1H), 6.63 – 6.56 (m, 2H), 6.46 – 6.43 (m,2H), 4.77 – 4.67 (m, 2H), 1.25 (t, J = 5.6 Hz, 12H). 13 C NMR (100 MHz, DMSO-d6) δ 143.26, 143.23, 142.9, 134.5, 134.4, 131.8, 131.69, 131.64, 124.7,121.4, 121.38, 121.34, 117.1, 117.0, 115.6, 114.05, 114.00, 113.9, 74.2,74.1, 23.89, 23.84, 23.6, 23.5. 31 P NMR (162 MHz, DMSO-d6) δ 85.1. HRMS (ESI)m / z calcd for C 18 H 22 NO3PS2 [M+Na] + 418.0671, found 418.0665.

[0060] Example 8

[0061] The difference from Example 1 is that the reaction substrate was isobutanol, electrolyzed for 90 min, purified by silica gel column chromatography, with petroleum ether / dichloromethane (volume ratio 3:2) as the eluent, yielding 84.6 mg, a yield of 50%, and a colorless oily substance; the product obtained was O,O-diisobutyl-S-(10H-phenoxazine-3-yl)dithiophosphate (3 h).

[0062] The structural characterization data of the O,O-diisobutyl-S-(10H-phenoxazine-3-yl)dithiophosphate compound prepared in Example 8 are as follows:

[0063]

[0064] 1H NMR (400 MHz, DMSO-d6) δ 8.54 (s, 1H), 6.89 – 6.87 (m, 1H), 6.75 –6.71 (m, 2H), 6.60 – 6.58 (m, 2H), 6.44 (t, J = 8.0 Hz, 2H), 3.89 – 3.80 (m,4H), 1.93 – 1.83 (m, 2H), 0.86 (d, J = 6.8, 12H). 13 C NMR (100 MHz, DMSO-d6) δ143.36, 143.33, 142.9, 134.7, 134.6, 131.97, 131.92, 131.8, 124.7, 121.69,121.65, 121.5, 116.4, 116.3, 115.6, 114.0, 113.99, 113.97, 73.78, 73.71,28.8, 28.7, 19.03, 19.00. 31 P NMR (162 MHz, DMSO-d6) δ 87.5. HRMS (ESI) m / zcalcd for C 20 H 26 NO3PS2 [M+H] + 424.1164, found 424.1161.

[0065] Example 9

[0066] The difference from Example 1 is that the reaction substrate was isoamyl alcohol, the reaction was electrolyzed for 100 min, purified by silica gel column chromatography, and the eluent was petroleum ether / dichloromethane (volume ratio 1:1) to obtain a colorless oily substance; the yield was 83.0 mg, the yield was 46%, and the product was O,O-diisopentyl-S-(10H-phenoxazine-3-yl)dithiophosphate (3i).

[0067] The structural characterization data of the O,O-diisopentyl-S-(10H-phenoxazine-3-yl)dithiophosphate compound prepared in Example 9 are as follows:

[0068]

[0069] 1H NMR (400 MHz, DMSO-d6) δ 8.53 (s, 1H), 6.88 – 6.85 (m, 1H), 6.76 –6.72 (m, 1H), 6.69 (t, J = 2.0 Hz, 1H), 6.59 (d, J = 4.4 Hz, 2H), 6.45 (t, J= 8.0 Hz, 2H), 4.15 – 4.03 (m, 4H), 1.68 – 1.58 (m, 2H), 1.55 – 1.42 (m, 4H), 0.87 – 0.85 (m, 12H). 13 C NMR (100 MHz, DMSO-d6) δ 143.4, 143.0, 134.8, 131.8,124.7, 121.5, 116.5, 115.6, 114.0, 66.6, 38.5, 24.5, 22.7, 22.5. 31 P NMR (162MHz, DMSO-d6) δ 87.8. HRMS (ESI) m / z calcd for C 22 H 30 NO3PS2 [M+H] + 452.1477, found 452.1477.

[0070] Example 10

[0071] The difference from Example 1 is that the reaction substrate was cyclopropanol, electrolyzed for 100 min, purified by silica gel column chromatography, and the eluent was petroleum ether / dichloromethane (volume ratio 2:3), yielding a yellow oily substance; the yield was 46.9 mg, with a yield of 30%, and the product was O,O-dicyclopropyl-S-(10H-phenoxazine-3-yl)dithiophosphate (3j).

[0072] The structural characterization data of the O,O-dicyclopropyl-S-(10H-phenoxazine-3-yl)dithiophosphate compound prepared in Example 10 are as follows:

[0073]

[0074] 1H NMR (400 MHz, DMSO-d6) δ 8.57 (s, 1H), 6.89 – 6.86 (m, 1H), 6.76 –6.72 (m, 1H), 6.68 (t, J = 2.0 Hz, 1H), 6.64 – 6.57 (m, 2H), 6.47 – 6.44 (m,2H), 4.12 – 4.07 (m, 2H), 0.79 – 0.66 (m, 8H). 13 C NMR (100 MHz, DMSO-d6) δ143.36, 143.33, 142.9, 134.84, 134.81, 132.0, 131.9, 131.7, 124.7, 121.56,121.53, 116.1, 116.0, 115.6, 114.15, 114.12, 114.0, 52.8, 52.7, 5.9, 5.8,5.56, 5.51. 31 P NMR (162 MHz, DMSO-d6) δ 89.8. HRMS (ESI) m / z calcd forC 18 H 18 NO3PS2 [M+Na] + 414.0358, found 414.0358.

[0075] Example 11

[0076] The difference from Example 1 is that the reaction substrate was cyclobutanol, electrolyzed for 110 min, purified by silica gel column chromatography, and the eluent was petroleum ether / dichloromethane (volume ratio 1:1) to obtain a colorless oily substance; the yield was 73.8 mg, the yield was 44%, and the product was O,O-dicyclobutyl-S-(10H-phenoxazine-3-yl)dithiophosphate (3k).

[0077] The structural characterization data of the O,O-dicyclobutyl-S-(10H-phenoxazine-3-yl)dithiophosphate compound prepared in Example 11 are as follows:

[0078]

[0079] 1H NMR (400 MHz, DMSO-d6) δ 8.54 (s, 1H), 6.86 – 6.83 (m, 1H), 6.76 –6.72 (m, 1H), 6.65 – 6.57 (m, 3H), 6.46 (t, J = 8.0 Hz, 2H), 4.89 – 4.79 (m,2H), 2.29 – 2.24 (m, 4H), 2.14 – 2.04 (m, 4H), 1.74 – 1.66 (m, 2H), 1.58 –1.46 (m, 2H). 13 C NMR (100 MHz, DMSO-d6) δ 143.35, 143.33, 143.0, 134.7, 134.6,131.9, 131.86, 131.80, 124.7, 121.59, 121.55, 121.4, 116.6, 116.5, 115.6,114.07, 114.04, 114.02, 71.5, 71.4, 32.1, 32.0, 31.66, 31.60, 12.9. 31 P NMR (162 MHz, DMSO-d6) δ 83.2. HRMS (ESI) m / z calcd for C 20 H 22 NO3PS2 [M+H] + 420.0851, found 420.0851.

[0080] Example 12

[0081] The difference from Example 1 is that the reaction substrate was cyclopentanol, electrolyzed for 120 min, purified by silica gel column chromatography, and the eluent was petroleum ether / dichloromethane (volume ratio 1:1), yielding a colorless oily substance; the yield was 87.6 mg, with a yield of 49%, and the product was O,O-dicyclopentyl-S-(10H-phenoxazine-3-yl)dithiophosphate (3l).

[0082] The structural characterization data of the O,O-dicyclopentyl-S-(10H-phenoxazine-3-yl)dithiophosphate compound prepared in Example 12 are as follows:

[0083]

[0084] 1H NMR (400 MHz, DMSO-d6) δ 8.51 (s, 1H), 6.87 – 6.83 (m, 1H), 6.76 –6.71 (m, 1H), 6.67 (t, J = 2.0 Hz, 1H), 6.62 – 6.56 (m, 2H), 6.47 – 6.43 (m,2H), 5.01 - 4.94 (m, 2H), 1.82 - 1.70 (m, 8H), 1.68 - 1.49 (m, 8H). 13 C NMR(100 MHz, DMSO-d6) δ 143.29, 143.27, 143.0, 134.56, 134.53, 131.8, 131.7,131.6, 124.7, 121.55, 121.51, 121.4, 116.99, 116.91, 115.6, 114.0, 113.93,113.90, 82.5, 82.4, 34.0, 33.9, 33.6, 33.5, 23.2, 23.1. 31 P NMR (162 MHz, DMSO-d6) δ 85.1. HRMS (ESI) m / z calcd for C 22 H 26 NO3PS2 [M+Na] + 470.0984, found470.0981.

[0085] Example 13

[0086] The difference from Example 1 is that the reaction substrate was cyclohexanol, electrolyzed for 80 min, purified by silica gel column chromatography, and the eluent was petroleum ether / dichloromethane (volume ratio 1:1), yielding a green oily substance; the yield was 43.7 mg, with a yield of 23%, and the product was O,O-dicyclohexyl-S-(10H-phenoxazine-3-yl)dithiophosphate (3m).

[0087] The structural characterization data of the O,O-dicyclohexyl-S-(10H-phenoxazine-3-yl)dithiophosphate compound prepared in Example 13 are as follows:

[0088]

[0089] 1H NMR (400 MHz, DMSO-d6) δ 8.53 (s, 1H), 6.89 – 6.86 (m, 1H), 6.76 – 6.70 (m, 2H), 6.63 – 6.56 (m, 2H), 6.46 – 6.42 (m, 2H), 4.55 – 4.46 (m, 2H),1.84 – 1.77 (m, 4H), 1.66 – 1.21 (m, 16H). 13 C NMR (100 MHz, DMSO-d6) δ143.26, 143.23, 142.9, 134.47, 134.44, 131.8, 131.5, 124.7, 121.45, 121.40,121.3, 117.1, 117.0, 115.6, 114.0, 113.9, 78.4, 78.3, 33.15, 33.11, 32.9,32.8, 25.0, 23.3, 23.2. 31 P NMR (162 MHz, DMSO-d6) δ 85.0. HRMS (ESI) m / zcalcd for C 24 H 30 NO3PS2 [M+H] + 476.1477, found 476.1479.

[0090] Example 14

[0091] The difference from Example 1 is that the reaction substrate was cycloheptanol, the reaction was electrolyzed for 80 min, purified by silica gel column chromatography, and the eluent was petroleum ether / dichloromethane (volume ratio 1:1) to obtain a green oily substance; the yield was 48.3 mg, the yield was 24%, and the product was O,O-dicycloheptanyl-S-(10H-phenoxazine-3-yl)dithiophosphate (3n).

[0092] The structural characterization data of the O,O-dicycloheptyl-S-(10H-phenoxazine-3-yl)dithiophosphate compound prepared in Example 14 are as follows:

[0093]

[0094] 1H NMR (400 MHz, DMSO-d6) δ 8.51 (s, 1H), 6.88 – 6.85 (m, 1H), 6.76 –6.72 (m, 1H), 6.70 (t, J = 2.0 Hz, 1H), 6.62 – 6.57 (m, 2H), 6.45 (t, J = 8.0Hz, 2H), 4.71 – 4.62 (m, 2H), 1.91 – 1.83 (m, 4H), 1.75 – 1.65 (m, 4H), 1.61 – 1.33 (m, 16H). 13 C NMR (100 MHz, DMSO-d6) δ 143.28, 143.26, 143.0, 134.5,134.4, 131.8, 131.6, 131.5, 124.7, 121.5, 121.4, 117.19, 117.11, 115.6,114.0, 113.92, 113.90, 81.1, 81.0, 35.36, 35.33, 35.08, 35.04, 27.9, 22.2,22.1. 31 P NMR (162 MHz, DMSO-d6) δ 85.4. HRMS (ESI) m / z calcd for C 26 H 34 NO3PS2[M+Na] + 526.1610, found 526.1606.

[0095] Example 15

[0096] The difference from Example 1 is that the reaction substrate was cyclopropylmethanol, the reaction was electrolyzed for 100 min, purified by silica gel column chromatography, and the eluent was petroleum ether / dichloromethane (volume ratio 2:3), yielding a yellow oily substance; the yield was 93.9 mg, with a yield of 56%, and the product was O,O-di(cyclopropylmethyl)-S-(10H-phenoxazine-3-yl)dithiophosphate (3o).

[0097] The structural characterization data of the O,O-bis(cyclopropylmethyl)-S-(10H-phenoxazine-3-yl)dithiophosphate compound prepared in Example 15 are as follows:

[0098]

[0099] 1H NMR (400 MHz, DMSO-d6) δ 8.56 (s, 1H), 6.91 – 6.88 (m, 1H), 6.76 –6.72 (m, 2H), 6.62 – 6.57 (m, 2H), 6.45 (t, J = 8.0 Hz, 2H), 3.99 – 3.88 (m,4H), 1.18 – 1.08 (m, 2H), 0.57 – 0.50 (m, 4H), 0.32 – 0.29 (m, 4H). 13 C NMR(100 MHz, DMSO-d6) δ 143.37, 143.34, 142.9, 134.7, 134.6, 131.9, 131.85,131.80, 124.7, 121.6, 121.56, 121.50, 116.68, 116.60, 115.6, 114.06, 114.02,72.86, 72.81, 11.2, 11.1, 3.9, 3.8. 31 P NMR (162 MHz, DMSO-d6) δ 87.0. HRMS(ESI) m / z calcd for C 20 H 22 NO3PS2 [M+H] + 420.0851, found 420.0856.

[0100] Example 16

[0101] The difference from Example 1 is that the reaction substrate was phenylethanol, the reaction was electrolyzed for 80 min, purified by silica gel column chromatography, and the eluent was petroleum ether / dichloromethane (volume ratio 1:2), yielding a yellow oily substance; the yield was 91.4 mg, with a yield of 44%, and the product was O,O-diphenylethyl-S-(10H-phenoxazine-3-yl)dithiophosphate (3p).

[0102] The structural characterization data of the O,O-diphenylethyl-S-(10H-phenoxazine-3-yl)dithiophosphate compound prepared in Example 16 are as follows:

[0103]

[0104] 1H NMR (400 MHz, DMSO-d6) δ 8.54 (s, 1H), 7.29 – 7.26 (m, 4H), 7.21 – 7.19 (m, 6H), 6.77 – 6.73 (m, 1H), 6.68 – 6.65 (m, 1H), 6.64 – 6.58 (m, 3H), 6.48 – 6.46 (m, 1H), 6.35 (d, J = 8.0 Hz, 1H), 4.28 – 4.16 (m, 4H), 2.89 (t,J = 6.8 Hz, 4H). 13 C NMR (100 MHz, DMSO-d6) δ 143.37, 143.34, 143.0, 137.7,134.74, 134.71, 131.84, 131.81, 131.7, 129.3, 128.8, 126.9, 124.7, 121.5,121.4, 116.19, 116.10, 115.6, 114.1, 114.09, 114.06, 68.57, 68.51, 36.0,35.9. 31 P NMR (162 MHz, DMSO-d6) δ 88.1. HRMS (ESI) m / z calcd for C 28 H 26 NO3PS2[M+H] + 520.1164, found 520.1165.

[0105] Example 17

[0106] The difference from Example 1 is that the reaction substrate was 4-methoxyphenol, the reaction was electrolyzed for 80 min, purified by silica gel column chromatography, and the eluent was petroleum ether / dichloromethane (volume ratio 1:2) to obtain a yellow oily substance; the yield was 90.0 mg, the yield was 43%, and the product was O,O-bis(4-methoxyphenyl)-S-(10H-phenoxazine-3-yl)dithiophosphate (3q).

[0107] The structural characterization data of the O,O-bis(4-methoxyphenyl)-S-(10H-phenoxazine-3-yl)dithiophosphate compound prepared in Example 17 are as follows:

[0108]

[0109] 1H NMR (400 MHz, DMSO-d6) δ 8.62 (s, 1H), 7.16 – 7.11 (m, 4H), 6.99 – 6.93 (m, 5H), 6.76 – 6.71 (m, 2H), 6.61 – 6.58 (m, 2H), 6.50 – 6.46 (m, 2H),3.74 (s, 6H). 13 C NMR (100 MHz, DMSO-d6) δ 157.34, 157.32, 144.1, 144.0,143.55, 143.52, 142.9, 135.26, 135.22, 132.3, 132.2, 131.6, 124.7, 122.54,122.50, 121.67, 121.63, 121.5, 115.6, 115.4, 115.3, 115.28, 115.26, 114.29,114.26, 114.1, 55.9. 31 P NMR (162 MHz, DMSO-d6) δ 84.7. HRMS (ESI) m / z calcdfor C 26 H 22 NO5PS2 [M+H] + 524.0750, found 524.0751.

[0110] Example 18

[0111] The difference from Example 1 is that the reaction substrate was phenothiazine, electrolyzed for 12 h, purified by silica gel column chromatography, and the eluent was petroleum ether / dichloromethane (volume ratio 1:1) to obtain a yellow solid; the yield was 105.7 mg, the yield was 69%, and the product was O,O-diethyl-S-(10H-phenothiazine-3-yl)dithiophosphate (3r).

[0112] The structural characterization data of the O,O-diethyl-S-(10H-phenthiazin-3-yl)dithiophosphate compound prepared in Example 18 are as follows:

[0113]

[0114] 1H NMR (400 MHz, DMSO-d6) δ 8.88 (s, 1H), 7.12 – 7.09 (m, 1H), 6.99(t, J = 6.8 Hz, 2H), 6.90 (d, J = 7.6 Hz, 1H), 6.77 (t, J = 7.6 Hz, 1H), 6.69- 6.66 (m, 2H), 4.17 – 4.09 (m, 4H), 1.24 (t, J = 7.2 Hz, 6H). 13 C NMR (100MHz, DMSO-d6) δ 143.97, 143.94, 141.4, 135.15, 135.10, 132.84, 132.80, 128.2,126.7, 122.8, 118.6, 118.5, 117.99, 117.96, 116.1, 115.35, 115.33, 115.2,64.38, 64.33, 16.0, 15.9. 31 P NMR (162 MHz, DMSO-d6) δ 87.2. HRMS (ESI) m / zcalcd for C 16 H 18 NO2PS3 [M+Na] + 406.0129, found 406.0133.

[0115] Example 19

[0116] The difference from Example 1 is that the reaction substrate was 2-chlorophenothiazine, electrolyzed for 7 h, purified by silica gel column chromatography, and the eluent was petroleum ether / dichloromethane (volume ratio 1:1) to obtain a yellow solid; the yield was 38.4 mg, the yield was 23%, and the product was S-(2-chloro-10H-phenothiazine-3-yl)-O,O-diethyl dithiophosphate (3s).

[0117] The structural characterization data of the S-(2-chloro-10H-phenthiazin-3-yl)-O,O-diethyl dithiophosphate compound prepared in Example 19 are as follows:

[0118]

[0119] 1H NMR (400 MHz, DMSO-d6) δ 9.03 (s, 1H), 7.10 (s, 1H), 7.01 (t, J =7.6 Hz, 1H), 6.92 (d, J = 7.6 Hz, 1H), 6.82 – 6.79 (m, 2H), 6.65 (d, J = 8.0Hz, 1H), 4.19 – 4.11 (m, 4H), 1.24 (t, J = 7.2 Hz, 6H). 13 C NMR (100 MHz, DMSO-d6) δ 145.1, 145.0, 140.3, 137.18, 137.13, 134.8, 134.7, 128.4, 126.9,123.3, 117.4, 117.3, 116.93, 116.90, 115.9, 115.5, 115.07, 115.04, 64.7,64.6, 16.0, 15.9. 31 P NMR (162 MHz, DMSO-d6) δ 86.1. HRMS (ESI) m / z calcd forC 16 H 17 ClNO2PS3 [M+H] + 417.9920, found 417.9927.

[0120] Example 20

[0121] The difference from Example 1 is that the reaction substrate was 2-methylthiophenthiazine, which was electrolyzed for 25 h and purified by silica gel column chromatography with petroleum ether / dichloromethane (volume ratio 1:5) as the eluent, yielding a yellow solid with a mass of 109.8 mg and a yield of 64%. The product obtained was O,O-diethyl-S-(2-(methylthio)-10H-phenthiazine-3-yl)dithiophosphate (3t).

[0122] The structural characterization data of the O,O-diethyl-S-(2-(methylthio)-10H-phenthiazin-3-yl) dithiophosphate compound prepared in Example 20 are as follows:

[0123]

[0124] 1H NMR (400 MHz, DMSO-d6) δ 8.96 (s, 1H), 7.00 (t, J = 8.0 Hz, 1H), 6.93 (d, J = 8.0 Hz, 2H), 6.78 (t, J = 7.6 Hz, 1H), 6.68 (d, J = 8.0 Hz, 1H), 6.55 (s, 1H), 4.18 – 4.12 (m, 4H), 2.41 (s, 3H), 1.23 (t, J = 7.2 Hz, 6H). 13 CNMR (100 MHz, DMSO-d6) δ 144.64, 144.61, 144.46, 144.41, 141.1, 134.18,134.15, 128.2, 126.8, 122.9, 116.4, 115.49, 115.41, 115.3, 113.0, 112.9,110.53, 110.50, 64.65, 64.60, 16.0, 15.9, 15.2. 31 P NMR (162 MHz, DMSO-d6) δ86.5. HRMS (ESI) m / z calcd for C 17 H 20 NO2PS4 [M+Na] + 452.0007, found 452.0011.

[0125] Example 21

[0126] The difference from Example 1 is that the reaction substrate was methanol, electrolyzed for 10 h, and purified by silica gel column chromatography with petroleum ether / ethyl acetate (volume ratio 1:1) as the eluent, yielding a yellow solid with a mass of 172.2 mg and a yield of 87%. The product obtained was O,O,O',O'-tetramethyl-S,S'-(10H-phenoxazine-3,7-diyl)bis(dithiophosphate) (3u).

[0127] The structural characterization data of the O,O,O',O'-tetramethyl-S,S'-(10H-phenoxazine-3,7-diyl)bis(dithiophosphate) compound prepared in Example 21 are as follows:

[0128]

[0129] 1H NMR (400 MHz, DMSO-d6) δ 8.93 (s, 1H), 6.92 – 6.89 (m, 2H), 6.72(t, J = 2.0 Hz, 2H), 6.46 (d, J = 8.4 Hz, 2H), 3.75 (d, J = 15.6 Hz, 12H). 13 CNMR (100 MHz, DMSO-d6) δ 143.18, 143.16, 133.75, 133.71, 132.16, 132.11,121.4, 121.3, 117.2, 117.1, 114.6, 114.5, 54.59, 54.54. 31 P NMR (162 MHz, DMSO-d6) δ 92.4. HRMS (ESI) m / z calcd for C 16 H 19 NO5P2S4 [M+Na] + 517.9513, found517.9521.

[0130] Example 22

[0131] The difference from Example 1 is that the product was electrolyzed for 12 hours and purified by silica gel column chromatography with petroleum ether / ethyl acetate (volume ratio 2:1) as the eluent, yielding a yellow solid with a mass of 207.2 mg and a yield of 94%. The product was O,O,O',O'-tetraethyl-S,S'-(10H-phenoxazine-3,7-diyl)bis(dithiophosphate) (3v).

[0132] The structural characterization data of the O,O,O',O'-tetraethyl-S,S'-(10H-phenoxazine-3,7-diyl)bis(dithiophosphate) compound prepared in Example 22 are as follows:

[0133]

[0134] 1 H NMR (400 MHz, DMSO-d6) δ 8.90 (s, 1H), 6.91 – 6.88 (m, 2H), 6.71 (s, 2H), 6.47 (d, J = 8.4 Hz, 2H), 4.17 – 4.09 (m, 8H), 1.24 (t, J = 7.2 Hz,12H). 13C NMR (100 MHz, DMSO-d6) δ 143.14, 143.11, 133.7, 133.6, 132.2, 132.1,121.66, 121.62, 117.5, 117.4, 114.5, 114.4, 64.39, 64.34, 16.0, 15.9. 31 P NMR (162 MHz, DMSO-d6) δ 87.2. HRMS (ESI) m / z calcd for C 20 H 27 NO5P2S4 [M+Na] + 574.0139, found 574.0143.

[0135] The reaction mechanism is referenced. Figure 1 Product 3a can further react with a sulfur radical to eventually yield the disubstituted product 3v. Simultaneously, protons in the system are reduced at the cathode to generate hydrogen gas. Another possible reaction pathway is as follows: phenoxazine can be activated at the anode to generate an excited-state active species, which then couples with a sulfur radical to give the monosubstituted product 3a; product 3a then reacts further with an equimolar amount of sulfur radical to ultimately generate the disubstituted product 3v.

[0136] Example 23

[0137] The difference from Example 1 is that the reaction substrate was n-propanol, electrolyzed for 7 h, and purified by silica gel column chromatography with petroleum ether / ethyl acetate (volume ratio 5:1) as the eluent, yielding a yellow solid with a mass of 199.1 mg and a yield of 82%. The product obtained was S,S'-(10H-phenoxazine-3,7-diyl)-O,O,O',O'-tetrapropylbis(dithiophosphate) (3w).

[0138] The structural characterization data of the S,S'-(10H-phenoxazine-3,7-diyl)-O,O,O',O'-tetrapropylbis(dithiophosphate) compound prepared in Example 23 are as follows:

[0139]

[0140] 1H NMR (400 MHz, DMSO-d6) δ 8.88 (s, 1H), 6.91 – 6.88 (m, 2H), 6.71(t, J = 2.0 Hz, 2H), 6.46 (d, J = 8.0 Hz, 2H), 4.07 – 3.97 (m, 8H), 1.66 –1.57 (m, 8H), 0.86 (t, J = 7.2 Hz, 12H). 13 C NMR (100 MHz, DMSO-d6) δ 143.13,143.11, 133.67, 133.64, 132.16, 132.11, 121.66, 121.63, 117.5, 117.4, 114.4,69.6, 69.5, 23.3, 23.2, 10.4. 31 P NMR (162 MHz, DMSO-d6) δ 87.4. HRMS (ESI) m / z calcd for C 24 H 35 NO5P2S4 [M+Na] + 630.0766, found 630.0763.

[0141] Example 24

[0142] The difference from Example 1 is that the reaction substrate was n-butanol, electrolyzed for 8 hours, and purified by silica gel column chromatography with petroleum ether / ethyl acetate (volume ratio 10:1) as the eluent, yielding a yellow solid with a mass of 222.8 mg and a yield of 84%. The product obtained was O,O,O',O'-tetrabutyl-S,S'-(10H-phenoxazine-3,7-diyl)bis(dithiophosphate) (3x).

[0143] The structural characterization data of the O,O,O',O'-tetrabutyl-S,S'-(10H-phenoxazine-3,7-diyl)bis(dithiophosphate) compound prepared in Example 24 are as follows:

[0144]

[0145] 1H NMR (400 MHz, DMSO-d6) δ 8.87 (s, 1H), 6.88 (d, J = 8.0 Hz, 2H), 6.69 (s, 2H), 6.46 (d, J = 8.4 Hz, 2H), 4.10 – 4.02 (m, 8H), 1.60 – 1.53 (m,8H), 1.35 – 1.25 (m, 8H), 0.86 (t, J = 7.2 Hz, 12H). 13 C NMR (100 MHz, DMSO-d6) δ 143.13, 143.11, 133.66, 133.63, 132.0, 131.9, 121.56, 121.52, 117.5,117.4, 114.39, 114.37, 67.8, 67.7, 31.8, 31.7, 18.7, 13.9. 31 P NMR (162 MHz, DMSO-d6) δ 87.4. HRMS (ESI) m / z calcd for C 28 H 43 NO5P2S4 [M+H] + 664.1572, found664.1573.

[0146] Example 25

[0147] The difference from Example 1 is that the reaction substrate was n-pentanol, electrolyzed for 8 hours, and purified by silica gel column chromatography with petroleum ether / ethyl acetate (volume ratio 12:1) as the eluent, yielding a yellow oily substance with a mass of 264.7 mg and a yield of 92%. The product obtained was O,O,O',O'-tetrapentyl-S,S'-(10H-phenoxazine-3,7-diyl)bis(dithiophosphate) (3y).

[0148] The structural characterization data of the O,O,O',O'-tetrapentyl-S,S'-(10H-phenoxazine-3,7-diyl)bis(dithiophosphate) compound prepared in Example 25 are as follows:

[0149]

[0150] 1H NMR (400 MHz, DMSO-d6) δ 8.87 (s, 1H), 6.89 – 6.86 (m, 2H), 6.66(s, 2H), 6.44 (d, J = 8.0 Hz, 2H), 4.10 – 3.98 (m, 8H), 1.61 – 1.55 (m, 8H),1.28 – 1.20 (m, 16H), 0.84 (t, J = 6.8 Hz, 12H). 13 C NMR (100 MHz, DMSO-d6) δ143.14, 143.12, 133.63, 133.60, 131.9, 121.3, 117.5, 117.4, 114.3, 68.1,68.0, 29.5, 29.4, 27.7, 22.2, 14.3. 31 P NMR (162 MHz, DMSO-d6) δ 87.1. HRMS(ESI) m / z calcd for C 32 H 51 NO5P2S4 [M+H] + 720.2198, found 720.2197.

[0151] Example 26

[0152] The difference from Example 1 is that the reaction substrate was n-hexanol, electrolyzed for 9 hours, and purified by silica gel column chromatography with petroleum ether / ethyl acetate (volume ratio 12:1) as the eluent, yielding a yellow oily substance with a mass of 254.3 mg and a yield of 82%. The product obtained was O,O,O',O'-tetrahexyl-S,S'-(10H-phenoxazine-3,7-diyl)bis(dithiophosphate) (3z).

[0153] The structural characterization data of the O,O,O',O'-tetrahexyl-S,S'-(10H-phenoxazine-3,7-diyl)bis(dithiophosphate) compound prepared in Example 26 are as follows:

[0154]

[0155] 1H NMR (400 MHz, DMSO-d6) δ 8.87 (s, 1H), 6.88 – 6.85 (m, 2H), 6.65 (s, 2H), 6.43 (d, J = 8.0 Hz, 2H), 4.10 – 3.98 (m, 8H), 1.60 – 1.53 (m, 8H),1.29 – 1.20 (m, 24H), 0.82 (t, J = 7.2 Hz, 12H). 13 C NMR (100 MHz, DMSO-d6) δ143.15, 143.12, 133.63, 133.60, 131.8, 121.3, 117.5, 117.4, 114.2, 68.1,68.0, 31.2, 29.8, 29.7, 25.3, 22.5, 14.3. 31 P NMR (162 MHz, DMSO-d6) δ 86.9.HRMS (ESI) m / z calcd for C 36 H 59 NO5P2S4 [M+H] + 776.2824, found 776.2816.

[0156] Example 27

[0157] The difference from Example 1 is that the reaction substrate was isopropanol, electrolyzed for 12 h, and purified by silica gel column chromatography with petroleum ether / ethyl acetate (volume ratio 4:1) as the eluent, yielding a yellow oily substance with a mass of 194.3 mg and a yield of 80%. The product obtained was O,O,O',O'-tetraisopropyl-S,S'-(10H-phenoxazine-3,7-diyl)bis(dithiophosphate) (3aa).

[0158] The structural characterization data of the O,O,O',O'-tetraisopropyl-S,S'-(10H-phenoxazine-3,7-diyl)bis(dithiophosphate) compound prepared in Example 27 are as follows:

[0159]

[0160] 1H NMR (400 MHz, DMSO-d6) δ 8.84 (s, 1H), 6.91 – 6.88 (m, 2H), 6.71 (s, 2H), 6.46 (d, J = 8.0 Hz, 2H), 4.77 – 4.67 (m, 4H), 1.25 (t, J = 5.6 Hz, 24H). 13 C NMR (100 MHz, DMSO-d6) δ 143.02, 143.00, 133.5, 133.4, 131.89,131.83, 121.55, 121.51, 118.07, 118.00, 114.35, 114.33, 74.2, 74.1, 23.88,23.83, 23.6, 23.5. 31 P NMR (162 MHz, DMSO-d6) δ 85.0. HRMS (ESI) m / z calcd forC 24 H 35 NO5P2S4 [M+H] + 608.0946, found 608.0944.

[0161] Example 28

[0162] The difference from Example 1 is that the reaction substrate was isobutanol, electrolyzed for 9 hours, and purified by silica gel column chromatography with petroleum ether / dichloromethane (volume ratio 3:2) as the eluent, yielding a yellow oily substance with a mass of 241.4 mg and a yield of 91%. The product obtained was O,O,O',O'-tetraisobutyl-S,S'-(10H-phenoxazine-3,7-diyl)bis(dithiophosphate) (3ab).

[0163] The structural characterization data of the O,O,O',O'-tetraisobutyl-S,S'-(10H-phenoxazine-3,7-diyl)bis(dithiophosphate) compound prepared in Example 28 are as follows:

[0164]

[0165] 1H NMR (400 MHz, DMSO-d6) δ 8.84 (s, 1H), 6.90 (d, J = 8.0 Hz, 2H), 6.71 (s, 2H), 6.45 (d, J = 8.0 Hz, 2H), 3.89 – 3.79 (m, 8H), 1.92 – 1.82 (m,4H), 0.86 (d, J = 6.8 Hz, 24H). 13 C NMR (100 MHz, DMSO-d6) δ 143.12, 143.10,133.64, 133.61, 132.1, 132.0, 121.7, 121.6, 117.4, 117.3, 114.36, 114.33,73.7, 73.6, 28.8, 28.7, 19.0, 18.9. 31 P NMR (162 MHz, DMSO-d6) δ 87.1. HRMS(ESI) m / z calcd for C 28 H 43 NO5P2S4 [M+Na] + 686.1392, found 686.1389.

[0166] Example 29

[0167] The difference from Example 1 is that the reaction substrate was isoamyl alcohol, electrolyzed for 7 hours, and purified by silica gel column chromatography with petroleum ether / dichloromethane (volume ratio 1:1) as the eluent, yielding a green oily substance with a mass of 253.2 mg and a yield of 88%. The product obtained was O,O,O',O'-tetraisopentyl-S,S'-(10H-phenoxazine-3,7-diyl)bis(dithiophosphate) (3ac).

[0168] The structural characterization data of the O,O,O',O'-tetraisopentyl-S,S'-(10H-phenoxazine-3,7-diyl)bis(dithiophosphate) compound prepared in Example 29 are as follows:

[0169]

[0170] 1H NMR (400 MHz, DMSO-d6) δ 8.87 (s, 1H), 6.89 (d, J = 8.0 Hz, 2H), 6.68 (s, 2H), 6.46 (d, J = 8.4 Hz, 2H), 4.12 – 4.04 (m, 8H), 1.67 – 1.57 (m,4H), 1.53 – 1.43 (m, 8H), 0.86 – 0.85 (m, 24H). 13 C NMR (100 MHz, DMSO-d6) δ143.15, 143.13, 133.67, 133.64, 131.99, 131.94, 121.49, 121.45, 117.5, 117.4,114.4, 114.3, 66.6, 66.5, 38.5, 38.4, 24.5, 22.7, 22.5. 31 P NMR (162 MHz, DMSO-d6) δ 87.3. HRMS (ESI) m / z calcd for C 32 H 51 NO5P2S4 [M+H] + 720.2198, found720.2194.

[0171] Example 30

[0172] The difference from Example 1 is that the reaction substrate was cyclopropanol, electrolyzed for 6 hours, and purified by silica gel column chromatography with petroleum ether / dichloromethane (volume ratio 2:3) as the eluent, yielding a yellow oily substance with a mass of 103.0 mg and a yield of 43%. The product obtained was O,O,O',O'-tetracyclopropyl-S,S'-(10H-phenoxazine-3,7-diyl)bis(dithiophosphate) (3ad).

[0173] The structural characterization data of the O,O,O',O'-tetracyclopropyl-S,S'-(10H-phenoxazine-3,7-diyl)bis(dithiophosphate) compound prepared in Example 30 are as follows:

[0174]

[0175] 1H NMR (400 MHz, DMSO-d6) δ 8.92 (s, 1H), 6.92 – 6.88 (m, 2H), 6.72(s, 2H), 6.48 (d, J = 8.0 Hz, 2H), 4.13 – 4.07 (m, 4H), 0.79 – 0.66 (m, 16H). 13 C NMR (100 MHz, DMSO-d6) δ 143.1, 143.0, 133.78, 133.75, 132.29, 132.24,121.7, 121.6, 117.1, 117.0, 114.57, 114.54, 52.87, 52.81, 5.9, 5.8, 5.56,5.50. 31 P NMR (162 MHz, DMSO-d6) δ 89.7. HRMS (ESI) m / z calcd for C 24 H 27 NO5P2S4[M+H] + 600.0320, found 600.0316.

[0176] Example 31

[0177] The difference from Example 1 is that the reaction substrate was cyclobutanol, electrolyzed for 8.5 h, and purified by silica gel column chromatography with petroleum ether / dichloromethane (volume ratio 1:1) as the eluent, yielding a green oily substance with a mass of 228.0 mg and a yield of 87%. The product obtained was O,O,O',O'-tetracyclobutyl-S,S'-(10H-phenoxazine-3,7-diyl)bis(dithiophosphate) (3ae).

[0178] The structural characterization data of the O,O,O',O'-tetracyclobutyl-S,S'-(10H-phenoxazine-3,7-diyl)bis(dithiophosphate) compound prepared in Example 31 are as follows:

[0179]

[0180] 1H NMR (400 MHz, DMSO-d6) δ 8.88 (s, 1H), 6.86 (d, J = 8.0 Hz, 2H), 6.67 (s, 2H), 6.47 (d, J = 8.0 Hz, 2H), 4.88 – 4.78 (m, 4H), 2.30 – 2.23 (m,8H), 2.13 – 2.02 (m, 8H), 1.72 – 1.64 (m, 4H), 1.57 – 1.45 (m, 4H). 13 C NMR(100 MHz, DMSO-d6) δ 143.08, 143.05, 133.69, 133.66, 132.1, 121.79, 121.76,117.5, 117.4, 114.4, 71.5, 71.4, 32.1, 32.0, 31.6, 31.5, 12.9. 31 P NMR (162MHz, DMSO-d6) δ 82.8. HRMS (ESI) m / z calcd for C 28 H 35 NO5P2S4 [M+H] + 656.0946, found 656.0943.

[0181] Example 32

[0182] The difference from Example 1 is that the reaction substrate was cyclopentanol, which was electrolyzed for 10 h and purified by silica gel column chromatography with petroleum ether / dichloromethane (volume ratio 1:1) as the eluent, yielding a green oily substance with a mass of 219.0 mg and a yield of 77%. The product obtained was O,O,O',O'-tetracyclopentyl-S,S'-(10H-phenoxazine-3,7-diyl)bis(dithiophosphate) (3af).

[0183] The structural characterization data of the O,O,O',O'-tetracyclopentyl-S,S'-(10H-phenoxazine-3,7-diyl)bis(dithiophosphate) compound prepared in Example 32 are as follows:

[0184]

[0185] 1H NMR (400 MHz, DMSO-d6) δ 8.83 (s, 1H), 6.89 – 6.86 (m, 2H), 6.69 (t, J = 2.0 Hz, 2H), 6.46 (d, J = 8.0 Hz, 2H), 5.01 – 4.95 (m, 4H), 1.83 –1.70 (m, 16H), 1.68 – 1.52 (m, 16H). 13 C NMR (100 MHz, DMSO-d6) δ 143.03,143.01, 133.48, 133.45, 131.9, 131.8, 121.59, 121.55, 117.9, 117.8, 114.3,114.2, 82.5, 82.4, 33.99, 33.95, 33.6, 33.5, 23.2, 23.1. 31 P NMR (162 MHz, DMSO-d6) δ 84.7. HRMS (ESI) m / z calcd for C 32 H 43 NO5P2S4 [M+Na] + 734.1392, found734.1396.

[0186] Example 33

[0187] The difference from Example 1 is that the reaction substrate was cyclopropylmethanol, electrolyzed for 11 h, and purified by silica gel column chromatography with petroleum ether / dichloromethane (volume ratio 2:3) as the eluent, yielding a yellow oily substance with a mass of 225.4 mg and a yield of 86%. The product obtained was O,O,O',O'-tetra(cyclopropylmethyl)-S,S'-(10H-phenoxazine-3,7-diyl)bis(dithiophosphate) (3 ag).

[0188] The structural characterization data of the O,O,O',O'-tetra(cyclopropylmethyl)-S,S'-(10H-phenoxazine-3,7-diyl)bis(dithiophosphate) compound prepared in Example 33 are as follows:

[0189]

[0190] 1H NMR (400 MHz, DMSO-d6) δ 8.89 (s, 1H), 6.94 – 6.91 (m, 2H), 6.76 (s, 2H), 6.47 (d, J = 8.0 Hz, 2H), 3.99 – 3.87 (m, 8H), 1.18 – 1.06 (m, 4H), 0.57 – 0.50 (m, 8H), 0.32 – 0.28 (m, 8H). 13 C NMR (100 MHz, DMSO-d6) δ 143.1,133.6, 132.1, 121.6, 117.6, 117.5, 114.4, 72.9, 72.8, 11.1, 11.0, 3.9, 3.8. 31 P NMR (162 MHz, DMSO-d6) δ 86.7. HRMS (ESI) m / z calcd for C 28 H 35 NO5P2S4 [M+H] + 656.0946, found 656.0945.

[0191] Example 34

[0192] The difference from Example 1 is that the reaction substrate was phenylethanol, which was electrolyzed for 12 h and purified by silica gel column chromatography with petroleum ether / dichloromethane (volume ratio 1:2) as the eluent, yielding a green oily substance with a mass of 290.8 mg and a yield of 85%. The product obtained was O,O,O',O'-tetraphenylethyl-S,S'-(10H-phenoxazine-3,7-diyl)bis(dithiophosphate) (3ah).

[0193] The structural characterization data of the O,O,O',O'-tetraphenylethyl-S,S'-(10H-phenoxazine-3,7-diyl)bis(dithiophosphate) compound prepared in Example 34 are as follows:

[0194]

[0195] 1H NMR (400 MHz, DMSO-d6) δ 8.86 (s, 1H), 7.28 – 7.24 (m, 8H), 7.20 –7.17 (m, 12H), 6.70 – 6.67 (m, 2H), 6.62 (s, 2H), 6.36 (d, J = 8.4 Hz, 2H), 4.26 – 4.17 (m, 8H), 2.88 (t, J = 6.8 Hz, 8H). 13 C NMR (100 MHz, DMSO-d6) δ143.12, 143.10, 137.6, 133.64, 133.61, 132.0, 129.3, 128.8, 126.9, 121.5,117.08, 117.00, 114.4, 68.6, 68.5, 35.9, 35.8. 31 P NMR (162 MHz, DMSO-d6) δ87.8. HRMS (ESI) m / z calcd for C 44 H 43 NO5P2S4 [M+H] + 856.1572, found 856.1565.

[0196] Example 35

[0197] The difference from Example 1 is that the reaction substrate was phenothiazine, electrolyzed for 24 h, and purified by silica gel column chromatography with petroleum ether / dichloromethane (volume ratio 1:1) as the eluent, yielding a green oily substance with a mass of 179.2 mg and a yield of 79%. The product obtained was O,O,O',O'-tetraethyl-S,S'-(10H-phenothiazine-3,7-diyl)bis(dithiophosphate) (3ai).

[0198] The structural characterization data of the O,O,O',O'-tetraethyl-S,S'-(10H-phenthiazine-3,7-diyl)bis(dithiophosphate) compound prepared in Example 35 are as follows:

[0199]

[0200] 1H NMR (400 MHz, DMSO-d6) δ 9.15 (s, 1H), 7.13 (d, J = 8.4 Hz, 2H), 7.03 (s, 2H), 6.67 (d, J = 8.0 Hz, 2H), 4.17 – 4.09 (m, 8H), 1.24 (t, J = 7.2Hz, 12H). 13 C NMR (100 MHz, DMSO-d6) δ 142.9, 142.8, 135.4, 135.3, 132.9,132.8, 119.5, 119.4, 117.4, 117.3, 115.75, 115.72, 64.4, 64.3, 16.0, 15.9. 31 PNMR (162 MHz, DMSO-d6) δ 86.9. HRMS (ESI) m / z calcd for C 20 H 27 NO4P2S5 [M+Na] + 589.9911, found 589.9918.

[0201] Example 36

[0202] The difference from Example 1 is that the reaction substrate was 2-chlorophenothiazine, electrolyzed for 19 h, and purified by silica gel column chromatography with petroleum ether / dichloromethane (volume ratio 1:2) as the eluent, yielding a yellow oily substance with a mass of 201.9 mg and a yield of 84%. The product obtained was S,S'-(2-chloro-10H-phenothiazine-3,7-diyl)-O,O,O',O'-tetraethylbis(dithiophosphate) (3aj).

[0203] The structural characterization data of the S,S'-(2-chloro-10H-phenthiazine-3,7-diyl)-O,O,O',O'-tetraethylbis(dithiophosphate) compound prepared in Example 36 are as follows:

[0204]

[0205] 1 H NMR (400 MHz, DMSO-d6) δ 9.30 (s, 1H), 7.15 – 7.14 (m, 2H), 7.06 (s, 1H), 6.79 (s, 1H), 6.66 (d, J = 8.4 Hz, 1H), 4.19 – 4.09 (m, 8H), 1.26 –1.21 (m, 12H). 13C NMR (100 MHz, DMSO-d6) δ 144.1, 144.0, 141.87, 141.84,137.4, 137.3, 135.5, 134.9, 132.9, 120.1, 120.0, 118.2, 118.1, 117.23,117.20, 116.37, 116.34, 116.07, 116.04, 115.4, 64.76, 64.70, 64.4, 64.3,16.03, 16.00, 15.94, 15.92. 31 P NMR (162 MHz, DMSO-d6) δ 86.6, 85.7. HRMS(ESI) m / z calcd for C 20 H 26 ClNO4P2S5 [M+H] + 601.9702, found 601.9694.

[0206] This green synthetic method for dithiophosphoryl-substituted azine compounds uses phenoxazine / phenothiazine compounds, phosphorus pentasulfide, and alcohols as substrates. Through diaphragm-free electrolysis at room temperature with constant current, selective dehydrogenation coupling of the three components is achieved, successfully preparing mono- and di-dithiophosphoryl-substituted products. This method completely eliminates the need for metal catalysts and added chemical oxidants, using inexpensive phosphorus pentasulfide as both a sulfur and phosphorus source, and electrons as a clean oxidizing agent. The method is mild, simple to operate, and has a wide range of applicable substrates, suitable for various fatty alcohols, cyclic alcohols, and substituted heterocyclic substrates. The product structure can be precisely controlled by adjusting the electrolysis time, with moderate to excellent yields of the target products and no significant decrease in yield. Mechanistic studies confirm that the reaction proceeds via a free radical pathway. The process is green, environmentally friendly, and highly atom-economical, aligning with green chemistry principles. It provides a novel route for the efficient construction of CS bonds in phenoxazine functional heterocycles, showing promising industrial applications in optoelectronic materials and pharmaceutical intermediates.

[0207] Furthermore, it should be noted that the direct current in the synthesis method of the present invention can be amplified according to the changes in the amount of reaction raw materials and electrolyte, such as from 6mA to 12mA. Specifically, it can be adjusted according to the changes in the amount of reaction raw materials, electrolyte and the volume of the electrolytic cell, with the aim of promoting the rapid completion of the reaction.

[0208] Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A method for synthesizing a dithiophosphoryl-substituted azine compound, characterized in that, A azine compound, phosphorus pentasulfide, and alcohol compound were uniformly mixed in an electrolyte, and then a direct current was passed through the electrolyte until the reaction was completed. The dithiophosphoryl-substituted azine compound was then obtained by separation. The azine compounds are phenoxazine compounds or phenothiazine compounds; The electrolyte is an acetonitrile solution containing tetrabutylammonium hydrogen sulfate; The molar ratio of the azine compound, phosphorus pentasulfide, and alcohol compound is 0.4:0.4:10.

0.

2. The method for synthesizing dithiophosphoryl-substituted azine compounds according to claim 1, characterized in that, The phenoxazine compound is a phenoxazine; The phenothiazine compound is one of phenothiazine, halophenothiazine, or alkyl-substituted phenothiazine; The alcohol compound is one of C1-C6 aliphatic straight-chain alcohols, cyclopropanol, cyclobutanol, cyclopentanol, phenethyl alcohol, and p-methoxyphenol.

3. The method for synthesizing dithiophosphoryl-substituted azine compounds according to claim 1, characterized in that, The concentration of tetrabutylammonium hydrogen sulfate in the electrolyte is 50 mmol / L.

4. A dithiophosphoryl-substituted azine compound, characterized in that, Prepared by any one of the methods in claims 1-3.

5. The dithiophosphoryl-substituted azine compound according to claim 4, characterized in that, The dithiophosphoryl-substituted azines are at least one of dithiophosphoryl monosubstituted azines or dithiophosphoryl disubstituted azines.

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