Synthesis method of dithiophosphonate compound

Abstract

The invention belongs to the technical field of synthesis of organic compounds, and discloses a synthesis method of a dithiophosphonate compound, which comprises the following steps of: reacting diphenylphosphine, elemental sulfur and an olefin compound or an alkyne compound under the conditions of no catalyst and no solvent to prepare the dithiophosphonate compound, the reaction time is 6-12 hours. According to the invention, diphenylphosphine and elemental sulfur are used as raw materials and can rapidly react to generate dithiophosphonic acid in situ. According to the present invention, the dithiophosphonic acid has strong acidity, such that the dithiophosphonic acid can catalyze the electrophilic addition reaction of the dithiophosphonic acid and the olefin or the alkyne so as to obtain the dithiophosphonate product, the reaction condition of the reaction is mild, the catalyst and the organic solvent are not required, the reaction by-product is less, and the green chemistry requirement is met;

Description

Technical Field

[0001] The present invention belongs to the technical field of organic compound synthesis and relates to a method for synthesizing dithiophosphonate compounds. Background Art

[0002] Due to their special chemical structures, dithiophosphonate compounds exhibit good pharmaceutical activities and are widely used in the research of pesticides and anticancer drugs. Therefore, the synthesis of dithiophosphonate compounds has received extensive attention from chemists in recent years.

[0003] The currently developed methods for synthesizing dithiophosphonates mainly fall into two categories. 1) Using functionalized phosphorus-sulfur reagents (such as dithiophosphonic acid, thiophosphoryl disulfide) as raw materials to undergo substitution or addition reactions with alkylating reagents (Bull.Chem.Soc.Jpn.1978,51,260; J.Am.Chem.Soc.1956,78,4447; J.Org.Chem.2020,85,14708). However, these functionalized sulfur-phosphorus reagents need to be prepared in advance, thus limiting their wide application. 2) Multi-step syntheses based on simple raw materials (Phosphorus and Sulfur.1981,11,157; J.Sulfur.Chem.2014,35,237; J.Am.Chem.Soc.1955,77,3526). For example, using dihydrocarbylphosphinyl chloride as a raw material, first reacting with a thiol to prepare a monothiophosphonate, and then further converting it into a dithiophosphonate under the action of Lawesson's reagent; using hydrocarbyloxyphosphine as a raw material, first reacting with Lawesson's reagent to convert it into a dihydrocarbylthiophosphorus, then undergoing an Atherton-Todd reaction to convert it into monothiophosphoryl chloride, and finally reacting with a thiol to obtain a dithiophosphonate; using dihydrocarbylphosphine chloride as a raw material and reacting with a thiol to obtain a monothiophosphinic acid ester, and then reacting with elemental sulfur to obtain a dithiophosphonate. These methods still have disadvantages such as requiring multi-step syntheses and having many separation and purification steps. Therefore, there is an urgent need to develop a new, simple and efficient method for synthesizing dithiophosphonates. Summary of the Invention

[0004] Aiming at the technical problems of many synthesis and separation steps existing in the synthesis of dithiophosphonates in the prior art, the present invention provides a method for synthesizing dithiophosphonate compounds. Using diphenylphosphine and elemental sulfur as raw materials, the two can quickly react in situ to generate dithiophosphonic acid. Since dithiophosphonic acid itself has strong acidity, it can catalyze its electrophilic addition reaction with an alkene or alkyne, and then obtain a dithiophosphonate product with fewer reaction steps; the reaction conditions of this reaction are mild, no catalyst and organic solvent are required, the reaction by-products are fewer, and the separation and purification operation is simple, meeting the requirements of green chemistry.

[0005] To achieve the above object, the present invention adopts the following technical solutions:

[0006] The present invention provides a method for synthesizing a dithiophosphonate compound, comprising the following steps: reacting diphenylphosphine, elemental sulfur with an olefin compound or an alkyne compound without a catalyst and without a solvent to prepare a dithiophosphonate compound, wherein the reaction temperature is 50-100 °C and the reaction time is 6-12 h.

[0007] Further, the molar ratio of the diphenylphosphine, elemental sulfur to the olefin compound or alkyne compound is 1:2:1.

[0008] Further, the olefin compound is selected from mono-substituted, di-substituted, tri-substituted or tetra-substituted olefins.

[0009] Further, the alkyne compound is selected from mono-substituted alkynes.

[0010] When using the olefin compound shown in Formula I as the raw material, the product dithiophosphonate compound is as shown in Formula III, and the reaction formula is as follows:

[0011]

[0012] Wherein: R 1 is phenyl; R 2 is selected from C1-C4 alkyl, optionally substituted C1-C4 alkyl, phenyl, optionally substituted phenyl, polycyclic aryl, five-membered heterocycle, six-membered heterocycle, fused heterocyclic aryl, cycloalkyl; R 3 is selected from hydrogen, C1-C4 alkyl; R 4 and R 5 are the same or different and are selected from hydrogen, C1-C4 alkyl.

[0013] Further, the substituents on the optionally substituted C1-C4 alkyl are selected from phenyl, oxygen or nitrogen.

[0014] Further, the substituents on the optionally substituted phenyl are selected from halogen, C1-C4 alkyl or methoxy.

[0015] Further, the polycyclic aryl is selected from naphthalene, anthracene or phenanthrene.

[0016] When using the olefin compound shown in Formula II as the raw material, the product dithiophosphonate compound is as shown in Formula IV, and the reaction formula is as follows:

[0017]

[0018] Wherein: R 1 is phenyl; R 6 is phenyl, optionally substituted phenyl, polycyclic aryl.

[0019] Further, the substituents of the optionally substituted phenyl are selected from halogen, C1-C4 alkyl or methoxy.

[0020] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0021] The present invention uses diphenylphosphine and elemental sulfur as raw materials, and the two can quickly react to in-situ generate dithiophosphonic acid. Since dithiophosphonic acid itself has strong acidity, it can catalyze its electrophilic addition reaction with olefins or alkynes, and then obtain dithiophosphonate products. Therefore, this reaction has few steps and can proceed efficiently without the addition of an external catalyst. Since dithiophosphonic acid can be generated in-situ and participate in the reaction, it avoids the pre-preparation and unnecessary separation and purification operations, has fewer by-products, and is more convenient to operate.

[0022] Compared with the synthesis methods in the prior art, the raw materials of the present invention are cheap and easily available, the reaction conditions are mild, there is no need to use a catalyst and organic solvents, there are fewer reaction by-products, which meets the requirements of green chemistry; this method has lower requirements for reaction conditions, the yield of the obtained product is relatively high, and it has obvious advantages compared with the known methods, and has potential wide application prospects. This method can be easily scaled up to gram-scale preparation, and the product yield is still relatively high, which is suitable for industrial scale-up preparation. Specific embodiments

[0023] The following examples are used to illustrate the present invention, but do not limit the protection scope of the present invention. Unless otherwise specified, the technical means used in the examples are conventional means well known to those skilled in the art. The test methods in the following examples are all conventional methods unless otherwise specified.

[0024] Example 1 Synthesis of (S)-1-phenylethyl diphenylphosphine dithiophosphonate

[0025]

[0026] Under a nitrogen atmosphere, diphenylphosphine (186 mg, 1.0 mmol), elemental sulfur (64.0 mg, 2.0 mmol) and styrene (104 mg, 1 mmol) were successively added to a 10 mL reaction tube, and the mixture was stirred at 70 °C for 12 h. TLC / GC-MS showed that the reaction was complete. The reaction mixture was eluted by column chromatography (ethyl acetate / petroleum ether 0 / 100 to 1 / 10 as the eluent), and the solvent was evaporated to obtain the product. The isolated yield of the product was 83%.

[0027] The 1H NMR spectrum of the product in this example is as follows: 11H NMR (600 MHz, CDCl3) δ 7.98 - 7.89 (m, 2H), 7.80 - 7.70 (m, 2H), 7.52 - 7.47 (m, 1H), 7.47 - 7.42 (m, 2H), 7.40 - 7.35 (m, 1H), 7.31 - 7.22 (m, 4H), 7.18 - 7.13 (m, 2H), 7.13 - 7.09 (m, 1H), 4.71 (dq, J = 12.6, 7.2 Hz, 1H), 1.67 (d, J = 7.2 Hz, 3H).

[0028] The 13C NMR spectrum of the product of this example is as follows: 13 13C NMR (151 MHz, CDCl3) δ 142.9 (d, J = 4.3 Hz), 135.2, 134.7, 134.1, 133.5, 131.9 (d, J = 2.6 Hz), 131.7, 131.6, 131.6 (d, J = 2.6 Hz), 131.5, 131.4, 128.7, 128.6, 128.5, 128.4, 128.3, 127.5, 127.4, 46.9, 24.1 (d, J = 4.8 Hz).

[0029] The 31P NMR spectrum of the product of this example is as follows: 31 31P NMR (243 MHz, CDCl3) δ 63.1.

[0030] Example 2 Synthesis of 1-(4-methoxyphenyl)ethyl diphenylphosphine dithiocarboxylate

[0031]

[0032] Under a nitrogen atmosphere, diphenylphosphine (186 mg, 1.0 mmol), sulfur (64.0 mg, 2.0 mmol) and 4-methoxystyrene (134 mg, 1 mmol) were successively added to a 10 mL reaction tube and stirred at 70 °C for 12 h. TLC / GC-MS showed that the reaction was complete. The reaction mixture was eluted by column chromatography (ethyl acetate / petroleum ether 0 / 100 - 1 / 10 as the eluent), and the solvent was evaporated to obtain the product. The isolated yield of the product was 85%.

[0033] The 1H NMR spectrum of the product of this example is as follows: 11H NMR (600 MHz, CDCl3) δ 7.92 (dd, J = 14.4, 7.2 Hz, 2H), 7.75 (dd, J = 14.4, 7.2 Hz, 2H), 7.52 - 7.47 (m, 1H), 7.46 - 7.41 (m, 2H), 7.41 - 7.36 (m, 1H), 7.32 - 7.27 (m, 2H), 7.17 (d, J = 8.4 Hz, 2H), 6.67 (d, J = 8.4 Hz, 2H), 4.70 (dq, J = 14.4, 7.2 Hz, 1H), 3.73 (s, 3H), 1.65 (d, J = 7.2 Hz, 3H).

[0034] The 13C NMR spectrum of the product of this example is as follows: 13 13C NMR (151 MHz, CDCl3) δ 158.8, 135.3, 134.9 (d, J = 4.4 Hz), 134.7, 134.2, 133.6, 131.9 (d, J = 2.4 Hz), 131.7 (d, J = 11.4 Hz), 131.4 (d, J = 11.0 Hz), 128.6, 128.5, 128.3 (d, J = 13.2 Hz), 113.8, 55.3, 46.6, 24.1 (d, J = 4.4 Hz).

[0035] The 31P NMR spectrum of the product of this example is as follows: 31 31P NMR (243 MHz, CDCl3) δ 62.6.

[0036] Example 3 Synthesis of 1-([1,1'-Biphenyl]-4-yl)ethyldiphenylphosphine Dithiocarboxylate

[0037]

[0038] Under a nitrogen atmosphere, diphenylphosphine (186 mg, 1.0 mmol), sulfur (64.0 mg, 2.0 mmol) and 4-phenylstyrene (180 mg, 1 mmol) were successively added to a 10 mL reaction tube and stirred at 70 °C for 12 h. TLC / GC-MS showed that the reaction was complete. The reaction mixture was eluted by column chromatography (ethyl acetate / petroleum ether 0 / 100 - 1 / 10 as the eluent), and the solvent was evaporated to obtain the product. The isolated yield of the product was 84%.

[0039] The 1H NMR spectrum of the product of this example is as follows: 11H NMR (600 MHz, CDCl3) δ 7.94 - 7.88 (m, 2H), 7.78 - 7.72 (m, 2H), 7.50 - 7.46 (m, 3H), 7.45 - 7.40 (m, 4H), 7.36 - 7.31 (m, 4H), 7.29 (d, J = 8.4 Hz, 2H), 7.26 - 7.21 (m, 2H), 4.83 - 4.71 (m, 1H), 1.71 (d, J = 7.2 Hz, 3H).

[0040] The carbon NMR spectrum of the product of this example is as follows: 13 13C NMR (151 MHz, CDCl3) δ 141.9 (d, J = 3.9 Hz), 140.9, 140.3, 135.3, 134.7, 133.8, 133.3, 131.9, 131.8 (d, J = 11.1 Hz), 131.4, 131.4, 131.3, 128.8, 128.7 (d, J = 13.1 Hz), 128.3 (d, J = 13.4 Hz), 127.9, 127.4, 127.1 (d, J = 5.7 Hz), 46.6, 23.9 (d, J = 5.4 Hz).

[0041] The phosphorus NMR spectrum of the product of this example is as follows: 31 31P NMR (243 MHz, CDCl3) δ 63.0.

[0042] Example 4 Synthesis of 1-(o-tolyl)ethyl diphenylphosphine dithiocarboxylate

[0043]

[0044] Under a nitrogen atmosphere, diphenylphosphine (186 mg, 1.0 mmol), sulfur (64.0 mg, 2.0 mmol) and 2-methylstyrene (118 mg, 1 mmol) were successively added to a 10 mL reaction tube, and the mixture was stirred at 70 °C for 12 h. TLC / GC-MS showed that the reaction was complete. The reaction mixture was eluted by column chromatography (ethyl acetate / petroleum ether 0 / 100 - 1 / 10 as the eluent), and the solvent was evaporated to obtain the product. The isolated yield of the product was 84%.

[0045] The 1H NMR spectrum of the product of this example is as follows: 11H NMR (600 MHz, CDCl3) δ 8.07 - 8.01 (m, 2H), 7.75 (dd, J = 14.4, 7.2 Hz, 2H), 7.54 - 7.45 (m, 3H), 7.42 - 7.34 (m, 2H), 7.33 - 7.28 (m, 2H), 7.14 - 7.07 (m, 2H), 7.04 (d, J = 7.2 Hz, 1H), 4.93 (dq, J = 13.8, 7.2 Hz, 1H), 2.33 (s, 3H), 1.58 (d, J = 7.2 Hz, 3H).

[0046] The 13C NMR spectrum of the product of this example is as follows: 13 13C NMR (151 MHz, CDCl3) δ 140.6 (d, J = 6.1 Hz), 135.5, 135.2, 134.9, 134.7, 134.3, 131.9 (d, J = 2.6 Hz), 131.8, 131.7, 131.4 (d, J = 11.4 Hz), 130.6, 128.6, 128.5, 128.5, 128.4, 127.4 (d, J = 25.6 Hz), 126.3, 43.6, 24.0, 19.7.

[0047] The 31P NMR spectrum of the product of this example is as follows: 31 31P NMR (243 MHz, CDCl3) δ 62.6.

[0048] Example 5 Synthesis of 1-(4-fluorophenyl)ethyl diphenylphosphine dithiocarboxylate

[0049]

[0050] Under a nitrogen atmosphere, diphenylphosphine (186 mg, 1.0 mmol), sulfur (64.0 mg, 2.0 mmol) and 4-fluorostyrene (122 mg, 1 mmol) were successively added to a 10 mL reaction tube, and the mixture was stirred at 70 °C for 12 h. TLC / GC-MS showed that the reaction was complete. The reaction mixture was eluted by column chromatography (ethyl acetate / petroleum ether 0 / 100 - 1 / 10 as the eluent), and the solvent was evaporated to obtain the product. The isolated yield of the product was 81%.

[0051] The 1H NMR spectrum of the product of this example is as follows: 11H NMR (600 MHz, CDCl3) δ 7.93 - 7.85 (m, 2H), 7.72 (dd, J = 14.4, 7.2 Hz, 2H), 7.52 - 7.47 (m, 1H), 7.47 - 7.42 (m, 2H), 7.42 - 7.37 (m, 1H), 7.31 - 7.26 (m, 2H), 7.23 - 7.17 (m, 2H), 6.78 (t, J = 8.4 Hz, 2H), 4.73 (dq, J = 14.4, 7.2 Hz, 1H), 1.66 (d, J = 7.2 Hz, 3H).

[0052] The 13C NMR spectrum of the product of this example is as follows: 13 13C NMR (151 MHz, CDCl3) δ 161.9 (d, J = 246.5 Hz), 138.7, 135.1, 134.6, 133.7, 133.1, 132.0 (d, J = 2.5 Hz), 131.8 (d, J = 11.3 Hz), 131.6 (d, J = 2.6 Hz), 131.3 (d, J = 11.4 Hz), 129.1 (d, J = 7.7 Hz), 128.7 (d, J = 13.1 Hz), 128.3 (d, J = 13.3 Hz), 115.2 (d, J = 21.3 Hz), 46.1, 24.1 (d, J = 5.6 Hz).

[0053] The 31P NMR spectrum of the product of this example is as follows: 31 31P NMR (243 MHz, CDCl3) δ 62.9.

[0054] Example 6 Synthesis of 1-(4-chlorophenyl)ethyl diphenylphosphine dithiocarboxylate

[0055]

[0056] Under a nitrogen atmosphere, diphenylphosphine (186 mg, 1.0 mmol), sulfur (64.0 mg, 2.0 mmol) and 4-chlorostyrene (138 mg, 1 mmol) were successively added to a 10 mL reaction tube and stirred at 70 °C for 12 h. TLC / GC-MS showed that the reaction was complete. The reaction mixture was eluted by column chromatography (ethyl acetate / petroleum ether 0 / 100 - 1 / 10 as the eluent), and the solvent was evaporated to obtain the product. The isolated yield of the product was 80%.

[0057] The 1H NMR spectrum of the product of this example is as follows: 11H NMR (600 MHz, CDCl3) δ 7.88 (dd, J = 14.4, 7.2 Hz, 2H), 7.71 (dd, J = 14.4, 7.2 Hz, 2H), 7.51 - 7.47 (m, 1H), 7.46 - 7.38 (m, 3H), 7.31 - 7.26 (m, 2H), 7.15 (d, J = 8.4 Hz, 2H), 7.04 (d, J = 8.4 Hz, 2H), 4.70 (dq, J = 14.4, 7.2 Hz, 1H), 1.66 (d, J = 7.2 Hz, 3H).

[0058] The carbon NMR spectrum of the product of this example is as follows: 13 13C NMR (151 MHz, CDCl3) δ 141.4 (d, J = 2.8 Hz), 135.1, 134.5, 133.5, 133.0, 132.9, 132.0 (d, J = 2.4 Hz), 131.8 (d, J = 11.2 Hz), 131.5 (d, J = 2.6 Hz), 131.3 (d, J = 11.1 Hz), 128.9, 128.7 (d, J = 13.7 Hz), 128.4, 128.3 (d, J = 13.2 Hz), 46.0, 23.8 (d, J = 5.7 Hz).

[0059] The phosphorus NMR spectrum of the product of this example is as follows: 31 31P NMR (243 MHz, CDCl3) δ 63.1.

[0060] Example 7 Synthesis of 1-(4-bromophenyl)ethyl diphenylphosphine dithiocarboxylate

[0061]

[0062] Under a nitrogen atmosphere, diphenylphosphine (186 mg, 1.0 mmol), sulfur (64.0 mg, 2.0 mmol) and 4-bromostyrene (182 mg, 1 mmol) were successively added to a 10 mL reaction tube and stirred at 70 °C for 12 h. TLC / GC-MS showed that the reaction was complete. The reaction mixture was eluted by column chromatography (ethyl acetate / petroleum ether 0 / 100 - 1 / 10 as the eluent), and the solvent was evaporated to obtain the product. The isolated yield of the product was 81%.

[0063] The 1H NMR spectrum of the product of this example is as follows: 11H NMR (600 MHz, CDCl3) δ 7.91 - 7.84 (m, 2H), 7.73 - 7.66 (m, 2H), 7.51 - 7.47 (m, 1H), 7.46 - 7.39 (m, 3H), 7.31 - 7.26 (m, 2H), 7.19 (d, J = 8.4 Hz, 2H), 7.08 (d, J = 8.4 Hz, 2H), 4.69 (dq, J = 14.4, 7.2 Hz, 1H), 1.66 (d, J = 7.2 Hz, 3H).

[0064] The carbon NMR spectrum of the product of this example is as follows: 13 13C NMR (151 MHz, CDCl3) δ 141.9 (d, J = 3.4 Hz), 135.1, 134.5, 133.4 132.8, 132.0, 131.8 (d, J = 11.5 Hz), 131.5 (d, J = 2.5 Hz), 131.4, 131.3 (d, J = 11.4 Hz), 129.2, 128.7 (d, J = 13.1 Hz), 128.3 (d, J = 13.2 Hz), 121.2. 46.1, 23.7 (d, J = 5.8 Hz).

[0065] The phosphorus NMR spectrum of the product of this example is as follows: 31 31P NMR (243 MHz, CDCl3) δ 63.1.

[0066] Example 8 Synthesis of 1-(naphthalen-2-yl)ethyl diphenylphosphine dithiocarboxylate

[0067]

[0068] Under nitrogen, diphenylphosphine (186 mg, 1.0 mmol), sulfur (64.0 mg, 2.0 mmol) and 2-vinylnaphthalene (154 mg, 1 mmol) were successively added to a 10 mL reaction tube, and the mixture was stirred at 70 °C for 12 h. TLC / GC-MS showed that the reaction was complete. The reaction mixture was eluted by column chromatography (ethyl acetate / petroleum ether 0 / 100 - 1 / 10 as the eluent), and the solvent was evaporated to obtain the product. The isolated yield of the product was 83%.

[0069] The 1H NMR spectrum of the product of this example is as follows: 11H NMR (600 MHz, CDCl3) δ 7.91 (dd, J = 14.4, 7.2 Hz, 2H), 7.73 - 7.66 (m, 3H), 7.65 - 7.61 (m, 2H), 7.58 (s, 1H), 7.50 - 7.45 (m, 1H), 7.45 - 7.36 (m, 5H), 7.16 - 7.11 (m, 1H), 7.11 - 7.04 (m, 2H), 4.89 (dq, J = 14.4, 7.2 Hz, 1H), 1.77 (d, J = 7.2 Hz, 3H).

[0070] The carbon NMR spectrum of the product of this example is as follows: 13 13C NMR (151 MHz, CDCl3) δ 139.9 (d, J = 3.8 Hz), 135.3, 134.7, 133.5, 133.0, 133.0, 132.7, 131.9, 131.7 (d, J = 11.4 Hz), 131.4 (d, J = 11.3 Hz), 131.2, 128.6 (d, J = 13.2 Hz), 128.4, 128.1, 128.0, 127.5, 126.3, 126.0 (d, J = 19.0 Hz), 125.4, 47.1, 23.8 (d, J = 4.9 Hz).

[0071] The phosphorus NMR spectrum of the product of this example is as follows: 31 31P NMR (243 MHz, CDCl3) δ 63.2.

[0072] Example 9 Synthesis of 1-(thiophen-2-yl)ethyl diphenylphosphine dithiocarboxylate

[0073]

[0074] Under a nitrogen atmosphere, diphenylphosphine (186 mg, 1.0 mmol), sulfur (64.0 mg, 2.0 mmol) and 2-thiophene ethylene (110 mg, 1 mmol) were successively added to a 10 mL reaction tube, and the mixture was stirred at 70 °C for 12 h. TLC / GC-MS showed that the reaction was complete. The reaction mixture was eluted by column chromatography (ethyl acetate / petroleum ether 0 / 100 - 1 / 10 as the eluent), and the solvent was evaporated to obtain the product. The isolated yield of the product was 78%.

[0075] The 1H NMR spectrum of the product of this example is as follows: 11H NMR (600 MHz, CDCl3) δ 7.92 (dd, J = 14.4, 7.2 Hz, 2H), 7.82 (dd, J = 14.4, 7.2 Hz, 2H), 7.52 - 7.38 (m, 4H), 7.34 (td, J = 7.8, 3.6 Hz, 2H), 7.08 (d, J = 5.4 Hz, 1H), 6.86 (d, J = 3.6 Hz, 1H), 6.70 (dd, J = 4.8, 3.6 Hz, 1H), 5.03 (dq, J = 14.4, 7.2 Hz, 1H), 1.74 (d, J = 7.2 Hz, 3H).

[0076] The 13C NMR spectrum of the product of this example is as follows: 13 13C NMR (151 MHz, CDCl3) δ 146.8 (d, J = 4.6 Hz), 135.1, 134.5, 134.1, 133.6, 132.0 (d, J = 2.5 Hz), 131.7, 131.6, 131.5 (d, J = 11.4 Hz), 128.7 (d, J = 13.1 Hz), 128.5 (d, J = 13.2 Hz), 126.5, 125.5, 124.9, 42.5, 25.3 (d, J = 4.1 Hz).

[0077] The 31P NMR spectrum of the product of this example is as follows: 31 31P NMR (243 MHz, CDCl3) δ 63.0.

[0078] Example 10 Synthesis of 1-phenylpropan-2-yl diphenylphosphine dithiocarboxylate

[0079]

[0080] Under a nitrogen atmosphere, diphenylphosphine (186 mg, 1.0 mmol), sulfur (64.0 mg, 2.0 mmol) and 3-phenylpropene (118 mg, 1 mmol) were successively added to a 10 mL reaction tube and stirred at 70 °C for 12 h. TLC / GC-MS showed that the reaction was complete. The reaction mixture was eluted by column chromatography (ethyl acetate / petroleum ether 0 / 100 - 1 / 10 as the eluent), and the solvent was evaporated to obtain the product. The isolated yield of the product was 72%.

[0081] The 1H NMR spectrum of the product of this example is as follows: 11H NMR (600 MHz, CDCl3) δ 7.97 - 7.86 (m, 4H), 7.52 - 7.37 (m, 6H), 7.27 - 7.23 (m, 2H), 7.22 - 7.18 (m, 1H), 7.16 - 7.12 (m, 2H), 3.77 - 3.65 (m, 1H), 3.07 (dd, J = 13.8, 5.4 Hz, 1H), 2.70 (dd, J = 13.8, 9.0 Hz, 1H), 1.27 (d, J = 6.6 Hz, 3H).

[0082] The 13C NMR spectrum of the product of this example is as follows: 13 13C NMR (151 MHz, CDCl3) δ 138.7, 135.5, 135.2, 134.9, 134.7, 131.8, 131.8, 131.8, 131.8, 131.6, 131.5 (d, J = 4.3 Hz), 131.4, 129.6, 128.6 (d, J = 13.3 Hz), 128.4, 126.6, 44.9 (d, J = 4.2 Hz), 44.8, 22.0 (d, J = 4.7 Hz).

[0083] The 31P NMR spectrum of the product of this example is as follows: 31 31P NMR (243 MHz, CDCl3) δ 62.8.

[0084] Example 11 Synthesis of 1-(1,3-dioxoisoindol-2-yl)ethyl diphenylphosphine dithiocarboxylate

[0085]

[0086] Under a nitrogen atmosphere, diphenylphosphine (186 mg, 1.0 mmol), sulfur (64.0 mg, 2.0 mmol) and N-vinylphthalimide (173 mg, 1 mmol) were successively added to a 10 mL reaction tube and stirred at 70 °C for 12 h. TLC / GC-MS showed that the reaction was complete. The reaction mixture was eluted by column chromatography (ethyl acetate / petroleum ether 0 / 100 - 1 / 10 as the eluent), and the solvent was evaporated to obtain the product. The isolated yield of the product was 82%.

[0087] The 1H NMR spectrum of the product of this example is as follows: 11H NMR (600 MHz, CDCl3) δ 7.87 (ddd, J = 15.6, 8.4, 1.2 Hz, 4H), 7.69 - 7.62 (m, 4H), 7.49 (dd, J = 7.8, 5.4 Hz, 1H), 7.46 - 7.40 (m, 2H), 7.14 - 7.05 (m, 3H), 6.09 (dq, J = 12.6, 7.2 Hz, 1H), 1.88 (d, J = 7.2 Hz, 3H).

[0088] The 13C NMR spectrum of the product of this example is as follows: 13 13C NMR (151 MHz, CDCl3) δ 166.2, 134.3, 134.0, 133.7, 132.8, 132.3, 132.2 (d, J = 2.1 Hz), 132.1 (d, J = 11.5 Hz), 131.5 (d, J = 12.3 Hz), 131.1 (d, J = 10.9 Hz), 128.8 (d, J = 13.7 Hz), 128.3 (d, J = 13.2 Hz), 123.3, 50.7, 22.4 (d, J = 6.1 Hz).

[0089] The 31P NMR spectrum of the product of this example is as follows: 31 31P NMR (243 MHz, CDCl3) δ 61.9.

[0090] Example 12 Synthesis of 3-(dimethylamino)-3-oxopropyl diphenylphosphine dithiocarboxylate

[0091]

[0092] Under a nitrogen atmosphere, diphenylphosphine (186 mg, 1.0 mmol), sulfur (64.0 mg, 2.0 mmol) and N,N-dimethylacrylamide (99 mg, 1 mmol) were successively added to a 10 mL reaction tube and stirred at 70 °C for 12 h. TLC / GC-MS showed that the reaction was complete. The reaction mixture was eluted by column chromatography (ethyl acetate / petroleum ether 0 / 100 - 1 / 10 as the eluent), and the solvent was evaporated to obtain the product. The isolated yield of the product was 83%.

[0093] The 1H NMR spectrum of the product of this example is as follows: 1 1H NMR (600 MHz, CDCl3) δ 8.00 - 7.93 (m, 4H), 7.53 - 7.48 (m, 2H), 7.48 - 7.43 (m, 4H), 3.26 - 3.16 (m, 2H), 2.91 (s, 3H), 2.82 (s, 3H), 2.67 (t, J = 6.6 Hz, 2H).

[0094] The 13C NMR spectrum of the product of this example is as follows:13 13C NMR (151 MHz, CDCl3) δ 170.6, 134.8, 134.3, 132.0 (d, J = 2.5 Hz), 131.6 (d, J = 11.4 Hz), 128.7 (d, J = 13.2 Hz), 37.0, 35.5, 34.3, 27.1.

[0095] The 31P NMR spectrum of the product of this example is as follows: 31 31P NMR (243 MHz, CDCl3) δ 64.7.

[0096] Example 13 Synthesis of 2-phenylpropan-2-yl diphenylphosphine dithiocarbonate

[0097]

[0098] Under a nitrogen atmosphere, diphenylphosphine (186 mg, 1.0 mmol), sulfur (64.0 mg, 2.0 mmol) and 1-methyl-1-phenylethylene (118 mg, 1 mmol) were successively added to a 10 mL reaction tube, and the mixture was stirred at 70 °C for 12 h. TLC / GC-MS showed that the reaction was complete. The reaction mixture was eluted by column chromatography (ethyl acetate / petroleum ether 0 / 100 - 1 / 10 as the eluent), and the solvent was evaporated to obtain the product. The isolated yield of the product was 80%.

[0099] The 1H NMR spectrum of the product of this example is as follows: 1 1H NMR (600 MHz, CDCl3) δ 7.90 (dd, J = 14.4, 7.8 Hz, 4H), 7.43 (d, J = 7.2 Hz, 4H), 7.40 - 7.34 (m, 4H), 7.17 (t, J = 7.8 Hz, 2H), 7.11 (t, J = 7.2 Hz, 1H), 1.98 (s, 6H).

[0100] The 13C NMR spectrum of the product of this example is as follows: 13 13C NMR (151 MHz, CDCl3) δ 145.3 (d, J = 4.3 Hz), 135.3, 134.7, 131.7 (d, J = 11.2 Hz), 131.5 (d, J = 2.4 Hz), 128.4 (d, J = 13.4 Hz), 128.1, 127.3, 126.5, 57.2 (d, J = 3.9 Hz), 31.1 (d, J = 2.7 Hz).

[0101] The 31P NMR spectrum of the product of this example is as follows: 31 31P NMR (243 MHz, CDCl3) δ 56.1.

[0102] Example 14 Synthesis of 2-(4-chlorophenyl)propan-2-yl diphenylphosphine dithiocarboxylate

[0103]

[0104] Under a nitrogen atmosphere, diphenylphosphine (186 mg, 1.0 mmol), sulfur (64.0 mg, 2.0 mmol), and 1-methyl-1-(4-chloro)styrene (152 mg, 1 mmol) were successively added to a 10 mL reaction tube and stirred at 70 °C for 12 h. TLC / GC-MS showed that the reaction was complete. The reaction mixture was eluted by column chromatography (ethyl acetate / petroleum ether 0 / 100 - 1 / 10 as the eluent), and the solvent was evaporated to obtain the product. The isolated yield of the product was 79%.

[0105] The 1H NMR spectrum of the product in this example is as follows: 1 H NMR(600MHz,CDCl3)δ7.86 - 7.77(m,4H),7.48 - 7.41(m,2H),7.39 - 7.33(m,4H),7.29(d,J = 8.4Hz,2H),6.99(d,J = 8.4Hz,2H),1.96(s,6H).

[0106] The 13C NMR spectrum of the product in this example is as follows: 13 C NMR(151MHz,CDCl3)δ143.1(d,J = 3.5Hz),134.9,134.3,133.0,131.7(d,J = 10.7Hz),131.5(d,J = 2.5Hz),128.4(d,J = 13.1Hz),128.2,127.9,56.1(d,J = 3.1Hz),31.3(d,J = 3.4Hz).

[0107] The 31P NMR spectrum of the product in this example is as follows: 31 P NMR(243MHz,CDCl3)δ56.3.

[0108] Example 15 Synthesis of bicyclo[2.2.1]heptan-2-yl diphenylphosphine dithiocarboxylate

[0109]

[0110] Under a nitrogen atmosphere, diphenylphosphine (186 mg, 1.0 mmol), sulfur (64.0 mg, 2.0 mmol), and bicyclo[2.2.1]hept-2-ene (94 mg, 1 mmol) were successively added to a 10 mL reaction tube and stirred at 70 °C for 12 h. TLC / GC-MS indicated that the reaction was complete. The reaction mixture was eluted by column chromatography (ethyl acetate / petroleum ether 0 / 100 - 1 / 10 as the eluent), and the solvent was evaporated to obtain the product. The isolated yield of the product was 85%.

[0111] The 1H NMR spectrum of the product in this example is as follows: 1 H NMR(600MHz,CDCl3)δ8.02 - 7.96(m,2H),7.95 - 7.88(m,2H),7.52 - 7.40(m,6H),3.40 - 3.28(m,1H),2.25(s,1H),2.18(d,J=4.2Hz,1H),1.83 - 1.73(m,1H),1.58 - 1.52(m,2H),1.51 - 1.44(m,1H),1.44 - 1.37(m,1H),1.23 - 1.15(m,2H),1.13 - 1.05(m,1H).

[0112] The 13C NMR spectrum of the product in this example is as follows: 13 C NMR(151MHz,CDCl3)δ135.3(d,J=9.5Hz),134.8(d,J=8.7Hz),131.8,131.8,131.8,131.8,131.6,131.5,131.5,131.4,128.6(d,J=13.3Hz),48.6,44.3,40.6(d,J=6.6Hz),36.7,36.4,28.7,28.4..

[0113] The 31P NMR spectrum of the product in this example is as follows: 31 P NMR(243MHz,CDCl3)δ62.1.

[0114] Example 16 Synthesis of 1-phenylpropyldiphenylphosphine dithiocarboxylate

[0115]

[0116] Under a nitrogen atmosphere, diphenylphosphine (186 mg, 1.0 mmol), sulfur (64.0 mg, 2.0 mmol), and 2-methyl-1-phenylethylene (118 mg, 1 mmol) were successively added into a 10 mL reaction tube and stirred at 70 °C for 12 h. TLC / GC-MS showed that the reaction was complete. The reaction mixture was eluted by column chromatography (ethyl acetate / petroleum ether 0 / 100 - 1 / 10 as the eluent), and the solvent was evaporated to obtain the product. The isolated yield of the product was 73%.

[0117] The 1H NMR spectrum of the product in this example is as follows: 1 H NMR(600MHz,CDCl3)δ7.90-7.84(m,2H),7.74-7.66(m,2H),7.51-7.46(m,1H),7.45-7.40(m,2H),7.34(ddd,J=7.2,2.4,1.2Hz,1H),7.23(ddd,J=7.8,3.6,1.8Hz,2H),7.16(dd,J=7.8,1.2Hz,2H),7.13-7.05(m,3H),4.50-4.37(m,1H),2.13-1.94(m,2H),0.85(t,J=7.2Hz,3H).

[0118] The 13C NMR spectrum of the product in this example is as follows: 13 C NMR(151MHz,CDCl3)δ141.4(d,J=3.4Hz),135.5,135.0,134.0,133.4,131.8,131.8,131.4(d,J=3.2Hz),131.2(d,J=10.9Hz),128.6(d,J=13.5Hz),128.3,128.2(d,J=13.8Hz),128.0,127.2,53.5,31.1(d,J=5.2Hz),12.3.

[0119] The 31P NMR spectrum of the product in this example is as follows: 31 P NMR(243MHz,CDCl3)δ63.5.

[0120] Example 17 Synthesis of 2-methyl-1-phenylpropan-2-yl diphenylphosphine dithiocarboxylate

[0121]

[0122] Under a nitrogen atmosphere, diphenylphosphine (186 mg, 1.0 mmol), sulfur (64.0 mg, 2.0 mmol) and 2,2-dimethyl-1-phenylethylene (132 mg, 1 mmol) were successively added into a 10 mL reaction tube, and the mixture was stirred at 70 °C for 12 h. TLC / GC-MS showed that the reaction was complete. The reaction mixture was eluted by column chromatography (ethyl acetate / petroleum ether 0 / 100 - 1 / 10 as the eluent), and the solvent was evaporated to obtain the product. The isolated yield of the product was 70%.

[0123] The 1H NMR spectrum of the product in this example is as follows: 1 H NMR(600MHz,CDCl3)δδ8.03 - 7.95(m,4H),7.51 - 7.46(m,2H),7.46 - 7.41(m,4H),7.31 - 7.21(m,5H),3.24(s,2H),1.43(s,6H).

[0124] The 13C NMR spectrum of the product in this example is as follows: 13 C NMR(151MHz,CDCl3)δ137.2,136.0,135.4,131.7,131.7,131.4,128.5(d,J = 13.1Hz),127.9,126.6,57.0,49.7,29.9(d,J = 4.7Hz).

[0125] The 31P NMR spectrum of the product in this example is as follows: 31 P NMR(243MHz,CDCl3)δ55.9.

[0126] Example 18 Synthesis of 2,3-dimethylbutan-2-yl diphenylphosphine dithiocarboxylate

[0127]

[0128] Under a nitrogen atmosphere, diphenylphosphine (186 mg, 1.0 mmol), sulfur (64.0 mg, 2.0 mmol) and 1,1,2,2-tetramethylethylene (84 mg, 1 mmol) were successively added into a 10 mL reaction tube, and the mixture was stirred at 70 °C for 12 h. TLC / GC-MS showed that the reaction was complete. The reaction mixture was eluted by column chromatography (ethyl acetate / petroleum ether 0 / 100 - 1 / 10 as the eluent), and the solvent was evaporated to obtain the product. The isolated yield of the product was 86%.

[0129] The 1H NMR spectrum of the product in this example is as follows: 11H NMR (600 MHz, CDCl3) δ 8.06 - 7.96 (m, 4H), 7.51 - 7.41 (m, 6H), 2.10 - 1.96 (m, 1H), 1.47 (s, 6H), 0.98 (d, J = 6.6 Hz, 6H).

[0130] The 13C NMR spectrum of the product of this example is as follows: 13 13C NMR (151 MHz, CDCl3) δ 136.2, 135.6, 131.7 (d, J = 11.3 Hz), 131.6 (d, J = 2.5 Hz), 128.4 (d, J = 13.1 Hz), 62.1 (d, J = 4.2 Hz), 39.7 (d, J = 4.3 Hz), 27.3 (d, J = 3.3 Hz), 18.0.

[0131] The 31P NMR spectrum of the product of this example is as follows: 31 31P NMR (243 MHz, CDCl3) δ 55.7.

[0132] Example 19 Synthesis of 3-methylhexan-3-yl diphenylphosphine dithiocarboxylate

[0133]

[0134] Under a nitrogen atmosphere, diphenylphosphine (186 mg, 1.0 mmol), sulfur (64.0 mg, 2.0 mmol) and polyisoprene (98 mg, 1 mmol) were successively added to a 10 mL reaction tube and stirred at 70 °C for 12 h. TLC / GC-MS showed that the reaction was complete. The reaction mixture was eluted by column chromatography (ethyl acetate / petroleum ether 0 / 100 - 1 / 10 as the eluent), and the solvent was evaporated to obtain the product. The isolated yield of the product was 83%.

[0135] The 1H NMR spectrum of the product of this example is as follows: 1 1H NMR (600 MHz, CDCl3) δ 7.98 (s, 4H), 7.40 (d, J = 15.6 Hz, 6H), 1.79 - 1.19 (m, 9H).

[0136] The 13C NMR spectrum of the product of this example is as follows: 13 13C NMR (151 MHz, CDCl3) δ 136.2, 135.6, 131.7, 128.6 (d, J = 12.7 Hz), 62.0, 42.1, 27.3 (d, J = 22.1 Hz), 19.7.

[0137] The 31P NMR spectrum of the product of this example is as follows: 31 31P NMR (243 MHz, CDCl3) δ 55.0.

[0138] Example 20 Synthesis of 1-Phenylvinyl Diphenylphosphine Dithiocarboxylate

[0139]

[0140] Under a nitrogen atmosphere, diphenylphosphine (186 mg, 1.0 mmol), sulfur (64.0 mg, 2.0 mmol) and phenylacetylene (102 mg, 1 mmol) were successively added into a 10 mL reaction tube, and the mixture was stirred at 70 °C for 12 h. TLC / GC-MS showed that the reaction was complete. The reaction mixture was eluted by column chromatography (ethyl acetate / petroleum ether 0 / 100 - 1 / 10 as the eluent), and the solvent was evaporated to obtain the product. The isolated yield of the product was 71%.

[0141] The 1H NMR spectrum of the product in this example is as follows: 1 H NMR(600MHz,CDCl3)δ7.94-7.87(m,4H),7.47-7.43(m,2H),7.40-7.33(m,6H),7.18-7.10(m,3H),5.98(d,J=3.6Hz,1H),5.77(d,J=3.6Hz,1H).

[0142] The 13C NMR spectrum of the product in this example is as follows: 13 C NMR(151MHz,CDCl3)δ139.5,136.6(d,J=7.0Hz),134.0,133.4,131.9,131.9,131.8,128.5(d,J=13.7Hz),128.3,128.0,127.5,127.3(d,J=8.2Hz).

[0143] The 31P NMR spectrum of the product in this example is as follows: 31 P NMR(243MHz,CDCl3)δ64.9.

[0144] Example 21 Synthesis of 1-(p-Tolyl)vinyl Diphenylphosphine Dithiocarboxylate

[0145]

[0146] Under a nitrogen atmosphere, diphenylphosphine (186 mg, 1.0 mmol), sulfur (64.0 mg, 2.0 mmol) and 4-Methylphenylacetylene (116 mg, 1 mmol) were successively added into a 10 mL reaction tube, and the mixture was stirred at 70 °C for 12 h. TLC / GC-MS showed that the reaction was complete. The reaction mixture was eluted by column chromatography (ethyl acetate / petroleum ether 0 / 100 - 1 / 10 as the eluent), and the solvent was evaporated to obtain the product. The isolated yield of the product was 73%.

[0147] The 1H NMR spectrum of the product in this example is as follows: 1 H NMR(600MHz,CDCl3)δ7.94-7.86(m,4H),7.48-7.43(m,2H),7.41-7.35(m,4H),7.27-7.23(m,2H),6.98-6.89(m,2H),5.93(d,J=3.6Hz,1H),5.70(d,J=3.6Hz,1H),2.26(s,3H).

[0148] The 13C NMR spectrum of the product in this example is as follows: 13 C NMR(151MHz,CDCl3)δ138.2,136.7,136.6(d,J=6.7Hz),134.1,133.5,131.9,131.8,128.7,128.5(d,J=13.2Hz),127.5,126.1(d,J=8.1Hz),21.2.

[0149] The 31P NMR spectrum of the product in this example is as follows: 31 P NMR(243MHz,CDCl3)δ64.7.

[0150] Example 22 Synthesis of 1-(4-methoxyphenyl)vinyl diphenylphosphine dithiocarboxylate

[0151]

[0152] Under a nitrogen atmosphere, diphenylphosphine (186 mg, 1.0 mmol), sulfur (64.0 mg, 2.0 mmol) and 4-methoxyphenylacetylene (132 mg, 1 mmol) were successively added to a 10 mL reaction tube, and the mixture was stirred at 70 °C for 12 h. TLC / GC-MS showed that the reaction was complete. The reaction mixture was eluted by column chromatography (ethyl acetate / petroleum ether 0 / 100 - 1 / 10 as the eluent), and the solvent was evaporated to obtain the product. The isolated yield of the product was 75%.

[0153] The 1H NMR spectrum of the product in this example is as follows: 1 H NMR(600MHz,CDCl3)δ7.96-7.86(m,4H),7.50-7.43(m,2H),7.42-7.37(m,4H),7.32-7.28(m,2H),6.70-6.63(m,2H),5.88(d,J=3.6Hz,1H),5.64(d,J=3.6Hz,1H),3.75(s,3H).

[0154] The 13C NMR spectrum of the product in this example is as follows: 1313C NMR (151 MHz, CDCl3) δ 159.7, 136.2 (d, J = 6.5 Hz), 134.1, 133.5, 132.1, 131.9, 131.9, 131.8, 128.9, 128.5 (d, J = 13.4 Hz), 125.3 (d, J = 7.6 Hz), 113.3, 55.4.

[0155] The 31P NMR spectrum of the product of this example is as follows: 31 31P NMR (243 MHz, CDCl3) δ 64.6.

[0156] Example 23 Synthesis of 1-(o-tolyl)vinyl diphenylphosphine dithiocarboxylate

[0157]

[0158] Under a nitrogen atmosphere, diphenylphosphine (186 mg, 1.0 mmol), sulfur (64.0 mg, 2.0 mmol) and 2-methylphenylacetylene (116 mg, 1 mmol) were successively added to a 10 mL reaction tube, and the mixture was stirred at 70 °C for 12 h. TLC / GC-MS showed that the reaction was complete. The reaction mixture was eluted by column chromatography (ethyl acetate / petroleum ether 0 / 100 - 1 / 10 as the eluent), and the solvent was evaporated to obtain the product. The isolated yield of the product was 72%.

[0159] The 1H NMR spectrum of the product of this example is as follows: 1 1H NMR (600 MHz, CDCl3) δ 7.90 - 7.75 (m, 4H), 7.44 - 7.39 (m, 2H), 7.36 - 7.30 (m, 4H), 7.03 - 6.94 (m, 3H), 6.88 - 6.82 (m, 1H), 6.01 (d, J = 3.6 Hz, 1H), 5.69 (d, J = 3.6 Hz, 1H), 2.28 (s, 3H).

[0160] The 13C NMR spectrum of the product of this example is as follows: 13 13C NMR (151 MHz, CDCl3) δ 139.8, 136.3 (d, J = 6.9 Hz), 135.3, 133.7, 133.2, 131.8, 131.7, 129.9, 129.7, 129.6, 128.4 (d, J = 13.6 Hz), 128.0, 125.3 20.2.

[0161] The 31P NMR spectrum of the product of this example is as follows: 31 31P NMR (243 MHz, CDCl3) δ 63.9.

[0162] Example 24 Synthesis of 1-(2-methoxyphenyl)vinyl diphenylphosphine dithiocarboxylate

[0163]

[0164] Under a nitrogen atmosphere, diphenylphosphine (186 mg, 1.0 mmol), sulfur (64.0 mg, 2.0 mmol) and 2-methoxyphenylacetylene (132 mg, 1 mmol) were successively added into a 10 mL reaction tube and stirred at 70 °C for 12 h. TLC / GC-MS showed that the reaction was complete. The reaction mixture was eluted by column chromatography (ethyl acetate / petroleum ether 0 / 100 - 1 / 10 as the eluent), and the solvent was evaporated to obtain the product. The isolated yield of the product was 73%.

[0165] The 1H NMR spectrum of the product in this example is as follows: 1 H NMR(600MHz,CDCl3)δ7.89-7.80(m,4H),7.44-7.38(m,2H),7.35-7.30(m,4H),7.13-7.08(m,1H),6.91(dd,J=7.2,1.8Hz,1H),6.67(d,J=8.4Hz,1H),6.63(td,J=7.2,1.2Hz,1H),5.98(d,J=3.6Hz,1H),5.84(d,J=3.6Hz,1H),3.77(s,3H).

[0166] The 13C NMR spectrum of the product in this example is as follows: 13 C NMR(151MHz,CDCl3)δ156.2,134.0,133.9(d,J=7.1Hz),133.5,131.8(d,J=10.8Hz),131.7(d,J=2.5Hz),130.6(d,J=7.7Hz),130.5,129.6,129.5,128.3(d,J=13.2Hz),120.1,110.4,55.6.

[0167] The 31P NMR spectrum of the product in this example is as follows: 31 P NMR(243MHz,CDCl3)δ64.8.

[0168] Example 25 Synthesis of 1-(2-bromophenyl)vinyl diphenylphosphine dithiocarboxylate

[0169]

[0170] Under a nitrogen atmosphere, diphenylphosphine (186 mg, 1.0 mmol), sulfur (64.0 mg, 2.0 mmol) and 2-bromo-phenylacetylene (180 mg, 1 mmol) were successively added into a 10 mL reaction tube and stirred at 70 °C for 12 h. TLC / GC-MS showed that the reaction was complete. The reaction mixture was eluted by column chromatography (ethyl acetate / petroleum ether 0 / 100 - 1 / 10 as the eluent), and the solvent was evaporated to obtain the product. The isolated yield of the product was 65%.

[0171] The 1H NMR spectrum of the product in this example is as follows: 1 H NMR(600MHz,CDCl3)δ7.90-7.78(m,4H),7.44-7.36(m,3H),7.35-7.29(m,4H),6.97-6.90(m,2H),6.87(td,J=7.2,1.2Hz,1H),6.06(d,J=3.6Hz,1H),5.86(d,J=3.6Hz,1H).

[0172] The 13C NMR spectrum of the product in this example is as follows: 13 C NMR(151MHz,CDCl3)δ140.8,136.0(d,J=7.0Hz),133.6,133.0,132.5(d,J=7.4Hz),132.3,131.8,131.8,131.7,131.4,129.3,128.4(d,J=13.5Hz),126.8,122.2.

[0173] The 31P NMR spectrum of the product in this example is as follows: 31 P NMR(243MHz,CDCl3)δ64.9.

[0174] Example 26 Synthesis of 1-(4-fluorophenyl)vinyl diphenylphosphine dithiocarboxylate

[0175]

[0176] Under a nitrogen atmosphere, diphenylphosphine (186 mg, 1.0 mmol), sulfur (64.0 mg, 2.0 mmol) and 4-fluoro-phenylacetylene (120 mg, 1 mmol) were successively added into a 10 mL reaction tube and stirred at 70 °C for 12 h. TLC / GC-MS showed that the reaction was complete. The reaction mixture was eluted by column chromatography (ethyl acetate / petroleum ether 0 / 100 - 1 / 10 as the eluent), and the solvent was evaporated to obtain the product. The isolated yield of the product was 68%.

[0177] The 1H NMR spectrum of the product in this example is as follows: 11H NMR (600 MHz, CDCl3) δ 7.92 - 7.85 (m, 4H), 7.48 - 7.43 (m, 2H), 7.41 - 7.35 (m, 4H), 7.33 - 7.28 (m, 2H), 6.83 - 6.74 (m, 2H), 5.92 (d, J = 3.6 Hz, 1H), 5.74 (d, J = 3.6 Hz, 1H).

[0178] The 13C NMR spectrum of the product of this example is as follows: 13 13C NMR (151 MHz, CDCl3) δ 162.7 (d, J = 248.3 Hz), 135.7, 135.7, 135.7, 133.9, 133.3, 132.0 (d, J = 2.6 Hz), 131.9, 131.8, 129.5 (d, J = 8.0 Hz), 128.5 (d, J = 13.5 Hz), 127.5 (d, J = 7.7 Hz), 114.8 (d, J = 21.7 Hz).

[0179] The 31P NMR spectrum of the product of this example is as follows: 31 31P NMR (243 MHz, CDCl3) δ 64.7.

[0180] Example 27 Synthesis of 1-(4-chlorophenyl)vinyl diphenylphosphine disulfide

[0181]

[0182] Under a nitrogen atmosphere, diphenylphosphine (186 mg, 1.0 mmol), sulfur (64.0 mg, 2.0 mmol) and 4-chloro-phenylacetylene (136 mg, 1 mmol) were successively added to a 10 mL reaction tube and stirred at 70 °C for 12 h. TLC / GC-MS showed that the reaction was complete. The reaction mixture was eluted by column chromatography (ethyl acetate / petroleum ether 0 / 100 - 1 / 10 as the eluent), and the solvent was evaporated to obtain the product. The isolated yield of the product was 67%.

[0183] The 1H NMR spectrum of the product of this example is as follows: 1 1H NMR (600 MHz, CDCl3) δ 7.88 (dd, J = 14.4, 7.2 Hz, 4H), 7.50 - 7.45 (m, 2H), 7.39 (td, J = 7.8, 3.6 Hz, 4H), 7.25 (s, 2H), 7.06 (d, J = 8.4 Hz, 2H), 5.98 (d, J = 3.6 Hz, 1H), 5.77 (d, J = 3.6 Hz, 1H).

[0184] The 13C NMR spectrum of the product of this example is as follows: 1313C NMR (151 MHz, CDCl3) δ 138.0, 135.7 (d, J = 6.7 Hz), 134.1, 133.8, 133.3, 132.0 (d, J = 2.5 Hz), 131.8 (d, J = 10.7 Hz), 128.9, 128.5 (d, J = 13.3 Hz), 128.1, 128.0.

[0185] The 31P NMR spectrum of the product of this example is as follows: 31 31P NMR (243 MHz, CDCl3) δ 64.8.

[0186] Example 28 Synthesis of 1-(4-bromophenyl)vinyl diphenylphosphine dithiocarboxylate

[0187]

[0188] Under a nitrogen atmosphere, diphenylphosphine (186 mg, 1.0 mmol), sulfur (64.0 mg, 2.0 mmol) and 4-bromo-phenylacetylene (180 mg, 1 mmol) were successively added to a 10 mL reaction tube and stirred at 70 °C for 12 h. TLC / GC-MS showed that the reaction was complete. The reaction mixture was eluted by column chromatography (ethyl acetate / petroleum ether 0 / 100 - 1 / 10 as the eluent), and the solvent was evaporated to obtain the product. The isolated yield of the product was 67%.

[0189] The 1H NMR spectrum of the product of this example is as follows: 1 1H NMR (600 MHz, CDCl3) δ 7.91 - 7.84 (m, 4H), 7.50 - 7.46 (m, 2H), 7.39 (ddd, J = 7.2, 3.6, 1.8 Hz, 4H), 7.24 - 7.16 (m, 4H), 5.99 (d, J = 3.6 Hz, 1H), 5.78 (d, J = 3.6 Hz, 1H).

[0190] The 13C NMR spectrum of the product of this example is as follows: 13 13C NMR (151 MHz, CDCl3) δ 138.5, 135.8 (d, J = 6.3 Hz), 133.8, 133.2, 132.0 (d, J = 2.5 Hz), 131.8 (d, J = 11.3 Hz), 131.0, 129.3, 128.5 (d, J = 13.2 Hz), 128.1 (d, J = 8.0 Hz), 122.4.

[0191] The 31P NMR spectrum of the product of this example is as follows: 31 31P NMR (243 MHz, CDCl3) δ 64.8.

[0192] Example 29 Synthesis of 1-(naphthalen-2-yl)vinyl diphenylphosphine dithiocarboxylate

[0193]

[0194] Under a nitrogen atmosphere, diphenylphosphine (186 mg, 1.0 mmol), sulfur (64.0 mg, 2.0 mmol), and 2-naphthylethyne (152 mg, 1 mmol) were successively added to a 10 mL reaction tube and stirred at 70 °C for 12 h. TLC / GC-MS showed that the reaction was complete. The reaction mixture was eluted by column chromatography (ethyl acetate / petroleum ether 0 / 100 - 1 / 10 as the eluent), and the solvent was evaporated to obtain the product. The isolated yield of the product was 83%.

[0195] The 1H NMR spectrum of the product in this example is as follows: 1 H NMR(600MHz,CDCl3)δ7.93-7.87(m,4H),7.76-7.70(m,2H),7.64-7.59(m,2H),7.47(dd,J=8.4,1.8Hz,1H),7.44-7.39(m,2H),7.38-7.35(m,2H),7.34-7.29(m,4H),6.13(d,J=3.6Hz,1H),5.89(d,J=3.6Hz,1H).

[0196] The 13C NMR spectrum of the product in this example is as follows: 13 C NMR(151MHz,CDCl3)δ136.7(d,J=9.6Hz),134.0,133.4,133.0,132.8,131.8(d,J=11.7Hz),128.4(d,J=12.9Hz),127.8(d,J=7.6Hz),127.7,127.5,127.3,126.4,126.2,124.9.

[0197] The 31P NMR spectrum of the product in this example is as follows: 31 P NMR(243MHz,CDCl3)δ64.8.

[0198] Example 30 Gram-scale synthesis of (S)-1-phenylethyl diphenylphosphine dithiocarboxylate

[0199]

[0200] Under a nitrogen atmosphere, diphenylphosphine (930 mg, 5.0 mmol), sulfur (320 mg, 10.0 mmol), and styrene (520 mg, 5.0 mmol) were successively added into a 10 mL reaction tube and stirred at 70 °C for 12 h. TLC / GC-MS showed that the reaction was complete. The reaction mixture was eluted by column chromatography (ethyl acetate / petroleum ether 0 / 100 - 1 / 10 as the eluent), and the solvent was evaporated to obtain the product. The isolated yield of the product was 85%.

[0201] The 1H NMR spectrum of the product in this example is as follows: 1 H NMR(600MHz,CDCl3)δ7.98-7.89(m,2H),7.80-7.70(m,2H),7.52-7.47(m,1H),7.47-7.42(m,2H),7.40-7.35(m,1H),7.31-7.22(m,4H),7.18-7.13(m,2H),7.13-7.09(m,1H),4.71(dq,J=12.6,7.2Hz,1H),1.67(d,J=7.2Hz,3H).

[0202] The 13C NMR spectrum of the product in this example is as follows: 13 C NMR(151MHz,CDCl3)δ142.9(d,J=4.3Hz),135.2,134.7,134.1,133.5,131.9(d,J=2.6Hz),131.7,131.6,131.6(d,J=2.6Hz),131.5,131.4,128.7,128.6,128.5,128.4,128.3,127.5,127.4,46.9,24.1(d,J=4.8Hz).

[0203] The 31P NMR spectrum of the product in this example is as follows: 31 P NMR(243MHz,CDCl3)δ63.1.

[0204] Example 3: Gram-scale synthesis of bicyclo[2.2.1]heptan-2-yl diphenylphosphine dithiocarboxylate

[0205]

[0206] Under a nitrogen atmosphere, diphenylphosphine (930 mg, 5.0 mmol), sulfur (320 mg, 10.0 mmol) and bicyclo[2.2.1]hept-2-ene (470 mg, 5.0 mmol) were successively added into a 10 mL reaction tube and stirred at 70 °C for 12 h. TLC / GC-MS showed that the reaction was complete. The reaction mixture was eluted by column chromatography (ethyl acetate / petroleum ether 0 / 100 - 1 / 10 as the eluent), and the solvent was evaporated to obtain the product. The isolated yield of the product was 85%.

[0207] The 1H NMR spectrum of the product in this example is as follows: 1 H NMR(600MHz,CDCl3)δ8.02 - 7.96(m,2H),7.95 - 7.88(m,2H),7.52 - 7.40(m,6H),3.40 - 3.28(m,1H),2.25(s,1H),2.18(d,J=4.2Hz,1H),1.83 - 1.73(m,1H),1.58 - 1.52(m,2H),1.51 - 1.44(m,1H),1.44 - 1.37(m,1H),1.23 - 1.15(m,2H),1.13 - 1.05(m,1H).

[0208] The 13C NMR spectrum of the product in this example is as follows: 13 C NMR(151MHz,CDCl3)δ135.3(d,J=9.5Hz),134.8(d,J=8.7Hz),131.8,131.8,131.8,131.8,131.6,131.5,131.5,131.4,128.6(d,J=13.3Hz),48.6,44.3,40.6(d,J=6.6Hz),36.7,36.4,28.7,28.4.

[0209] The 31P NMR spectrum of the product in this example is as follows: 31 P NMR(243MHz,CDCl3)δ62.1.

[0210] Example 3: Gram-scale synthesis of 3-methylhexan-3-yl diphenylphosphine dithiocarboxylate

[0211]

[0212] Under a nitrogen atmosphere, diphenylphosphine (930 mg, 5.0 mmol), sulfur (320 mg, 10.0 mmol) and polyisoprene (490 mg, 5 mmol) were successively added into a 10 mL reaction tube and stirred at 70 °C for 12 h. TLC / GC-MS showed that the reaction was complete. The reaction mixture was eluted by column chromatography (ethyl acetate / petroleum ether 0 / 100 - 1 / 10 as the eluent), and the solvent was evaporated to obtain the product. The isolated yield of the product was 74%.

[0213] The 1H NMR spectrum of the product in this example is as follows: 1 H NMR(600MHz,CDCl3)δ7.98(s,4H),7.40(d,J=15.6Hz,6H),1.79-1.19(m,9H).

[0214] The 13C NMR spectrum of the product in this example is as follows: 13 C NMR(151MHz,CDCl3)δ136.2,135.6,131.7,128.6(d,J=12.7Hz),62.0,42.1,27.3(d,J=22.1Hz),19.7.

[0215] The 31P NMR spectrum of the product in this example is as follows: 31 P NMR(243MHz,CDCl3)δ55.0.

[0216] Example 33 Gram-scale synthesis of 1-phenylethenyl diphenylphosphine dithiocarboxylate

[0217]

[0218] Under a nitrogen atmosphere, diphenylphosphine (930 mg, 5.0 mmol), sulfur (320 mg, 10.0 mmol) and phenylacetylene (510 mg, 5 mmol) were successively added into a 10 mL reaction tube and stirred at 70 °C for 12 h. TLC / GC-MS showed that the reaction was complete. The reaction mixture was eluted by column chromatography (ethyl acetate / petroleum ether 0 / 100 - 1 / 10 as the eluent), and the solvent was evaporated to obtain the product. The isolated yield of the product was 70%.

[0219] The 1H NMR spectrum of the product in this example is as follows: 1 H NMR(600MHz,CDCl3)δ7.94-7.87(m,4H),7.47-7.43(m,2H),7.40-7.33(m,6H),7.18-7.10(m,3H),5.98(d,J=3.6Hz,1H),5.77(d,J=3.6Hz,1H).

[0220] The 13C NMR spectrum of the product in this example is as follows:13 13C NMR (151 MHz, CDCl3) δ 139.5, 136.6 (d, J = 7.0 Hz), 134.0, 133.4, 131.9, 131.9, 131.8, 128.5 (d, J = 13.7 Hz), 128.3, 128.0, 127.5, 127.3 (d, J = 8.2 Hz).

[0221] The 31P NMR spectrum of the product of this example is as follows: 31 31P NMR (243 MHz, CDCl3) δ 64.9.

[0222] Example 34 Synthesis of (S)-1-phenylethyldiphenylphosphine dithiocarboxylate using toluene as a solvent

[0223]

[0224] Under a nitrogen atmosphere, diphenylphosphine (186 mg, 1.0 mmol), sulfur (64.0 mg, 2.0 mmol), styrene (104 mg, 1 mmol) and toluene (0.5 mL) were successively added to a 10 mL reaction tube, and the mixture was stirred at 70 °C for 12 h. TLC / GC-MS showed that the reaction was complete. The reaction mixture was eluted by column chromatography (ethyl acetate / petroleum ether 0 / 100 - 1 / 10 as the eluent), and the solvent was evaporated to obtain the product. The isolated yield of the product was 51%.

[0225] The 1H NMR spectrum of the product of this example is as follows: 1 1H NMR (600 MHz, CDCl3) δ 7.98 - 7.89 (m, 2H), 7.80 - 7.70 (m, 2H), 7.52 - 7.47 (m, 1H), 7.47 - 7.42 (m, 2H), 7.40 - 7.35 (m, 1H), 7.31 - 7.22 (m, 4H), 7.18 - 7.13 (m, 2H), 7.13 - 7.09 (m, 1H), 4.71 (dq, J = 12.6, 7.2 Hz, 1H), 1.67 (d, J = 7.2 Hz, 3H).

[0226] The 13C NMR spectrum of the product of this example is as follows: 13 13C NMR (151 MHz, CDCl3) δ 142.9 (d, J = 4.3 Hz), 135.2, 134.7, 134.1, 133.5, 131.9 (d, J = 2.6 Hz), 131.7, 131.6, 131.6 (d, J = 2.6 Hz), 131.5, 131.4, 128.7, 128.6, 128.5, 128.4, 128.3, 127.5, 127.4, 46.9, 24.1 (d, J = 4.8 Hz).

[0227] The phosphorus NMR spectrum of the product of this example is as follows: 31 P NMR(243MHz,CDCl3)δ63.1.

[0228] Example 35 Synthesis of (S)-1-phenylethyl diphenylphosphine dithiocarboxylate using tetrahydrofuran as the solvent

[0229]

[0230] Under a nitrogen atmosphere, diphenylphosphine (186 mg, 1.0 mmol), sulfur (64.0 mg, 2.0 mmol), styrene (104 mg, 1 mmol) and tetrahydrofuran (0.5 mL) were successively added to a 10 mL reaction tube, and the mixture was stirred at 70 °C for 12 h. TLC / GC-MS showed that the reaction was complete. The reaction mixture was eluted by column chromatography (ethyl acetate / petroleum ether 0 / 100 - 1 / 10 as the eluent), and the solvent was evaporated to obtain the product. The isolated yield of the product was 35%.

[0231] The proton NMR spectrum of the product of this example is as follows: 1 H NMR(600MHz,CDCl3)δ7.98-7.89(m,2H),7.80-7.70(m,2H),7.52-7.47(m,1H),7.47-7.42(m,2H),7.40-7.35(m,1H),7.31-7.22(m,4H),7.18-7.13(m,2H),7.13-7.09(m,1H),4.71(dq,J=12.6,7.2Hz,1H),1.67(d,J=7.2Hz,3H).

[0232] The carbon NMR spectrum of the product of this example is as follows: 13 C NMR(151MHz,CDCl3)δ142.9(d,J=4.3Hz),135.2,134.7,134.1,133.5,131.9(d,J=2.6Hz),131.7,131.6,131.6(d,J=2.6Hz),131.5,131.4,128.7,128.6,128.5,128.4,128.3,127.5,127.4,46.9,24.1(d,J=4.8Hz).

[0233] The phosphorus NMR spectrum of the product of this example is as follows: 31 P NMR(243MHz,CDCl3)δ63.1.

[0234] Example 36 Synthesis of (S)-1-phenylethyl diphenylphosphine dithiocarboxylate using chloroform as the solvent

[0235]

[0236] Under a nitrogen atmosphere, diphenylphosphine (186 mg, 1.0 mmol), sulfur (64.0 mg, 2.0 mmol), styrene (104 mg, 1 mmol) and chloroform (0.5 mL) were successively added into a 10 mL reaction tube, and the mixture was stirred at 70 °C for 12 h. TLC / GC-MS showed that the reaction was complete. The reaction mixture was eluted by column chromatography (ethyl acetate / petroleum ether 0 / 100 - 1 / 10 as the eluent), and the solvent was evaporated to obtain the product. The isolated yield of the product was 48%.

[0237] The 1H NMR spectrum of the product in this example is as follows: 1 H NMR(600MHz,CDCl3)δ7.98 - 7.89(m,2H),7.80 - 7.70(m,2H),7.52 - 7.47(m,1H),7.47 - 7.42(m,2H),7.40 - 7.35(m,1H),7.31 - 7.22(m,4H),7.18 - 7.13(m,2H),7.13 - 7.09(m,1H),4.71(dq,J=12.6,7.2Hz,1H),1.67(d,J=7.2Hz,3H).

[0238] The 13C NMR spectrum of the product in this example is as follows: 13 C NMR(151MHz,CDCl3)δ142.9(d,J=4.3Hz),135.2,134.7,134.1,133.5,131.9(d,J=2.6Hz),131.7,131.6,131.6(d,J=2.6Hz),131.5,131.4,128.7,128.6,128.5,128.4,128.3,127.5,127.4,46.9,24.1(d,J=4.8Hz).

[0239] The 31P NMR spectrum of the product in this example is as follows: 31 P NMR(243MHz,CDCl3)δ63.1.

[0240] Example 37 Synthesis of (S)-1-phenylethyl diphenylphosphine dithiocarboxylate

[0241]

[0242] Under a nitrogen atmosphere, diphenylphosphine (186 mg, 1.0 mmol), sulfur (64.0 mg, 2.0 mmol) and styrene (104 mg, 1 mmol) were successively added into a 10 mL reaction tube, and the mixture was stirred at 50 °C for 12 h. TLC / GC-MS showed that the reaction was complete. The reaction mixture was eluted by column chromatography (ethyl acetate / petroleum ether 0 / 100 - 1 / 10 as the eluent), and the solvent was evaporated to obtain the product. The isolated yield of the product was 71%.

[0243] The 1H NMR spectrum of the product in this example is as follows: 1 H NMR (600 MHz, CDCl3) δ 7.98 - 7.89 (m, 2H), 7.80 - 7.70 (m, 2H), 7.52 - 7.47 (m, 1H), 7.47 - 7.42 (m, 2H), 7.40 - 7.35 (m, 1H), 7.31 - 7.22 (m, 4H), 7.18 - 7.13 (m, 2H), 7.13 - 7.09 (m, 1H), 4.71 (dq, J = 12.6, 7.2 Hz, 1H), 1.67 (d, J = 7.2 Hz, 3H).

[0244] The 13C NMR spectrum of the product in this example is as follows: 13 C NMR (151 MHz, CDCl3) δ 142.9 (d, J = 4.3 Hz), 135.2, 134.7, 134.1, 133.5, 131.9 (d, J = 2.6 Hz), 131.7, 131.6, 131.6 (d, J = 2.6 Hz), 131.5, 131.4, 128.7, 128.6, 128.5, 128.4, 128.3, 127.5, 127.4, 46.9, 24.1 (d, J = 4.8 Hz).

[0245] The 31P NMR spectrum of the product in this example is as follows: 31 P NMR (243 MHz, CDCl3) δ 63.1.

[0246] Example 38 Synthesis of (S)-1-Phenylethyldiphenylphosphine Dithiocarboxylate

[0247]

[0248] Under a nitrogen atmosphere, diphenylphosphine (186 mg, 1.0 mmol), sulfur (64.0 mg, 2.0 mmol) and styrene (104 mg, 1 mmol) were successively added into a 10 mL reaction tube, and the mixture was stirred at 100 °C for 12 h. TLC / GC-MS showed that the reaction was complete. The reaction mixture was eluted by column chromatography (ethyl acetate / petroleum ether 0 / 100 - 1 / 10 as the eluent), and the solvent was evaporated to obtain the product. The isolated yield of the product was 83%.

[0249] The 1H NMR spectrum of the product of this example is as follows: 1 H NMR(600MHz,CDCl3)δ7.98-7.89(m,2H),7.80-7.70(m,2H),7.52-7.47(m,1H),7.47-7.42(m,2H),7.40-7.35(m,1H),7.31-7.22(m,4H),7.18-7.13(m,2H),7.13-7.09(m,1H),4.71(dq,J=12.6,7.2Hz,1H),1.67(d,J=7.2Hz,3H).

[0250] The 13C NMR spectrum of the product of this example is as follows: 13 C NMR(151MHz,CDCl3)δ142.9(d,J=4.3Hz),135.2,134.7,134.1,133.5,131.9(d,J=2.6Hz),131.7,131.6,131.6(d,J=2.6Hz),131.5,131.4,128.7,128.6,128.5,128.4,128.3,127.5,127.4,46.9,24.1(d,J=4.8Hz).

[0251] The 31P NMR spectrum of the product of this example is as follows: 31 P NMR(243MHz,CDCl3)δ63.1.

[0252] The above-mentioned embodiments are only the preferred embodiments of the present invention, which are only used to explain the present invention and do not limit the scope of implementation of the present invention. For those skilled in the art of this technology, of course, other implementation manners can be easily made according to the technical content disclosed in this specification by means of substitution or change. Therefore, all changes and improvements made on the principle of the present invention should be included in the scope of the patent application of the present invention.

Claims

1. A method for synthesizing a dithiophosphonate compound, characterized in that: The following steps are involved: Diphenylphosphine, elemental sulfur and olefin compounds or alkyne compounds are reacted in the absence of catalyst and solvent to prepare dithiophosphonate compounds, the reaction temperature is 50-100° C., and the reaction time is 6-12 hours.

2. The synthesis method according to claim 1, characterized in that The molar ratio of the diphenylphosphine, elemental sulfur and olefin compound or alkyne compound is 1:2:

1.

3. The synthesis method according to claim 1, characterized in that The olefin compound is selected from monosubstituted, disubstituted, trisubstituted or tetrasubstituted olefins.

4. The synthesis method according to claim 1, characterized in that The alkyne compound is selected from a substituted alkyne.

5. The synthesis method according to claim 1 or 3, characterized in that: The following steps are involved: Diphenylphosphine, elemental sulfur and the olefin compound shown in formula I are reacted in the absence of a catalyst and a solvent to prepare the dithiophosphonate compound shown in formula III. The above reaction formula is as follows: Where: R 1 is phenyl; R 2 is selected from C1-C4 alkyl, optionally substituted C1-C4 alkyl, phenyl, optionally substituted phenyl, polycyclic aromatic group, five-membered heterocyclic ring, six-membered heterocyclic ring, fused heterocyclic aromatic group, and cycloalkyl; R 3 Selected from hydrogen, C1-C4 alkyl; R 4 and R 5 The same or different groups are selected from hydrogen, C1-C4 alkyl.

6. The synthesis method according to claim 5, characterized in that The substituents on the optionally substituted C1-C4 alkyl group are selected from phenyl, oxygen or nitrogen.

7. The synthesis method according to claim 5, characterized in that The substituent on the optionally substituted phenyl group is selected from halogen, C1-C4 alkyl or methoxy.

8. The synthesis method according to claim 5, characterized in that The polycyclic aromatic group is selected from naphthalene, anthracene or phenanthrene.

9. The synthesis method according to claim 1 or 4, characterized in that: The following steps are involved: The dithiophosphonate compound shown in Formula IV is prepared by reacting diphenylphosphine, elemental sulfur and the alkyne compound shown in Formula II under catalyst-free and solvent-free conditions. The above reaction formula is as follows: Where: R 1 is phenyl; R 6 It is a phenyl group, an optionally substituted phenyl group, or a polycyclic aromatic group.

10. The synthesis method according to claim 9, characterized in that The substituent of the optionally substituted phenyl group is selected from halogen, C1-C4 alkyl or methoxy.

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