Triaza-aryl phosphine sulfur compound and preparation method thereof

Abstract

The invention provides a triazaaryl phosphine-sulfur compound and a preparation method thereof.The triazaaryl phosphine-sulfur compound shown in the formula (I) is an organic phosphine compound of a triazaaryl phosphine-sulfur structure directly synthesized through white phosphorus, and the process avoids the problems that chlorine with great pollution is used in traditional phosphorus chemical industry production and subsequent emission is caused; and the method is a more environment-friendly production method. In addition, the method disclosed by the invention is simple in step, mild in reaction condition and simple in post-treatment, and the yield of medium or above can be obtained.

Description

Technical Field

[0001] This invention relates to the field of organophosphorus chemistry and chemical engineering, and more specifically, to a triazaarylphosphine sulfur compound and its preparation method. Background Technology

[0002] Organophosphine sulfides have wide applications in the synthesis of organic catalysts, ligands, and functional materials. As a representative class of these compounds, triazaarylphosphine sulfides possess lone pairs of electrons in their sulfur atom structure, enabling them to participate in coordination. Furthermore, these compounds exhibit diverse π-conjugated systems, with resonant interactions between phosphorus, nitrogen, and sulfur atoms, resulting in rich optical properties. Therefore, triazaarylphosphine sulfides show great promise for applications in ligand synthesis and optoelectronic materials (see Patent Document 1 and Non-Patent Documents 1-4).

[0003] As disclosed in Non-Patent Literature 1-5, the traditional synthetic route for triazaarylphosphine sulfides involves a multi-step chlorination process: white phosphorus → phosphorus trichloride → triazaarylphosphine sulfides. The conversion from white phosphorus to phosphorus trichloride requires the use of highly polluting and toxic chlorine gas; the conversion from phosphorus trichloride to triazaarylphosphine sulfides requires the use of azaaryl compounds or corresponding lithium salts as raw materials. The chlorine-containing waste salts and waste acids generated in this step are difficult to recover, causing serious environmental pollution (Non-Patent Literature 5-6). Furthermore, the reaction between phosphorus trichloride and azaaryl lithium salts generally needs to be carried out at low temperatures, resulting in significant energy consumption. Therefore, the traditional route is insufficient in terms of both environmental protection and economic efficiency, which limits the industrial-scale production of triazaarylphosphine sulfides.

[0004] Therefore, developing a chlorination-free, mild, and simple method for synthesizing triazaarylphosphine sulfur compounds has significant practical value. In line with the development needs of modern organophosphorus chemical processes, this invention focuses on researching a method for synthesizing triazaarylphosphine sulfur compounds from white phosphorus under mild, chlorination-free conditions.

[0005] Existing technical documents

[0006] Patent documents:

[0007] Patent Document 1: CN110407875A.

[0008] Non-patent literature:

[0009] Non-patent literature 1: Transit.Met.Chem.2002,27,177-183.

[0010] Non-patent literature 2: J.Am.Chem.Soc.2022,144,6946-6953.

[0011] Non-patent literature 3: Chem. Sci. 2022, 13, 5893-5901.

[0012] Non-patent literature 4: J.Org.Chem.2023,88,13678-13685.

[0013] Non-patent literature: 5: Natl. Sci. Rev. 2024, 11, nwae162.

[0014] Non-patent literature 6: J. Appl. Electrochem. 2023, 53, 963-975. Summary of the Invention

[0015] The technical problem that the invention aims to solve

[0016] This invention was made in view of the above-mentioned problems, and its purpose is to provide a novel triazaarylphosphine sulfur compound and its preparation method. The preparation method is a method that uses readily available chemical raw material—white phosphorus—through simple reaction steps and mild reaction conditions, which can not only efficiently synthesize triazaarylphosphine sulfur compounds, but also greatly reduce the environmental pollution caused during the production process.

[0017] Solution for solving the problem

[0018] The technical solution of the present invention is as follows:

[0019] One aspect of the present invention is a triazaarylphosphine sulfide compound, which is a triazaarylphosphine sulfide compound represented by formula (I) below, characterized in that...

[0020]

[0021] In formula (I), The term represents a aziridine group, wherein the three aziridine groups may be the same or different; the aziridine group is a substituted or unsubstituted pyrrole, imidazole, indole, carbazole, or phenothiazine group, and the substituent is hydrogen, halogen, alkyl, or alkoxy; wherein the halogen is fluorine, chlorine, or bromine; the alkyl group is a C1-C4 alkyl group; and the alkoxy group is a C1-C4 alkoxy group.

[0022] In a preferred embodiment, the azaaryl group is a substituted or unsubstituted pyrrole, indole, carbazole, or phenothiazine group.

[0023] Another aspect of the present invention is a method for preparing a triazaarylphosphine sulfide compound, which is a method for preparing a triazaarylphosphine sulfide compound represented by formula (I).

[0024]

[0025] The preparation method is as follows:

[0026] 1) Add white phosphorus, disulfide or diselenide and solvent sequentially to reactor ① filled with nitrogen or argon, and mix and stir to obtain solution A; add the azaaryl compound of formula (II), base and solvent sequentially to reactor ② filled with nitrogen or argon, and mix and stir to obtain solution B.

[0027] 2) Add the above solution B dropwise to the above solution A while stirring at room temperature. The reaction time should be more than 0.5 hours. Then add sulfur powder and stir at room temperature. Continue the reaction time for more than 0.2 hours to prepare compound (I).

[0028]

[0029] Reaction route

[0030] In the azaaryl compounds of formula (II), the azaaryl group is a substituted or unsubstituted pyrrole, imidazole, indole, carbazole, or phenothiazine group.

[0031] The three azaaryl groups may be the same or different; the azaaryl groups are substituted or unsubstituted pyrrole, imidazole, indole, carbazole, or phenothiazine groups; the substituents are hydrogen, halogen, alkyl, or alkoxy; the halogens are fluorine, chlorine, or bromine; the alkyl groups are C1-C4 alkyl groups; and the alkoxy groups are C1-C4 alkoxy groups.

[0032] The disulfide is diphenyl disulfide, 4,4'-dimethyl diphenyl disulfide, 4,4'-dimethoxydiphenyl disulfide, 4,4'-difluorodiphenyl disulfide, 4,4'-dichlorodiphenyl disulfide, 4,4'-dibromodiphenyl disulfide, 4,4'-dinitrodiphenyl disulfide, 4,4'-diaminodiphenyl disulfide, 4,4'-dicarboxylic acid diphenyl disulfide, 4,4'-dihydroxydiphenyl disulfide, 3,3'-dihydroxydiphenyl disulfide, 3,3'-difluorodiphenyl disulfide, 2,2'-diaminodiphenyl sulfide, 2,2'-dithiobenzoic acid, or dibenzothiazole disulfide. Di(2-naphthyl)disulfide, di(1-naphthyl)disulfide, 2,2'-dipyridine disulfide, dibenzyl disulfide, di-n-butyl disulfide, wherein the diselenide is diphenyldiselenide, 4,4'-dimethyldiphenyldiselenide, 4,4'-dimethoxydiphenyldiselenide, 4,4'-difluorodiphenyldiselenide, 4,4'-dichlorodiphenyldiselenide, 4,4'-dibromodiphenyldiselenide, 4,4'-dinitrodiphenyldiselenide, 3,3'-di-tert-butyldiphenyldiselenide, 2,2'-dimethoxydiphenyldiselenide, di(2-anthrayl)diselenide, di(2-naphthyl)diselenide, dibenzyldiselenide.

[0033] The amount of disulfide or diselenide used is in the range of 0.5 to 5.0 molar equivalents relative to the amount of white phosphorus (based on phosphorus atoms). Normally, white phosphorus is difficult to react directly with azaaryl compounds to obtain triazaarylphosphine. However, in this reaction, it is directly synthesized under the mediation of disulfide or diselenide. The general mechanism is as follows: In step 1), the azaaryl compound of formula (II) first generates an azaaryl anion under the action of a base, resulting in solution B. Then, in step 2), with the addition of solution B, a small amount of azaaryl anion acts as a base to promote the reaction of white phosphorus in solution A with disulfide or diselenide, yielding a trivalent phosphine compound containing three phosphorus-sulfur bonds or three phosphorus-selenium bonds. Finally, these trivalent phosphine intermediates can undergo a substitution reaction with the subsequently added azaaryl anion to obtain triazaarylphosphine. Simultaneously, the released sulfur- or selenium-containing compounds can be oxidized and regenerated into disulfide and diselenide, thus achieving recycling.

[0034] The alkali is an alkali metal compound, an alkaline earth metal compound, or an organic amine, wherein the alkali metal compound or alkaline earth metal compound is its hydride, hydroxide, carbonate, acetate, or organic alkoxide. The amount of alkali used relative to white phosphorus (calculated as phosphorus atoms) ranges from 2.0 to 5.0 molar equivalents.

[0035] The ratio of sulfur powder (calculated as sulfur atoms) to white phosphorus (calculated as phosphorus atoms) is 1.0 to 3.0 molar equivalents.

[0036] The solvent is an organic solvent, which can dissolve the reactants and does not react with the azaaryl compounds and white phosphorus. Examples include tetrahydrofuran, diethyl ether, 1,4-dioxane, ethylene glycol dimethyl ether, n-hexane, and toluene.

[0037] For the ratio of the azaaryl compound of formula (II) to white phosphorus, the ratio of the azaaryl compound of formula (II) to white phosphorus (in terms of phosphorus atoms) is 2.0 to 9.0 molar equivalents.

[0038] The effects of the invention

[0039] According to the present invention, a triazaarylphosphine sulfur compound and its preparation method are provided. Traditional synthesis methods use chlorine gas, which is not only highly polluting and hazardous, but also involves relatively complex procedures. In contrast, the preparation method of the present invention uses white phosphorus (P4) to directly synthesize the triazaarylphosphine sulfur compound in the presence of disulfide or diselenate, thereby avoiding the use of chlorine gas. Furthermore, the disulfide and diselenate used in the method can be recycled, making it a more economical and environmentally friendly production method.

[0040] Furthermore, it can be seen from the preparation method of the present invention that the raw materials of the present invention are inexpensive and readily available, while the reaction conditions are mild, the post-processing is simple, and a medium to high yield can be obtained. Therefore, the reaction is an economical and practical reaction.

[0041] In addition, the triazaarylphosphine sulfur compounds provided by this invention have diverse π-conjugated systems, which can be used for the research and development of optoelectronic materials; furthermore, the sulfur atoms in the structure have lone pairs of electrons, which can participate in coordination, and have good application prospects in the synthesis of organic ligands. Detailed Implementation

[0042] The following specific embodiments further illustrate the above-described contents of the present invention in detail, but should not be construed as limiting the scope of protection of the present invention in any way. All technical solutions implemented based on the above-described contents of the present invention fall within the scope of the present invention. The present invention provides a general and / or specific description of the materials and test methods used in the experiments. Those skilled in the art will understand that, unless otherwise specified, the room temperature mentioned in the following text has a technically known meaning in the art, generally referring to 20–25°C; all chemicals mentioned are commercially available.

[0043] The triazaarylphosphine sulfur compound of the present invention is the triazaarylphosphine sulfur compound shown in formula (I).

[0044]

[0045] In formula (I), the three azaaryl groups may be the same or different; the azaaryl group is a substituted or unsubstituted pyrrole, imidazole, indole, carbazole, or phenothiazine group; the substituent is hydrogen, halogen, alkyl, or alkoxy; the halogen is fluorine, chlorine, or bromine; the alkyl group is a C1-C4 alkyl group; and the alkoxy group is a C1-C4 alkoxy group. Preferably, the azaaryl group is a substituted or unsubstituted pyrrole, indole, carbazole, or phenothiazine group; among the substituents, the halogen is preferably fluorine or chlorine; the alkyl group is preferably methyl, ethyl, n-propyl, or dimethylaminomethyl; and the alkoxy group is preferably methoxy or ethoxy.

[0046] Preparation of compounds

[0047] The method for preparing the triazaarylphosphine sulfide compound of the present invention is the method for preparing the triazaarylphosphine sulfide compound shown in formula (I) above.

[0048] The preparation method is as follows:

[0049] 1) Add white phosphorus, disulfide or diselenide and solvent sequentially to reactor ① filled with nitrogen or argon, mix and stir to obtain solution A; add the azaaryl compound of formula (II), base and solvent sequentially to reactor ② filled with nitrogen or argon, mix and stir to obtain solution B.

[0050] 2) Add the above solution B dropwise to the above solution A while stirring at room temperature. The reaction time should be more than 0.5 hours. Then add sulfur powder and continue to react for more than 0.2 hours while stirring at room temperature. This will prepare compound (I).

[0051]

[0052] Reaction route

[0053] In the compound of formula (I), the three azaaryl groups may be the same or different; the azaaryl group is a substituted or unsubstituted pyrrole, imidazole, indole, carbazole, or phenothiazine group; the substituent is hydrogen, halogen, alkyl, or alkoxy; the halogen is fluorine, chlorine, or bromine; the alkyl group is a C1-C4 alkyl group; and the alkoxy group is a C1-C4 alkoxy group.

[0054] Wherein, the azaaryl group is preferably a substituted or unsubstituted pyrrole, indole, carbazole, or phenothiazine group; among the substituents, the halogen is preferably fluorine or chlorine; the alkyl group is preferably methyl, ethyl, n-propyl, or dimethylaminomethyl; and the alkoxy group is preferably methoxy or ethoxy.

[0055] For the ratio of the azaaryl compound of formula (II) to white phosphorus, the ratio of the azaaryl compound of formula (II) to white phosphorus (calculated in terms of phosphorus atoms) is 2.0 to 9.0 molar equivalents, preferably 2.5 to 8.5 molar equivalents, and more preferably 3.0 to 5.0 molar equivalents.

[0056] The disulfide used can be diphenyl disulfide, 4,4'-dimethyl diphenyl disulfide, 4,4'-dimethoxy diphenyl disulfide, 4,4'-difluorodiphenyl disulfide, 4,4'-dichlorodiphenyl disulfide, 4,4'-dibromodiphenyl disulfide, 4,4'-dinitrodiphenyl disulfide, 4,4'-diaminodiphenyl disulfide, 4,4'-dicarboxylic acid diphenyl disulfide, etc. 4,4'-Dihydroxydiphenyl disulfide, 3,3'-Dihydroxydiphenyl disulfide, 3,3'-Difluorodiphenyl disulfide, 2,2'-Diaminodiphenyl sulfide, 2,2'-Dithiodibenzoic acid, dibenzothiazole disulfide, di(2-naphthyl)disulfide, di(1-naphthyl)disulfide, 2,2'-dipyridine disulfide, dibenzyl disulfide, di-n-butyl disulfide, wherein the diselenide is a di- Phenyl diselenide, 4,4'-dimethyldiphenyl diselenide, 4,4'-dimethoxydiphenyl diselenide, 4,4'-difluorodiphenyl diselenide, 4,4'-dichlorodiphenyl diselenide, 4,4'-dibromodiphenyl diselenide, 4,4'-dinitrodiphenyl diselenide, 3,3'-di-tert-butyldiphenyl diselenide, 2,2'-dimethoxydiphenyl diselenide, di(2-anthrayl)diselenide, di(2-naphthyl)diselenide, dibenzyl diselenide; wherein, preferably, diphenyl disulfide, 4,4'-dimethyldiphenyl disulfide, 4,4'-difluorodiphenyl disulfide, 4,4'-dichlorodiphenyl disulfide, 4,4'-dibromodiphenyl disulfide, di-n-butyl disulfide, diphenyl diselenide and 4,4'-dimethyldiphenyl diselenide; more preferably, diphenyl disulfide and diphenyl diselenide.

[0057] The ratio of the disulfide or diselenide to white phosphorus (based on phosphorus atoms) is 0.5 to 5.0 molar amounts, preferably 1.0 to 4.5 molar amounts, and more preferably 1.5 to 3.0 molar amounts.

[0058] The base used is an alkali metal compound, an alkaline earth metal compound, or an organic amine. The alkali metal compound and alkaline earth metal compound are their hydrides, hydroxides, carbonates, acetates, or organic alkoxides. The alkali metal and alkaline earth metal hydrides are sodium hydride, potassium hydride, or magnesium hydride; the alkali metal and alkaline earth metal hydroxides are sodium hydroxide, potassium hydroxide, magnesium hydroxide, or barium hydroxide; the alkali metal and alkaline earth metal carbonates are lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, or magnesium carbonate; the alkali metal and alkaline earth metal acetates are sodium acetate or potassium acetate; the alkali metal and alkaline earth metal organic alkoxides are sodium ethoxide, sodium tert-butoxide, or potassium tert-butoxide; and the organic amine is triethylamine, 4-dimethylaminopyridine (DMAP), or 1,4-diazabicyclo[2.2.2]octane (DABCO). The preferred bases are sodium hydride, potassium hydride, cesium carbonate, or potassium tert-butoxide, with sodium hydride being more preferred.

[0059] The ratio of the alkali used to white phosphorus (based on phosphorus atoms) is in the range of 2.0 to 5.0 molar equivalents, preferably 2.5 to 4.0 molar equivalents, and more preferably 3.0 to 4.0 molar equivalents.

[0060] The ratio of sulfur powder (calculated as sulfur atoms) to white phosphorus (calculated as phosphorus atoms) is 1.0 to 3.0 molar equivalents, preferably 1.5 to 3.0 molar equivalents, and more preferably 1.5 to 2.5 molar equivalents.

[0061] The preferred reaction time in the above method is: initially reacting at room temperature for 0.5–6 hours, more preferably 1–5 hours, and even more preferably 1–4 hours; then continuing the reaction at room temperature for 0.2–3 hours, more preferably 0.5–2 hours, and even more preferably 0.5–1.5 hours.

[0062] Any organic solvent used in the above reaction can dissolve the reactants and not react with the azirroyl compounds and white phosphorus. Examples include tetrahydrofuran, diethyl ether, 1,4-dioxane, ethylene glycol dimethyl ether, n-hexane, and toluene.

[0063] The preparation method of the above compounds is described in detail below through examples.

[0064] Synthesis of compound (I)

[0065] Example 1: Synthesis of 1-{[di(indol-1-yl)]thionyl-λ5-methphospho}indole (Tri(1H-indol-1-yl)phosphine sulfide)

[0066]

[0067] In a glove box filled with nitrogen or argon, white phosphorus (0.075 mmol), 4,4'-dimethyldiphenyl disulfide (0.45 mmol), and THF (3.0 mL) were added sequentially to a 10 mL flask ① equipped with a stirrer. The mixture was stirred at room temperature for 5 min until all the solids were dissolved to obtain solution A. Indole (0.9 mmol), sodium hydride (0.9 mmol), and THF (3.0 mL) were added sequentially to a 10 mL flask ② equipped with a stirrer. The mixture was stirred until all bubbles disappeared to obtain solution B. Solution B was added dropwise to solution A over 10 min. The mixture was then stirred at room temperature for 1 h. Sulfur powder (0.45 mmol based on sulfur atoms) was then added, and the mixture was stirred at room temperature for another 0.5 h. After the reaction was complete, the reaction solution was concentrated and separated by column chromatography to obtain product 1 in 93% yield (yield calculation based on phosphorus atoms).

[0068] Key NMR data for Product 1: 1H NMR (400MHz, CDCl3) δ6.63 (d, J = 3.3 Hz, 6H), 7.20 (dt, J = 22.6, 7.4 Hz, 6H), 7.61 (d, J = 7.7 Hz, 3H), 7.74 (d, J = 8.2 Hz, 3H). 13 C NMR (101MHz, CDCl3) δ 109.3 (d, J = 8.5Hz), 114.8, 121.6, 123.3, 124.4, 128.1 (d, J = 6.1Hz), 131.9 (d, J = 9.1Hz), 137.5 (d, J = 5.9Hz). 31 P{ 1 H}NMR(162MHz,CDCl3)δ32.45(s).HRMS m / z:[M+H] + calcdfor C 24 H 19 N3PS + 412.1032; Found: 412.1027.

[0069] Example 2: Synthesis of 1-{[bis(5-methylindol-1-yl)]thionyl-λ5-methphospho}-5-methylindol (Tris(5-methyl-1H-indol-1-yl)phosphine sulfide)

[0070]

[0071] In a glove box filled with nitrogen or argon, white phosphorus (0.075 mmol), diphenyldiselenoether (0.8 mmol), and THF (3.0 mL) were added sequentially to a 10 mL flask ① equipped with a stirrer. The mixture was stirred at room temperature for 5 min until all the solids were dissolved to obtain solution A. 5-methylindole (1.1 mmol), sodium hydride (0.9 mmol), and THF (3.0 mL) were added sequentially to a 10 mL flask ② equipped with a stirrer. The mixture was stirred until all bubbles disappeared to obtain solution B. Solution B was added dropwise to solution A over 10 min. The mixture was then stirred at room temperature for 1.3 h, followed by the addition of sulfur powder (0.49 mmol). The reaction was continued at room temperature for another 0.7 h. After the reaction was complete, the reaction solution was concentrated and separated by column chromatography to obtain product 2 in 93% yield (yield calculation based on phosphorus atoms).

[0072] Key NMR data for product 2: 1H NMR (400MHz, CDCl3) δ2.54 (s, 9H), 6.67 (d, J = 3.2Hz, 3H), 6.81 (d, J = 3.9Hz, 3H), 7.14 (d, J = 8.6Hz, 3H), 7.54 (s, 3H), 7.80 (d, J = 8.1Hz, 3H). 13 C NMR (101MHz, CDCl3) δ21.3, 108.8 (d, J = 8.6Hz), 114.3, 121.3, 125.8, 128.1 (d, J = 6.1Hz), 132.1 (d, J = 9.0Hz), 132.6, 135.6 (d, J = 5.8Hz). 31 P NMR(162MHz,CDCl3)δ32.84(s).HRMSm / z:[M+H] + calcd for C 27 H 25 N3PS + 454.1501; Found: 454.1502.

[0073] Example 3: Synthesis of 1-{[bis(4-methylindol-1-yl)]thionyl-λ5-methphospho}-4-methylindol (Tris(4-methyl-1H-indol-1-yl)phosphine sulfide)

[0074]

[0075] In a glove box filled with nitrogen or argon, white phosphorus (0.075 mmol), diphenyl disulfide (0.45 mmol), and THF (3.0 mL) were added sequentially to a 10 mL flask ① equipped with a stirrer. The mixture was stirred at room temperature for 5 min until all the solids were dissolved to obtain solution A. 4-methylindole (1.3 mmol), sodium hydride (1.1 mmol), and THF (3.0 mL) were then added sequentially to a 10 mL flask ② equipped with a stirrer. The mixture was stirred until all bubbles disappeared to obtain solution B. Solution B was added dropwise to solution A over 10 min. The mixture was then stirred at room temperature for 1.6 h, followed by the addition of sulfur powder (0.52 mmol), and the reaction was continued at room temperature for another 0.5 h. After the reaction was complete, the reaction solution was concentrated and separated by column chromatography to obtain product 3 in 95% yield (yield calculation based on phosphorus atoms).

[0076] Key NMR data for product 3: 1H NMR (400MHz, CDCl3) δ2.62 (d, J = 2.2Hz, 9H), 6.75 (dq, J = 7.0, 3.6Hz, 6H), 7.08-7.24 (m, 6H), 7.70 (dd, J = 8.3, 3.4Hz, 3H). 13 CNMR (101MHz, CDCl3) δ18.8, 107.5 (d, J = 8.6Hz), 112.3, 123.6, 124.4, 127.5 (d, J = 6.1Hz), 131.0, 131.6 (d, J = 8.9Hz), 137.3 (d, J = 5.9Hz). 31 P{ 1 H}NMR(162MHz,CDCl3)δ33.11(s).HRMS m / z:[M+H] + calcdfor C 27 H 25 N3PS + 454.1501; Found: 454.1498.

[0077] Example 4: Synthesis of 1-{[bis(3-methylindol-1-yl)]thionyl-λ5-methphospho}-3-methylindol (Tris(3-methyl-1H-indol-1-yl)phosphine sulfide)

[0078]

[0079] In a glove box filled with nitrogen or argon, white phosphorus (0.075 mmol), diphenyl disulfide (0.53 mmol), and THF (3.0 mL) were added sequentially to a 10 mL flask ① equipped with a stirrer. The mixture was stirred at room temperature for 5 min until all the solids were dissolved to obtain solution A. 3-methylindole (0.9 mmol), sodium hydride (1.2 mmol), and THF (3.0 mL) were added sequentially to a 10 mL flask ② equipped with a stirrer. The mixture was stirred until all bubbles disappeared to obtain solution B. Solution B was added dropwise to solution A over 10 min. The mixture was then stirred at room temperature for 1.2 h, followed by the addition of sulfur powder (0.47 mmol). The reaction was continued at room temperature for another 0.6 h. After the reaction was complete, the reaction solution was concentrated and separated by column chromatography to obtain product 4 in 98% yield (yield calculation based on phosphorus atoms).

[0080] Key NMR data for product 4: 1H NMR (400MHz, CDCl3) δ2.18 (s, 9H), 6.43 (d, J = 3.5Hz, 3H), 7.21 (dt, J = 26.7, 7.4Hz, 6H), 7.54 (d, J = 7.8Hz, 3H), 7.73 (d, J = 8.3Hz, 3H). 13 C NMR (101MHz, CDCl3) δ9.8, 114.9, 118.0 (d, J = 8.3Hz), 119.5, 122.7, 124.2, 124.7 (d, J = 5.9Hz), 132.8 (d, J = 8.9Hz), 137.8 (d, J = 5.6Hz). 31 P{ 1 H}NMR(162MHz,CDCl3)δ32.08(s).HRMS m / z:[M+H] + calcd for C 27 H 25 N3PS + 454.1501; Found: 454.1505.

[0081] Example 5: Synthesis of 1-{[bis(5-methoxyindol-1-yl)]thionyl-λ5-methphosphoyl}-5-methoxyindol (Tris(5-methoxy-1H-indol-1-yl)phosphine sulfide)

[0082]

[0083] In a glove box filled with nitrogen or argon, white phosphorus (0.075 mmol), diphenyl disulfide (0.49 mmol), and THF (3.0 mL) were sequentially added to a 10 mL flask ① equipped with a stirrer. The mixture was stirred at room temperature for 5 min until all the solids were dissolved to obtain solution A. 5-methoxyindole (1.0 mmol), sodium hydride (1.0 mmol), and THF (3.0 mL) were sequentially added to a 10 mL flask ② equipped with a stirrer. The mixture was stirred until all bubbles disappeared to obtain solution B. Solution B was added dropwise to solution A over 10 min. The mixture was then stirred at room temperature for 1.4 h, followed by the addition of sulfur powder (0.45 mmol). The reaction was continued at room temperature for another 0.9 h. After the reaction was complete, the reaction solution was concentrated and separated by column chromatography to obtain product 5 in 94% yield (yield calculation based on phosphorus atoms).

[0084] Key NMR data for product 5: 1H NMR (400MHz, CDCl3) δ3.8 (s, 9H), 6.5-6.6 (m, 3H), 6.6 (t, J = 3.7Hz, 3H), 6.8 (dd, J = 9.1, 2.6Hz, 3H), 7.1 (t, J = 2.1Hz, 3H), 7.6 (d, J = 9.1Hz, 3H). 13 CNMR (101MHz, CDCl3) δ55.8, 103.8, 109.1 (d, J = 8.7Hz), 113.5, 115.4, 128.8 (d, J = 5.9Hz), 132.1 (d, J = 6.1Hz), 132.8 (d, J = 9.1Hz), 156.3. 31 P{ 1 H}NMR(162MHz,CDCl3)δ32.60(s).HRMS m / z:[M+H] + calcd for C 27 H 25 N3O3PS + 502.1349; Found: 502.1348.

[0085] Example 6: Synthesis of 1-{[bis(5-fluoroindol-1-yl)]thionyl-λ5-methphospho}-5-fluoroindol (Tris(5-fluoro-1H-indol-1-yl)phosphine sulfide)

[0086]

[0087] In a glove box filled with nitrogen or argon, white phosphorus (0.075 mmol), diphenyl disulfide (0.61 mmol), and THF (3.0 mL) were added sequentially to a 10 mL flask ① equipped with a stirrer. The mixture was stirred at room temperature for 5 min until all the solids were dissolved to obtain solution A. 5-fluoroindole (1.2 mmol), sodium hydride (0.9 mmol), and THF (3.0 mL) were added sequentially to a 10 mL flask ② equipped with a stirrer. The mixture was stirred until all bubbles disappeared to obtain solution B. Solution B was added dropwise to solution A over 10 min. The mixture was then stirred at room temperature for 1.6 h, followed by the addition of sulfur powder (0.51 mmol) and continued stirring at room temperature for another 0.6 h. After the reaction was complete, the reaction solution was concentrated and separated by column chromatography to obtain product 6 in 89% yield (yield calculation based on phosphorus atoms).

[0088] Key NMR data for product 6: 1H NMR (400MHz, CDCl3) δ6.67 (p, J=3.6Hz, 6H), 6.97 (td, J=9.0, 2.6Hz, 3H), 7.31 (dt, J=8.8, 2.1Hz, 3H), 7.70 (dd, J=9.1, 4.3Hz, 3H). 13 C NMR (126MHz, CDCl3) δ107.1 (d, J = 23.9Hz), 109.5 (dd, J = 8.5, 4.1Hz), 112.8 (d, J = 25.7Hz), 115.6 (d, J = 9.5Hz), 129.5 (d, J = 5.9Hz), 132.9 (t, J = 9.7Hz), 133.7 (d, J = 6.3Hz), 159.7 (d, J = 240.7Hz). 31 P{ 1 H}NMR(162MHz,CDCl3)δ31.95(s). 19 F NMR(471MHz,CDCl3)δ-119.47(s).HRMS m / z:[M+H] + calcd for C 24 H 16 F3N3PS + 466.0749; Found: 466.0748.

[0089] Example 7: Synthesis of 1-{[bis(5-chloroindol-1-yl)]thionyl-λ5-methphosphoyl}-5-chloroindol (Tris(5-chloro-1H-indol-1-yl)phosphine sulfide)

[0090]

[0091] In a glove box filled with nitrogen or argon, white phosphorus (0.075 mmol), diphenyl disulfide (0.47 mmol), and THF (3.0 mL) were added sequentially to a 10 mL flask ① equipped with a stirrer. The mixture was stirred at room temperature for 5 min until all the solids were dissolved to obtain solution A. 5-chloroindole (0.9 mmol), sodium hydride (1.1 mmol), and THF (3.0 mL) were added sequentially to a 10 mL flask ② equipped with a stirrer. The mixture was stirred until all bubbles disappeared to obtain solution B. Solution B was added dropwise to solution A over 10 min. The mixture was then stirred at room temperature for 1.7 h, followed by the addition of sulfur powder (0.53 mmol). The reaction was continued at room temperature for another 0.5 h. After the reaction was complete, the reaction solution was concentrated and separated by column chromatography to obtain product 7 in 81% yield (yield calculation based on phosphorus atoms).

[0092] Key NMR data for product 7: 1H NMR (400MHz, CDCl3) δ6.65 (dt, J=9.5, 3.5Hz, 6H), 7.19 (dd, J=8.8, 2.1Hz, 3H), 7.52-7.81 (m, 6H). 13 C NMR (101MHz, CDCl3) δ 109.1 (d, J = 8.4Hz), 115.5, 121.3, 124.9, 129.1 (d, J = 5.9Hz), 129.4, 133.1 (d, J = 9.1Hz), 135.7 (d, J = 6.1Hz). 31 P{ 1 H}NMR(162MHz,CDCl3)δ31.38(s).HRMS m / z:[M+H] + calcd for C 24 H 15 Cl3N3NaPS + 535.9682; Found: 535.9678.

[0093] Example 8: 1-[(bis{3-[(dimethylamino)methyl]indol-1-yl})thionyl-λ5-methylphospho]-3-[(dimethylamino)methyl]indol(Tris(3-((dimethylamino)methyl)-1H-indol-1-yl)phosphinesulfide)

[0094]

[0095] In a glove box filled with nitrogen or argon, white phosphorus (0.075 mmol), diphenyl disulfide (0.72 mmol), and THF (3.0 mL) were added sequentially to a 10 mL flask ① equipped with a stirrer. The mixture was stirred at room temperature for 5 min until all the solids were dissolved to obtain solution A. 3-[(dimethylamino)methyl]indole (1.4 mmol), sodium hydride (0.9 mmol), and THF (3.0 mL) were added sequentially to a 10 mL flask ② equipped with a stirrer. The mixture was stirred until all bubbles disappeared to obtain solution B. Solution B was added dropwise to solution A over 10 min. The mixture was then stirred at room temperature for 2.8 h, followed by the addition of sulfur powder (0.48 mmol), and the reaction was continued at room temperature for another 1 h. After the reaction was complete, the reaction solution was concentrated and separated by column chromatography, yielding product 8 in 83% yield (yield calculation based on phosphorus atoms).

[0096] Key NMR data for product 8: 1H NMR (400MHz, CDCl3) δ2.19 (s, 18H), 3.47 (s, 6H), 6.67 (d, J = 3.6Hz, 3H), 7.14 (ddd, J = 8.4 ,7.2,1.2Hz,3H),7.22(td,J=7.6,1.0Hz,3H),7.61-7.68(m,3H),7.72(d,J=7.9Hz,3H). 13 C NMR (101MHz, CDCl3) δ45.3, 54.3, 114.6, 119.7 (d, J = 8.0Hz), 120.4, 123.1, 124.4, 126.5 (d, J = 5.9Hz), 131.9 (d, J = 8.6Hz), 137.8 (d, J = 5.3Hz). 31 P{ 1 H}NMR(162MHz,CDCl3)δ32.82(s).HRMS m / z:[M+H] + calcd for C 33 H 40 N6PS + 583.2767; Found: 583.2773.

[0097] Example 9: 1-{[bis(pyrrol-1-yl)]thionyl-λ5-methphosphoyl}pyrrole (Tri(1H-pyrrol-1-yl)phosphine sulfide)

[0098]

[0099] In a glove box filled with nitrogen or argon, white phosphorus (0.075 mmol), diphenyl disulfide (0.53 mmol), and THF (3.0 mL) were added sequentially to a 10 mL flask ① equipped with a stirrer. The mixture was stirred at room temperature for 5 min until all the solids were dissolved to obtain solution A. Pyrrole (1.1 mmol), sodium hydride (1.1 mmol), and THF (3.0 mL) were added sequentially to a 10 mL flask ② equipped with a stirrer. The mixture was stirred until all bubbles disappeared to obtain solution B. Solution B was added dropwise to solution A over 10 min. The mixture was then stirred at room temperature for 1.3 h, followed by the addition of sulfur powder (0.54 mmol). The reaction was continued at room temperature for another 1 h. After the reaction was complete, the reaction solution was concentrated and separated by column chromatography to obtain product 9 in 88% yield (yield calculation based on phosphorus atoms).

[0100] Key NMR data for product 9: 1 H NMR (400MHz, CDCl3) δ6.41 (dt, J=3.9, 2.2Hz, 6H), 6.81 (dt, J=4.1, 2.2Hz, 6H).13 C NMR (101MHz, CDCl3) δ114.3 (d, J = 10.4Hz), 123.5 (d, J = 6.9Hz). 31 P{ 1 H}NMR(202MHz,CDCl3)δ42.44(s).HRMS m / z:[M+H] + calcd for C 12 H 13 N3PS + 262.0562; Found: 262.0561.

[0101] Example 10: 1-{[bis(2-methylpyrrol-1-yl)]thionyl-λ5-methphosphoyl}-2-methylpyrrole (Tris(2-methyl-1H-pyrrol-1-yl)phosphine sulfide)

[0102]

[0103] In a glove box filled with nitrogen or argon, white phosphorus (0.075 mmol), diphenyldiselenoether (0.45 mmol), and THF (3.0 mL) were added sequentially to a 10 mL flask ① equipped with a stirrer. The mixture was stirred at room temperature for 5 min until all the solids were dissolved to obtain solution A. 2-methylpyrrole (1.3 mmol), sodium hydride (1.0 mmol), and THF (3.0 mL) were then added sequentially to a 10 mL flask ② equipped with a stirrer. The mixture was stirred until all bubbles disappeared to obtain solution B. Solution B was added dropwise to solution A over 10 min. The mixture was then stirred at room temperature for 3.4 h, followed by the addition of sulfur powder (0.45 mmol), and the reaction was continued at room temperature for another 0.6 h. After the reaction was complete, the reaction solution was concentrated and separated by column chromatography to obtain product 10 in 90% yield (yield calculation based on phosphorus atoms).

[0104] Key NMR data for product 10: 1 H NMR (400MHz, CDCl3) δ2.36 (s, 9H), 6.05 (td, J = 3.5, 1.9Hz, 3H), 6.10-6.21 (m, 6H). 13 C NMR (101MHz, CDCl3) δ14.9, 111.9 (d, J = 10.7Hz), 114.7 (d, J = 9.9Hz), 123.7 (d, J = 6.2Hz), 134.4 (d, J = 6.9Hz). 31 P{ 1 H}NMR(243MHz,CDCl3)δ37.39(s).HRMS m / z:[M+H] +calcd for C 15 H 19 N3PS + 304.1032; Found: 304.1023.

[0105] Example 11: Synthesis of 9-{[di(carbazol-9-yl)]thionyl-λ5-methphosphoyl}carbazole (Tri(9H-carbazol-9-yl)phosphine sulfide)

[0106]

[0107] In a glove box filled with nitrogen or argon, white phosphorus (0.075 mmol), diphenyl disulfide (0.45 mmol), and THF (3.0 mL) were added sequentially to a 10 mL flask ① equipped with a stirrer. The mixture was stirred at room temperature for 5 min until all the solids were dissolved to obtain solution A. Carbazole (1.2 mmol), sodium hydride (1.1 mmol), and THF (3.0 mL) were added sequentially to a 10 mL flask ② equipped with a stirrer. The mixture was stirred until all bubbles disappeared to obtain solution B. Solution B was added dropwise to solution A over 10 min. The mixture was then stirred at room temperature for 1.5 h. After filtration, sulfur powder (0.57 mmol) was added to the filtrate, and the mixture was stirred at room temperature for another 0.5 h. After the reaction was complete, the reaction solution was concentrated and separated by column chromatography to obtain product 11 in 75% yield (yield calculation based on phosphorus atoms).

[0108] Key NMR data for product 11: 1 H NMR (400MHz, CDCl3) δ7.02(ddd,J=8.5,7.2,1.4Hz,6H),7.20(d,J=8.5Hz,6H),7.27(t,J=7.7Hz,6H),8.05(dd,J=7.8,1.6Hz,6H). 13 C NMR (101MHz, CDCl3) δ116.1, 120.2, 123.4, 126.9, 127.3 (d, J = 7.5Hz), 140.4 (d, J = 5.5Hz). 31 PNMR(162MHz,CDCl3)δ33.87(s).HRMS m / z:[M+H] + calcd for C 36 H 25 N3PS + 562.1501; Found: 562.1508.

[0109] Example 12: Synthesis of 10-{[di(pyrrol-1-yl)]thionyl-λ5-methphosphoyl}-phenothiazine ((10H-phenothiazin-10-yl)di(1H-pyrrol-1-yl)phosphine sulfide)

[0110]

[0111] In a glove box filled with nitrogen or argon, white phosphorus (0.075 mmol), diphenyl disulfide (0.60 mmol), and THF (3.0 mL) were added sequentially to a 10 mL flask ① equipped with a stirrer. The mixture was stirred at room temperature for 5 min until all the solids were dissolved to obtain solution A. Then, phenothiazine (0.35 mmol), pyrrole (0.67 mmol), sodium hydride (0.9 mmol), and THF (3.0 mL) were added sequentially to a 10 mL flask ② equipped with a stirrer. The mixture was stirred until all bubbles disappeared to obtain solution B. Solution B was added dropwise to solution A over 10 min. The mixture was then stirred at room temperature for 2.7 h, filtered, and sulfur powder (0.61 mmol) was added to the filtrate. The mixture was stirred at room temperature for another 0.8 h. After the reaction was complete, the reaction solution was concentrated and separated by column chromatography to obtain product 12 in 58% yield (yield calculation based on phosphorus atoms).

[0112] Key NMR data for product 12: 1 H NMR (400MHz, CDCl3) δ6.14 (dt, J=3.9, 2.2Hz, 4H), 7.08 (pd, J=7.4, 1.7Hz, 4H) ,7.30(dt,J=4.0,2.2Hz,4H),7.38(dt,J=7.2,1.7Hz,2H),7.65-7.75(m,2H). 13 C NMR (101MHz, CDCl3) δ 113.4 (d, J = 10.6Hz), 122.7 (d, J = 2.3Hz), 124.0 (d, J = 6.6Hz), 126.2, 127.5, 127.9, 131.2 (d, J = 5.0Hz), 140.7 (d, J = 7.5Hz). 31 P NMR(162MHz,CDCl3)δ44.14(s).HRMS m / z:[M+H] + calcd for C 20 H 17 N3PS2 + 394.0596; Found: 394.0594.

[0113] Application Example 1: Synthesis of 4-nitrobiphenyl

[0114]

[0115] In a glove box filled with nitrogen or argon, palladium dichloride (0.006 mmol), product 5 (Example 5 above, 0.012 mmol), p-nitrobromobenzene (0.3 mmol), phenylboronic acid (0.33 mmol), potassium carbonate (0.9 mmol), and N,N-dimethylformamide (1.5 mL) were sequentially added to a reaction flask equipped with a stirrer. The mixture was stirred at room temperature for 24 h, filtered, and separated by column chromatography to obtain p-nitrobiphenyl in 96% yield.

[0116] Key NMR data for p-nitrobenzene: 1 H NMR (400MHz, CDCl3) δ7.41-7.56(m,3H),7.59-7.67(m,2H),7.68-7.77(m,2H),8.24-8.33(m,2H). 13 C NMR (101MHz, CDCl3)δ 13 C NMR (101MHz, CDCl3) δ124.1,127.4,127.8,129.0,129.2,138.7,147.1,147.6.

[0117] Therefore, the triazaarylphosphine sulfur compounds of the present invention can be well applied in the synthesis of organic ligands.

[0118] Industrial availability

[0119] The triazaarylphosphine sulfur compounds synthesized by the preparation method of this invention have broad application prospects in the fields of organic ligand and optoelectronic material synthesis.

Claims

1. A triazaphosphine sulphide compound, which is a triazaphosphine sulphide compound represented by the following formula (I), characterized in that, wherein the three triazaphenyl groups can be the same or different; the triazaphenyl group is a substituted or unsubstituted pyrrole, imidazole, indole, carbazole, phenothiazine group; the substituent group is hydrogen, halogen, alkyl, alkoxy; the halogen is fluorine, chlorine, bromine; the alkyl is C1-C4 alkyl; the alkoxy is C1-C4 alkoxy.

2. The triazaphosphine sulfide compound according to claim 1, characterized by the triazaphenyl group is a substituted or unsubstituted pyrrole, indole, carbazole, phenothiazine group; the halogen is fluorine, chlorine; the alkyl is methyl, ethyl, n-propyl, dimethylaminomethyl; the alkoxy is methoxy, ethoxy. 3.A preparation method of a triazaphosphine sulphide compound, which is a preparation method of a triazaphosphine sulphide compound represented by the following formula (I), wherein the three triazaphenyl groups can be the same or different; the triazaphenyl group is a substituted or unsubstituted pyrrole, imidazole, indole, carbazole, phenothiazine group; the substituent group is hydrogen, halogen, alkyl, alkoxy; the halogen is fluorine, chlorine, bromine; the alkyl is C1-C4 alkyl; the alkoxy is C1-C4 alkoxy; the preparation method is as follows: 1) into a nitrogen or argon filled reactor ①, sequentially add white phosphorus, disulfide or diselenide and solvent, mixed and stirred to obtain solution A; into a nitrogen or argon filled reactor ②, sequentially add formula (II) triazaphenyl compound, base and solvent, mixed and stirred to obtain solution B; 2) the above solution B is added dropwise into the above solution A, stirring at room temperature, the first reaction time is more than 0.5 hours, then sulfur powder is added, stirring at room temperature, the continued reaction time is more than 0.2 hours, thereby preparing formula (I) compound; wherein the amount of formula (II) triazaphenyl compound used is 2.0-9.0 times molar equivalent relative to white phosphorus calculated by phosphorus atom.

4. The process for preparing a triazaphosphine sulfide compound according to claim 3, characterized by, in step 2), the first reaction time in the above method is 0.5-6 hours, and the continued reaction time is 0.2-3 hours.

5. The method of claim 3, wherein the method is characterized by, In step 1), the disulfide is diphenyl disulfide, 4,4'-dimethyldiphenyl disulfide, 4,4'-dimethoxydiphenyl disulfide, 4,4'-difluorodiphenyl disulfide, 4,4'-dichlorodiphenyl disulfide, 4,4'-dibromodiphenyl disulfide, 4,4'-dinitrodiphenyl disulfide, 4,4'-diaminodiphenyl disulfide, 4,4'-dicarboxydiphenyl disulfide, 4,4'-dihydroxydiphenyl disulfide, 3,3'-dihydroxydiphenyl disulfide, 3,3'-difluorodiphenyl disulfide, 2,2'-diaminodiphenyl sulfide, 2,2'-dithiodibenzoic acid, dithiobisbenzothiazole, bis(2-naphthyl) disulfide, bis(1-naphthyl) disulfide, 2,2'-dipyridyl disulfide, dibenzyl disulfide, di-n-butyl disulfide, the diselenide is diphenyl diselenide, 4,4'-dimethyldiphenyl diselenide, 4,4'-dimethoxydiphenyl diselenide, 4,4'-difluorodiphenyl diselenide, 4,4'-dichlorodiphenyl diselenide, 4,4'-dibromodiphenyl diselenide, 4,4'-dinitrodiphenyl diselenide, 3,3'-di-t-butyl diphenyl diselenide, 2,2'-dimethoxydiphenyl diselenide, bis(2-anthryl) diselenide, bis(2-naphthyl) diselenide, dibenzyl diselenide.

6. The method of claim 3, wherein the method is characterized by, In step 1), the base is an alkali metal compound, an alkaline earth metal compound, or an organic amine, and the alkali metal compound and the alkaline earth metal compound are respectively a hydride, a hydroxide, a carbonate, an acetate, or an organic alcoholate thereof.

7. The method of claim 3, wherein the method is characterized by, In step 1), the use ratio of the disulfide or diselenide to white phosphorus calculated in terms of phosphorus atoms is 0.5 to 5.0 times the molar equivalent, and the use ratio of the base to white phosphorus calculated in terms of phosphorus atoms is 2.0 to 5.0 times the molar equivalent. In step 2), the use ratio of the sulfur powder calculated in terms of sulfur atoms to white phosphorus calculated in terms of phosphorus atoms is 1.0 to 3.0 times the molar equivalent.

Images