A beta-carbonyl dithiophosphoric ester compound, a preparation method and application thereof

Abstract

The application belongs to the technical field of organic synthesis, and particularly relates to a kind of beta-carbonyl dithiophosphoric acid ester compounds, preparation method and application. The application is prepared by using cheap and easily available styrene, P4S 10 And alcohol as raw material, tetrabutylammonium tetrafluoroborate ( n Bu4NBF4) as electrolyte, acetonitrile (CH3CN) as solvent, beta-carbonyl dithiophosphoric acid ester compound is prepared in room temperature and air atmosphere. Compared with the preparation method reported previously, the application has the advantages of green, environmental protection, safety, high efficiency and energy saving, the raw material is easy to obtain, and the operation is simple, and has potential industrial application prospect.

Description

Technical Field

[0001] This invention belongs to the field of organic synthesis technology, specifically relating to a β-carbonyl dithiophosphate compound, its preparation method, and its application. Background Technology

[0002] β-Carbonyl dithiophosphates are an important and valuable class of compounds, widely used in pesticide research and forming crucial structural components in pesticides. For example, Dimethoate is a widely used, high-yield insecticide effective against various piercing-sucking pests on crops, such as aphids, leafhoppers, whiteflies, leaf miners, and certain scale insects. It also has some effect on mites. Mogok, as an insecticide and herbicide, can increase grain yield and inhibit androgen secretion. Phosphate, a pre-emergence herbicide, has been proven effective against barnyard grass, downregulating amino acid metabolism and primarily promoting crop carbohydrate metabolism and secondary metabolite biosynthesis with minimal impact on soil metabolism. Rice-based insecticides are suitable for controlling various pests on rice, cotton, fruit trees, and vegetables, including rice stem borers, rice planthoppers, leafhoppers, bollworms, aphids, leafhoppers, cabbage caterpillars, and diamondback moths.

[0003] In traditional methods, the skeleton of β-carbonyl dithiophosphate compounds is constructed by reacting brominated dithiophosphates with silanol ethers. However, this method involves cumbersome reaction steps, harsh reaction conditions, and the introduction and removal of activating groups. Alternatively, β-carbonyl dithiophosphates can also be synthesized by a nucleophilic substitution reaction between a chlorocarbonyl compound and a potassium O,O-dialkyl phosphate dithioester under heating conditions. However, this method also requires heating and is subject to harsh reaction conditions.

[0004] Therefore, how to provide a green, environmentally friendly, safe, efficient, readily available, and easy-to-operate β-carbonyl dithiophosphate compound and its preparation method is a technical problem that urgently needs to be solved by those skilled in the art. Summary of the Invention

[0005] In view of this, to solve this problem, the present invention discloses a β-carbonyl dithiophosphate compound, its preparation method, and its application. The present invention provides a simple and convenient method for the large-scale preparation of β-carbonyl dithiophosphate compounds using an electrochemical approach, which has advantages such as energy saving and environmental protection, readily available raw materials, mild and safe reaction conditions, and wide adaptability.

[0006] To address the shortcomings of the traditional methods mentioned above, styrene and P4S are used under electrocatalytic conditions. 10Using ROH as reactant and MeCN as solvent, a multi-component one-pot method is used to prepare β-carbonyl dithiophosphate compounds. The reaction steps are simple, the raw materials are readily available, and no oxidant or prefunctionalized substrate is required. Through a one-step reaction, olefin bifunctionalization is achieved under mild reaction conditions. The synthesis of β-carbonyl dithiophosphate compounds through a green and efficient method will be a more attractive and challenging goal.

[0007] This invention proposes a highly efficient and environmentally friendly method for the preparation of styrene through electrochemical oxidation, thereby constructing β-carbonyl dithiophosphate compounds. This method utilizes clean electrons as redox reagents, abundant and inexpensive oxygen as the oxygen source, and tetrabutylammonium tetrafluoroborate as the electrolyte. It requires no metal catalysts or additional oxidizing or reducing agents, and features mild reaction conditions, a simple reaction apparatus, and reusable electrode materials.

[0008] To achieve the above objectives, the present invention adopts the following technical solution:

[0009] The first technical objective of this invention is to provide a β-carbonyl dithiophosphate compound, the structure of which is as follows:

[0010]

[0011] Among them, R 1 It is a straight-chain alkyl, branched-chain alkyl, halogen, alkoxy, heterocyclic olefin, R 2 It can be a straight-chain alkyl, a branched alkyl, or a cycloalkyl.

[0012] The second technical objective of this invention is to provide a method for synthesizing the β-carbonyl dithiophosphate ester compounds as described above.

[0013] The synthesis method is as follows:

[0014]

[0015] Substituent R 1 R 2 As defined above.

[0016] Specifically, using styrene or substituted styrene as raw materials, under electrocatalytic conditions, P4S 10 It reacts with alcohols to form β-carbonyl dithiophosphate compounds.

[0017] Synthesis mechanism such as Figure 1 The specific details are as follows;

[0018] First, P4S 10(2) It reacts with EtOH to generate O,O-diethyl dithioester (5). Then, O,O-diethyl dithiophosphate (5) undergoes single-electron oxidation at the anode to generate sulfur radical I. Sulfur radical I is easily dimerized to O,O-diethyl S-phosphate thioate (6). Subsequently, radical intermediate I undergoes radical addition reaction with styrene (1a) to obtain benzyl radical intermediate II. Radical intermediate II is captured by O2 in the air to obtain radical intermediate III. Finally, radical intermediate III is further converted into product 4a.

[0019] Optionally, the molar ratio of substituted styrene / styrene and alcohol is 1:10-1:60, the reaction time is 4-8 hours, and the reaction temperature is 25-30℃. The reaction is carried out under constant current conditions, and a certain amount of additives are added to the reaction system. After the reaction is completed, the products are separated to obtain the β-carbonyl dithiophosphate compound.

[0020] Furthermore, the reaction is carried out in a reaction vessel equipped with a cathode and an anode, which are positioned opposite each other at a distance of 3-10 mm. Part or all of the cathode and anode are immersed in the reaction liquid of the reaction system, and the area of ​​the opposing surfaces of the anode and cathode immersed in the reaction liquid is 64-150 mm². 2 A current is applied between the cathode and anode in the reaction system.

[0021] It should be noted that after the reaction was completed, the β-carbonyl dithiophosphate compounds were separated and purified by column chromatography under TLC monitoring.

[0022] Furthermore, the reaction anode material is one of graphite, nickel, and platinum, and the reaction cathode material is one of graphite, nickel, and platinum, preferably graphite; the reaction solvent is one of dichloromethane, ethyl acetate, and acetonitrile, preferably acetonitrile; the reaction electrolyte is one of tetrabutylammonium tetrafluoroborate, tetramethylammonium tetrafluoroborate, tetrabutylammonium hexafluorophosphate, and ferric ammonium sulfate, and the molar concentration of the electrolyte in the solution is 0.006M-0.12M, preferably tetrabutylammonium tetrafluoroborate; the additive is one of 18-crown ether-6, ferrocene, and N-hydroxyphthalimide, preferably 18-crown ether-6.

[0023] Furthermore, the constant electrochemical reaction current is 6-11 mA, preferably 7 mA; the reaction time is 5-8 hours, preferably 6-7 hours; the reaction temperature is room temperature; and the reaction atmosphere is air.

[0024] It should be noted that this invention discloses a method for preparing β-carbonyl dithiophosphate compounds. Under electrochemical conditions, styrene and P4S are used. 10Using alcohols as raw materials, tetrabutylammonium tetrafluoroborate as the electrolyte, and inexpensive, readily available, and reusable graphite electrode materials, the synthesis cost and environmental impact are reduced. The corresponding β-carbonyl dithiophosphate compounds are prepared by reacting the reaction mixture at room temperature in air for 6 hours. Compared with previously reported preparation methods, this invention has advantages such as being green, environmentally friendly, safe, efficient, using readily available raw materials, and simple to operate.

[0025] The third technical objective of this invention is to provide an application of the β-carbonyl dithiophosphate compound as described above in pesticides.

[0026] Specifically, such as Figure 2 As shown, Dimethoate is a widely used and high-yielding insecticide suitable for controlling various piercing-sucking pests on crops, such as aphids, leafhoppers, whiteflies, leaf miners, and certain scale insects. It has good control effects and also has some effect on mites. Mogok, as an insecticide and herbicide, can increase grain yield and inhibit male hormone secretion. Phosphate is a pre-emergence herbicide that has been proven effective against barnyard grass, downregulates amino acid metabolism, mainly promotes crop carbohydrate metabolism and secondary metabolite biosynthesis, and has minimal impact on soil metabolism. Rice-Fengsan is suitable for controlling various pests on crops such as rice, cotton, fruit trees, and vegetables. It can be used to control rice stem borers, rice planthoppers, leafhoppers, bollworms, aphids, leafhoppers, cabbage caterpillars, and diamondback moths.

[0027] Compared with the prior art, the beneficial effects of the present invention are:

[0028] This invention employs an electrochemical method, eliminating the need for toxic and harmful reagents and solvents. The electrolyte is recyclable, reducing synthesis costs and environmental hazards. The reaction apparatus is simple, and the electrode materials are reusable, facilitating industrial production. The reaction conditions are mild, requiring no harsh conditions such as high temperature or high pressure. The raw materials used are readily available and inexpensive. The reaction is achieved through a multi-component one-pot method, making operation simple.

[0029] In summary, the method disclosed in this invention utilizes "electrons" as a cleaning agent. Without adding metals, acids, or alkalis, it requires no additional oxidizing or reducing agents. The conditions are mild, energy-saving, and environmentally friendly. The raw materials are inexpensive and readily available. The operation is simple, safe, and reliable. It can be used for large-scale preparation with a high product yield. Attached Figure Description

[0030] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on the provided drawings without creative effort.

[0031] Figure 1 This is a schematic diagram of the synthesis mechanism of the β-carbonyl dithiophosphate compounds of this invention.

[0032] Figure 2 This is a diagram showing the interaction of functional groups in the β-carbonyl dithiophosphate compounds of this invention.

[0033] Figure 3 These are the proton spectrum (a), carbon spectrum (b), and phosphorus spectrum (c) of invention 4a.

[0034] Figure 4 These are the hydrogen spectrum (a), carbon spectrum (b), and phosphorus spectrum (c) of compound 4b of the present invention.

[0035] Figure 5 These are the hydrogen spectrum (a), carbon spectrum (b), and phosphorus spectrum (c) of compound 4c of the present invention.

[0036] Figure 6 These are the proton spectrum (a), carbon spectrum (b), and phosphorus spectrum (c) of compound 4d of the present invention.

[0037] Figure 7 These are the hydrogen spectrum (a), carbon spectrum (b), phosphorus spectrum (c), and fluorine spectrum (d) of compound 4e of the present invention.

[0038] Figure 8 These are the hydrogen spectrum (a), carbon spectrum (b), and phosphorus spectrum (c) of compound 4i of the present invention. Detailed Implementation

[0039] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0040] The term "embodiment" used herein, as an example, is not necessarily to be construed as superior to or better than other embodiments. Performance testing in the embodiments of this application, unless otherwise specified, employs conventional testing methods in the art. It should be understood that the terminology used in this application is merely for describing particular implementations and is not intended to limit the scope of this disclosure.

[0041] Unless otherwise stated, the technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application pertains; other experimental methods and technical means not specifically mentioned herein refer to experimental methods and technical means commonly used by one of ordinary skill in the art.

[0042] To better illustrate the content of this application, numerous specific details are provided in the following detailed embodiments. Those skilled in the art should understand that this application can be implemented even without certain specific details. In the embodiments, some methods, means, instruments, and devices well-known to those skilled in the art are not described in detail in order to highlight the main points of this application.

[0043] Without conflict, the technical features disclosed in the embodiments of this application can be combined arbitrarily, and the resulting technical solution belongs to the content disclosed in the embodiments of this application.

[0044] This invention discloses a method for preparing β-carbonyl dithiophosphate compounds.

[0045] To better understand the present invention, the following embodiments are provided for further detailed description of the present invention, but they should not be construed as limiting the present invention. Any non-essential improvements and adjustments made by those skilled in the art based on the above-described invention are also considered to fall within the protection scope of the present invention.

[0046] Example 1

[0047]

[0048] In air, styrene (0.1 mmol) and P4S... 10 A mixture of 66.7 mg (0.15 mmol) and EtOH (290 μL, 5 mmol) was added to an undivided electrochemical flask (10 mL) equipped with graphite plates as both anode and cathode. The resulting mixture was stirred and electrolyzed at a constant current of 7 mA for 6 h at room temperature, using acetonitrile as the reaction solvent (2.5 mL), tetrabutyltetrafluoroborate as the electrolyte (0.2 mmol), and 18-crown-6 (0.1 mmol) as an additive. After the reaction was complete, the resulting mixture was evaporated under reduced pressure and purified by silica gel column chromatography using an appropriate gradient of petroleum ether and ethyl acetate to obtain the desired product 4a in 71% yield.

[0049] The target product was confirmed by nuclear magnetic resonance spectroscopy.

[0050] O,O-diethyl S-(2-oxo-2-phenylethyl) dithiophosphate (4a):TLC(Petroleum / EtOAc=10:1,v / v),R f =0.42; Yellow oil (21.6mg, 71%). 1H NMR (600MHz, CDCl3) δ7.98 (dd, J=8.1, 1.0Hz, 2H), 7.62-7.60 (m, 1H), 7.49 (t, J=7.9,2H),4.37(d,J=14.5Hz,2H),4.26-4.13(m,4H),1.36(t,J=7.1Hz,6H). 13 C NMR (150MHz, CDCl3) δ 193.1 (d, J = 4.5Hz), 135.5, 134.0, 129.0, 128.7, 64.5 (d, J = 6.0Hz), 40.9 (d, J = 3.0Hz), 16.0 (d, J = 7.5Hz). 31 P NMR (243MHz, CDCl3) δ93.98 (s).

[0051] Example 2

[0052]

[0053] The reaction steps and operations were the same as in Example 1, except that 4-methylstyrene 1b (0.1 mmol, 13 μL) was added to the reaction system and post-treated to obtain the yellow liquid target product 4b (20.2 mg, yield 63%).

[0054] The target product was confirmed by nuclear magnetic resonance spectroscopy.

[0055] O,O-diethyl S-(2-oxo-2-(p-tolyl)ethyl)dithiophosphate (4b):TLC(Petroleum / EtOAc = 10:1, v / v),R f =0.41; Yellow oil (20.2mg, 63%). 1 H NMR (600MHz, CDCl3) δ7.88(d,J=8.2Hz,2H),7.28(d,J=8.0Hz,2H),4.34(d,J=14.3Hz,2H),4.26-4.12(m,4H),2.42(s,3H),1.35(t,J=7.1Hz,6H). 13 C NMR (150MHz, CDCl3) δ192.7 (d, J = 7.5Hz), 145.0, 133.0, 129.7, 128.8, 64.5 (d, J = 7.5Hz), 40.8 (d, J = 3.0Hz), 21.9, 16.0 (d, J = 9.0Hz). 31 P NMR (600MHz, CDCl3) δ94.04 (s).

[0056] Example 3

[0057]

[0058] The reaction procedure and operation were the same as in Example 1, except that 4-chlorostyrene 1c (0.1 mmol, 12 μL) was added to the reaction system. The reaction was stopped, and after post-treatment, the target product 4c (20.2 mg, yield 60%) was obtained as a yellow liquid.

[0059] The target product was confirmed by nuclear magnetic resonance spectroscopy.

[0060] S-(2-(4-chlorophenyl)-2-oxoethyl)O,O-diethyl dithiophosphate (4c):TLC(Petroleum / EtOAc=10:1,v / v),R f =0.41; Yellow oil (20.2mg, 60%). 1 H NMR (600MHz, DMSO-d6) δ8.00(d,J=8.5Hz,2H),7.64(d,J=8.5Hz,2H),4.50(d,J=15.5Hz,2H),4.14-4.05(m,4H),1.26(t,J=7.0Hz,6H). 13 CNMR (150MHz, DMSO-d6) δ192.4 (d, J = 4.5Hz), 138.8, 133.8, 130.4, 129.0, 63.9 (d, J = 4.5Hz), 40.1, 15.5 (d, J = 9.0Hz). 31 P NMR (243MHz, CDCl3) δ92.39 (s).

[0061] Example 4

[0062]

[0063] The reaction procedure and operation were the same as in Example 1, except that 4-bromostyrene 1d (0.1 mmol, 13 μL) was added to the reaction system. The reaction was stopped, and after post-treatment, the target product 4d (26.2 mg, yield 68%) was obtained as a yellow liquid.

[0064] The target product was confirmed by nuclear magnetic resonance spectroscopy.

[0065] S-(2-(4-bromophenyl)-2-oxoethyl)O,O-diethyl dithiophosphate (4d):TLC(Petroleum / EtOAc=10:1,v / v),R f =0.37; Yellow oil (26.2mg, 68%). 1H NMR (600MHz, CDCl3) δ7.86-7.84(m,2H),7.65-7.63(m,2H),4.32(d,J=14.9Hz,2H),4.25-4.12(m,4H),1.35(t,J=7.1Hz,6H). 13 C NMR (150MHz, CDCl3) δ 192.3 (d, J = 6.0Hz), 134.2, 132.3, 130.2, 129.3, 64.6 (d, J = 6.0Hz), 40.8 (d, J = 1.5Hz), 16.0 (d, J = 9.0Hz). 31 P NMR (243MHz, CDCl3) δ93.92 (s).

[0066] Example 5

[0067]

[0068] The reaction procedure and operation were the same as in Example 1, except that 0.1 mmol (13 μL) of 4-fluorostyrene 1e was added to the reaction system. The reaction was stopped, and after post-treatment, the target product 4e (20.5 mg, yield 64%) was obtained as a yellow liquid.

[0069] The target product was confirmed by nuclear magnetic resonance spectroscopy.

[0070] O,O-diethyl S-(2-(4-fluorophenyl)-2-oxoethyl)dithiophosphate (4e):TLC(Petroleum / EtOAc=10:1,

[0071] v / v), R f =0.40; Yellow oil (20.5mg, 64%). 1 HNMR(600MHz, CDCl3)δ8.04-8.00(m,2H),

[0072] 7.18-7.14(m,2H),4.33(d,J=14.8Hz,2H),4.26-4.12(m,4H),1.35(td,J=7.1,0.5Hz,6H). 13 CNMR (150MHz, CDCl3) δ191.6 (d, J = 6.0Hz), 166.3 (d, J = 255.0Hz), 131.9 (d, J = 3.0Hz), 131.4 ( d,J=10.5Hz), 116.2(d,J=21.0Hz), 64.6(d,J=6.0Hz), 40.8(d,J=3.0Hz), 15.9(d,J=9.0Hz). 19F NMR(565MHz, CDCl3)δ-25.66(s). 31 P NMR (243MHz, CDCl3) δ94.02 (s).

[0073] Example 6

[0074]

[0075] The reaction procedure and operation were the same as in Example 1, except that 1f of 2-naphthalenestyrene (0.1 mmol, 15.42 mg) was added to the reaction system. The reaction was stopped, and after post-treatment, the target product 4f (10.1 mg, yield 28%) was obtained as a yellow liquid.

[0076] The target product was confirmed by nuclear magnetic resonance spectroscopy.

[0077] O,O-diethyl S-(2-(naphthyl-2-yl)-2-oxoethyl)dithiophosphate (4f):TLC(Petroleum / EtOAc=10:1,v / v),R f =0.38; Yellow oil (10.1mg, 28%). 1 H NMR(600MHz,DMSO-d6)δ8.74(s,1H),8.16(d,J=8.0Hz,1H),8.06-8.01(m,2H),7.99(dd,J=8.6, 1.7Hz,1H),7.72-7.64(m,2H),4.65(d,J=15.5Hz,2H),4.18-4.07(m,4H),1.27(t,J=7.0Hz,6H). 13 C NMR(150MHz,DMSO-d6)δ193.1(d,J=4.5Hz),135.2,132.4,132.1,130.7,129.7,129.0,1 28.5, 127.7, 127.2, 123.7, 63.9 (d, J = 4.5Hz), 40.1, 39.9 (d, J = 4.5Hz) 15.6 (d, J = 9.0Hz). 31 PNMR(243MHz,DMSO-d6)δ92.60(s).

[0078] Example 7

[0079]

[0080] The reaction procedure and operation were the same as in Example 1, except that 1 g (0.1 mmol, 14.41 mg) of 5-vinylbenzofuran was added to the reaction system. The reaction was stopped, and after post-treatment, 4 g (12.0 mg, 35% yield) of the target product as a yellow liquid was obtained.

[0081] The target product was confirmed by nuclear magnetic resonance spectroscopy.

[0082] S-(2-(benzofuran-5-yl)-2-oxoethyl)O,O-diethyl dithiophosphate (4g):TLC(Petroleum / EtOAc=10:1,v / v),R f =0.33; Yellow oil (12.0mg, 35%). 1 H NMR (600MHz, DMSO-d6) δ8.40(d,J=1.5Hz,1H),8.15(d,J=2.2Hz,1H),7.96(dd,J=8.7,1.7Hz,1H),7.75( d,J=8.7Hz,1H),7.13(d,J=1.4Hz,1H),4.58(d,J=15.1Hz,2H),4.17-4.06(m,4H),1.27(t,J=7.0Hz,6H). 13 CNMR (150MHz, DMSO-d6) δ192.6 (d, J = 3.0Hz), 157.0, 147.8, 130.6, 127.5, 125.0, 123.1, 111.7, 107.5, 63.8 (d, J = 4.5Hz), 40.0, 15.5 (d, J = 9.0Hz). 31 PNMR(243MHz,DMSO-d6)δ92.61(s).HRMS(ESI)m / z:Calcd for:C 14 H 17 O4PS2Na + [M+Na] + :367.0198,found 367.0194.

[0083] Example 8

[0084]

[0085] The reaction procedure and operation were the same as in Example 1, except that 5-vinylbenzofuran (0.1 mmol, 16.03 mg) was added to the reaction system for 1 hour. The reaction was stopped, and after post-treatment, the target product (13.2 mg, yield 36%) was obtained as a yellow liquid for 4 hours.

[0086] The target product was confirmed by nuclear magnetic resonance spectroscopy.

[0087] S-(2-(benzo[b]thiophen-5-yl)-2-oxoethyl)O,O-diethyl dithiophosphate (4h):TLC(Petroleum / EtOAc=10:1,v / v),R f =0.32; Yellow oil (13.2mg, 37%). 1 HNMR (600MHz, CDCl3) δ8.46 (s, 1H), 7.97-7.93 (m, 2H), 7.55 (d, J = 5.5Hz, 1H), 7.46 (d,J=5.4Hz,1H),4.45(d,J=14.4Hz,1H),4.27-4.14(m,2H),1.36(t,J=7.1Hz,6H). 13 C NMR (150MHz, CDCl3) δ192.9 (d, J = 6.0Hz), 145.1 (s), 139.6 (s), 131.9 (s), 128.4 (s), 124.8 ( d,J=3.0Hz), 123.6(s), 123.0(s), 64.6(d,J=6.0Hz), 41.0(d,J=3.0Hz), 16.0(d,J=7.5Hz). 31 P NMR(243MHz,DMSO-d6)δ92.59(s).HRMS(ESI)m / z:Calcd for C 14 H 17 O3PS3Na + [M+Na] + :382.9969,found 382.9967.

[0088] Example 9

[0089]

[0090] The reaction procedure and operation were the same as in Example 1, except that propanol 3b (5 mmol, 375 μL) was added to the reaction system. The reaction was stopped, and after post-treatment, the target product 4i (19.9 mg, yield 60%) was obtained as a yellow liquid.

[0091] The target product was confirmed by nuclear magnetic resonance spectroscopy.

[0092] S-(2-oxo-2-phenylethyl)O,O-dipropyl dithiophosphate (4i):TLC(Petroleum / EtOAc = 10:1, v / v)

[0093] R f =0.42; Yellow oil (19.9mg, 60%).1 H NMR (600MHz, DMSO-d6) δ7.98 (dd, J=8.3, 1.1Hz,

[0094] 2H),7.70-7.67(m,1H),7.58-7.55(m,2H),4.51(d,J=15.5Hz,2H),4.04-3.97(m,4H),1.67-1.61(m,4H),0.88(t,J=7.4Hz,6H). 13 C NMR (150MHz, DMSO-d6) δ193.2 (d, J = 4.5Hz), 135.1, 133.8, 128.9, 128.4, 69.1 (d, J = 6.0Hz), 40.0, 22.7 (d, J = 9.0Hz), 10.0. 31 PNMR(243MHz,DMSO-d6)δ93.18(s).HRMS(ESI)m / z:Calcd for:C 14 H 21 O3PS2Na + [M+Na] + 355.0561, found 355.0551.

[0095] Example 10

[0096]

[0097] The reaction procedure and operation were the same as in Example 1, except that butanol 3c (5 mmol, 455 μL) was added to the reaction system. The reaction was stopped, and after post-treatment, the target product 4j (27.0 mg, yield 75%) was obtained as a yellow liquid.

[0098] The target product was confirmed by nuclear magnetic resonance spectroscopy.

[0099] O,O-dibutylS-(2-oxo-2-phenylethyl)dithiophosphate (4j):TLC(Petroleum / EtOAc=10:1,v / v),R f =0.51; Yellow oil (27.0mg, 75%). 1 HNMR(600MHz,DMSO-d6)δ7.98(dd,J=7.5Hz,2H),7.69(t,J=7.3Hz,1H),7.57(t,J=7.6Hz,2H),4.5 0(d,J=15.6Hz,2H),4.10-4.00(m,4H),1.62-1.58(m,4H),1.36-1.30(m,4H),0.87(t,J=7.4,6H).13 C NMR (150MHz, DMSO-d6)δ

[0100] 193.1(d,J=4.5Hz),135.1,133.8,128.8,128.4,67.3,40.0,31.2(d,J=7.5Hz),18.3,13.3. 31 PNMR (243MHz, CDCl3) δ 94.44 (s).

[0101] Example 11

[0102]

[0103] The reaction procedure and operation were the same as in Example 1, except that 3d of pentanol (5 mmol, 543 μL) was added to the reaction system. The reaction was stopped, and after post-treatment, the target product 4k (27.0 mg, yield 70%) was obtained as a yellow liquid.

[0104] The target product was confirmed by nuclear magnetic resonance spectroscopy.

[0105] S-(2-oxo-2-phenylethyl)O,O-dipentyl dithiophosphate (4k):TLC(Petroleum / EtOAc = 10:1, v / v)

[0106] R f =0.52; Yellow oil (27.0mg, 70%). 1 HNMR(600MHz,DMSO-d6)δ7.98(m,2H),7.68(t,J=

[0107] 7.4Hz,1H),7.56(t,J=7.6Hz,2H),4.50(d,J=15.5Hz,2H),4.09-3.98(m,4H),1.64-1.59(m,4H),1.30-1.27(m,8H),0.84(t,J=7.0Hz,6H). 13 C NMR (150MHz, DMSO-d6) δ193.1 (d, J = 4.2Hz), 135.1, 133.8, 128.8, 128.4, 67.6 (d, J = 6.0Hz), 39.9, 28.9 (d, J = 7.5Hz), 27.2, 21.6, 13.8. 31 P NMR(243MHz,CDCl3)δ94.34(s).HRMS(ESI)m / z:Calcd for:C 18 H 29 O3PS2Na + [M+Na]+ 411.1187, found 411.1176.

[0108] Example 12

[0109]

[0110] The reaction procedure and operation were the same as in Example 1, except that isopropanol 3e (5 mmol, 382 μL) was added to the reaction system. The reaction was stopped, and after post-treatment, 4l of the target product (20.3 mg, yield 61%) was obtained as a yellow liquid.

[0111] The target product was confirmed by nuclear magnetic resonance spectroscopy.

[0112] O,O-diisopropyl S-(2-oxo-2-phenylethyl)dithiophosphate (4l):TLC(Petroleum / EtOAc=10:1,v / v),R f =0.50; Yellow oil (20.3mg, 61%). 1 HNMR(600MHz,DMSO-d6)δ7.98(d,J=7.1Hz,2H),7.68(t,J=7.3Hz,1H),7.56(t ,J=6.9Hz,2H),4.76-4.70(m,2H),4.50(d,J=15.4Hz,2H),1.32-1.24(m,12H). 13 C NMR (150MHz, DMSO-d6) δ193.2 (d, J = 4.5Hz), 135.2, 133.8, 128.9, 128.4, 73.5 (d, J = 7.5Hz), 40.2 (d, J = 3.0Hz), 23.3 (d, J = 3.0Hz), 23.0 (d, J = 4.5Hz). 31 P NMR(243MHz,DMSO-d6)δ88.64(s).

[0113] Example 13

[0114]

[0115] The reaction procedure and operation were the same as in Example 1, except that cyclopropanol 3f (5 mmol, 317 μL) was added to the reaction system. The reaction was stopped, and after post-treatment, the target product 4m (21.3 mg, yield 65%) was obtained as a yellow liquid.

[0116] The target product was confirmed by nuclear magnetic resonance spectroscopy.

[0117] O,O-dicyclobutyl S-(2-oxo-2-phenylethyl) dithiophosphate (4m):TLC(Petroleum / EtOAc = 10:1, v / v)

[0118] R f =0.50; Yellow oil (21.3mg, 65%). 1 H NMR (600MHz, DMSO-d6) δ7.97 (d, J = 7.4Hz, 2H),

[0119] 7.66-7.62(m,1H),7.54-7.51(m,2H),4.50-4.46(m,2H),4.08-4.04(m,2H),0.82(s,4H),0.64(t,J=7.5Hz,4H). 13 C NMR(150MHz,DMSO-d6)δ192.7(d,J=6.0Hz),134.9,133.6,128.6,128.2,79.7(t, J=33.0), 51.9 (t, J=4.5Hz), 40.1 (d, J=1.5Hz), 5.0 (d, J=6Hz), 4.8 (d, J=4.5Hz). 31 PNMR(243MHz,DMSO-d6)δ94.15(s).HRMS(ESI)m / z:Calcd for:C 14 H 17 O3PS2Na + [M+Na] + :351.0249,found 351.0240.

[0120] Example 14

[0121]

[0122] The reaction procedure and operation were the same as in Example 1, except that 3 g (5 mmol, 399 μL) of 1-cyclopropylmethyl was added to the reaction system. The reaction was stopped, and after post-treatment, the target product 4n (20.6 mg, yield 58%) was obtained as a yellow liquid.

[0123] The target product was confirmed by nuclear magnetic resonance spectroscopy.

[0124] O,O-bis(cyclopropylmethyl)S-(2-oxo-2-phenylethyl)dithiophosphate (4n):TLC(Petroleum / EtOAc = 10:1,

[0125] v / v), R f=0.51; Yellow oil (20.6mg, 58%). 1 HNMR(600MHz,DMSO-d6)δ7.99-7.98(m,2H),

[0126] 7.69(t,J=7.4Hz,1H),7.58-7.55(m,2H),4.53(d,J=15.1Hz,2H),3.94-3.87(m,4H),1.20-1.13(m,2H),0.55-0.52(m,4H),0.32-0.30(m,4H). 13 C NMR (150MHz, DMSO-d6) δ 193.2 (d, J = 4.5Hz), 135.1, 133.8, 128.9, 128.4, 72.4 (d, J = 6.0Hz), 39.9 (d, J = 3.0Hz), 10.6 (d, J = 9.0Hz), 3.4 (d, J = 9.0Hz). 31 P NMR(243MHz,DMSO-d6)δ95.92(s).HRMS(ESI)m / z:Calcd for:

[0127] C 16 H 21 O3PS2Na + [M+Na] + :379.0562,found 379.0558.

[0128] Example 15

[0129]

[0130] The reaction procedure and operation were the same as in Example 1, except that cycloheptanol (5 mmol, 575 μL) was added to the reaction system for 3 hours. The reaction was stopped, and after post-treatment, the target product 4O (17.6 mg, yield 40%) was obtained as a yellow liquid.

[0131] The target product was confirmed by nuclear magnetic resonance spectroscopy.

[0132] R f =0.49; Yellow oil (17.6mg, 40%).1 H NMR (600MHz, DMSO-d6) δ7.97(d,J=7.7Hz,2H),7.68(t,J=7.3Hz,1H),7.56(t,J=7.6Hz,2H),4.69-4.62(m,2H ),4.49(d,J=15.7Hz,2H),1.94-1.89(m,4H),1.76-1.70(m,4H),1.57(s,4H),1.49(s,8H),1.39-1.35(m,4H). 13 C NMR(150MHz,DMSO-d6)δ193.2(d,J=4.5Hz),135.2,133.8,128.9,128.4,80.5(d,J=7.5Hz),4 0.1(d,J=6.0Hz) 34.8(d,J=4.5Hz), 34.5(d,J=4.5Hz), 27.5(d,J=6.0Hz), 21.7(d,J=13.5Hz). 31 P NMR(243MHz,DMSO-d6)δ90.32(s).HRMS(ESI)m / z:Calcdfor:C 22 H 33 O3PS2Na + [M+Na] + :463.1501,found 463.1489.

[0133] Comparative Example 1

[0134] The reaction steps and operations were the same as in Example 1, except that the reaction was carried out without electricity. The reaction was stopped, and post-treatment did not yield the target product 4.

[0135] This means that the reaction cannot occur without electricity.

[0136] Comparative Example 2

[0137] The reaction steps and operations were the same as in Example 1, except that the reaction was carried out under a N2 atmosphere. The reaction was stopped, and the target product 4 was obtained in trace yields after post-processing.

[0138] This indicates that N2 conditions are unfavorable for the reaction to proceed.

[0139] Comparative Example 3

[0140] The reaction procedure and operation were the same as in Example 1, except that the reaction was carried out in the absence of electrolytes. The reaction was stopped, and the target product 4 (12.2 mg, yield 40%) was obtained after post-processing.

[0141] This indicates that the absence of electrolytes is detrimental to the reaction.

[0142] Experimental Example 1

[0143] The reaction steps and operations are the same as in Example 1, except that the reaction occurs at... 18 The reaction was carried out under O2 conditions. The reaction was stopped, and the target product was obtained after post-processing. 18 O-4a. This indicates that O2 is the oxygen source for this reaction.

[0144] Experiment Example 2

[0145] The reaction steps and operations are the same as in Example 1, except that H2 is added to the reaction system. 18 O, the reaction was stopped, and no product was detected after post-processing and high-resolution characterization. 18 O-4a indicates that H2O is not the oxygen source for this reaction.

[0146] The above description of the disclosed embodiments enables those skilled in the art to make or use the invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the invention. Therefore, the invention is not to be limited to the embodiments shown herein, but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A method for synthesizing β-carbonyl dithiophosphate compounds, characterized in that, ， Among them, R 1 It is a straight-chain alkyl, branched-chain alkyl, halogen, alkoxy, heterocyclic olefin, R 2 It can be a straight-chain alkyl, a branched alkyl, or a cycloalkyl; The reaction is carried out in a reaction vessel equipped with a cathode and an anode, which are positioned opposite each other at a distance of 3-10 mm. Part or all of the cathode and anode are immersed in the reaction liquid of the reaction system, and the area of ​​the opposite surface of the anode and cathode immersed in the reaction liquid is 64-150 mm². 2 A current is applied between the cathode and anode in the reaction system; The reaction anode material is one of graphite, nickel, and platinum; the reaction cathode material is one of graphite, nickel, and platinum; the reaction solvent is one of dichloromethane, ethyl acetate, and acetonitrile; the reaction electrolyte is one of tetrabutylammonium tetrafluoroborate, tetramethylammonium tetrafluoroborate, tetrabutylammonium hexafluorophosphate, and ferric ammonium sulfate, with a molar concentration of 0.006 M-0.12 M in the solution; the additives are 18-crown ether-6, ferrocene, and... N One of the 1,4-hydroxyphthalimides.

2. As described in claim 1 β A method for synthesizing α-carbonyl dithiophosphate compounds, characterized in that, Using styrene or substituted styrene as raw materials, under electrocatalytic conditions, P4S 10 alcohol formation β- Carbonyl dithiophosphate compounds.

3. As described in claim 2 β A method for synthesizing α-carbonyl dithiophosphate compounds, characterized in that, The molar ratio of substituted styrene / styrene and alcohol is 1:10-1:60, the reaction time is 4-8 hours, and the reaction temperature is 25-30℃.

4. As described in claim 1 β A method for synthesizing α-carbonyl dithiophosphate compounds, characterized in that, The reaction current is 6-11 mA, the reaction time is 5-8 hours, the reaction temperature is room temperature, and the reaction atmosphere is air.

Images