Beta-carbonyl dithiophosphate compound as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of organic synthesis, and particularly relates to a beta-carbonyl dithiophosphate compound as well as a preparation method and application thereof. Under electrochemical reaction conditions, styrene, P4S10 and alcohol which are cheap and easy to obtain are used as raw materials, tetrabutylammonium tetrafluoroborate (nBu4NBF4) is used as an electrolyte, acetonitrile (CH3CN) is used as a solvent, and the beta-carbonyl dithiophosphate compound is prepared at room temperature in an air atmosphere. Compared with a previously reported preparation method, the method has the advantages of being green, environmentally friendly, safe, efficient and energy-saving, raw materials are easy to obtain, operation is easy and convenient, and potential industrial application prospects are achieved.

Description

Technical Field

[0001] The present invention belongs to the technical field of organic synthesis, and particularly relates to a β-carbonyl dithiophosphate compound, a preparation method and an application thereof. Background Art

[0002] β-Carbonyl dithiophosphates are a class of important and highly valuable compounds, which are often widely used in the field of pesticide research and are important backbone fragments of pesticides. For example, Dimethoate is an insecticide with a wide range of uses and large production. It is suitable for controlling piercing-sucking mouthpart pests on various crops, such as aphids, leafhoppers, whiteflies, leaf-mining pests and certain scale insects, etc., and has good control effects. It also has certain control effects on mites. As an insecticide and herbicide, Morpholine can increase grain yield and anti-androgen secretion. Anilofos is a pre-emergence herbicide that has been proven to be effective against barnyard grass. It can down-regulate amino acid metabolism, mainly promote carbohydrate metabolism and biosynthesis of secondary metabolites in crops, and have the least impact on soil metabolism. Phenthoate is suitable for controlling various pests on crops such as rice, cotton, fruit trees, and vegetables, and can be used to control Chilo suppressalis, Tryporyza incertulas, Nilaparvata lugens, Oulema oryzae, Helicoverpa armigera, aphids, leafhoppers, Pieris rapae, Plutella xylostella, etc.

[0003] In traditional methods, the skeleton of β-carbonyl dithiophosphate compounds is constructed by reacting bromodithiophosphate with silyl enol ether. However, this method has cumbersome reaction steps, harsh reaction conditions, and involves the introduction and leaving of activating groups. In addition, β-carbonyl dithiophosphate can also be synthesized by the nucleophilic substitution reaction of chloro-carbonyl compounds with potassium O,O-dialkyl phosphorodithioate under heating conditions. However, this method needs to be carried out under heating conditions, and the reaction conditions are harsh.

[0004] Therefore, how to provide a β-carbonyl dithiophosphate compound and its preparation method that are green, environmentally friendly, safe, efficient, with easily available raw materials and simple operation is a technical problem that those skilled in the art urgently need to solve. Summary of the Invention

[0005] In view of this, to solve this problem, the present invention discloses a β-carbonyl dithiophosphate compound, a preparation method and an application thereof. The present invention discloses a method for simply and conveniently preparing a large amount of β-carbonyl dithiophosphate compounds by an electrochemical method, which has the advantages of energy conservation, environmental protection, easily available raw materials, mild and safe reaction conditions, wide adaptability, etc.

[0006] Aiming at the defects of the above traditional methods, under electrocatalytic conditions, using styrene, P4S 10, Using ROH as a reactant and MeCN as a solvent, the β-carbonyl dithiophosphates are prepared by a multi-component one-pot method. The reaction steps are simple, the raw materials are simple and easily available, no oxidant is required, no pre-functionalized substrate is needed, and the difunctionalization of olefins is achieved through a one-step reaction under mild reaction conditions. Synthesizing β-carbonyl dithiophosphates by a green and efficient method will be a more attractive and challenging goal.

[0007] The present invention provides an efficient, green and environmentally friendly preparation method for the functionalization of styrene through electrochemical oxidation to construct β-carbonyl dithiophosphates. This method uses clean "electrons" as redox reagents, abundant and inexpensive oxygen as the oxygen source, tetrabutylammonium tetrafluoroborate as the electrolyte, without the need for a metal catalyst, and without the additional addition of an oxidant or a reductant. It has the characteristics of mild reaction conditions, simple reaction equipment, and reusable electrode materials.

[0008] To achieve the above object, the present invention adopts the following technical solutions:

[0009] The first technical object of the present invention is to provide a β-carbonyl dithiophosphate compound, and the structure of the β-carbonyl dithiophosphate compound is as follows:

[0010]

[0011] Wherein, R 1 is a straight-chain alkyl group, a branched-chain alkyl group, a halogen, an alkoxy group, a heteroaromatic olefin, and R 2 is a straight-chain alkyl group, a branched-chain alkyl group, or a cycloalkyl group.

[0012] The second technical object of the present invention is to provide a synthesis method of the β-carbonyl dithiophosphate compound as described above.

[0013] The synthesis method is as follows:

[0014]

[0015] The substituents R 1 , R 2 are as defined above.

[0016] Specifically, using styrene or substituted styrene as a raw material, under electrocatalytic conditions, β-carbonyl dithiophosphates are formed with P4S 10 and an alcohol.

[0017] The synthesis mechanism is as Figure 1 , and the specific description is as follows;

[0018] First, P4S 10(2) reacts with EtOH to form O,O - diethyl dithiophosphate (5). Then, O,O - diethyl dithiophosphate (5) undergoes single - electron oxidation at the anode to generate sulfur radical I, and sulfur radical I easily dimerizes to form O,O - diethyl S - thiophosphoric acid hydrogen (6); subsequently, the radical intermediate I undergoes a radical addition reaction with styrene (1a) to obtain a benzyl radical intermediate II, and the radical intermediate II is captured by O₂ in the air to obtain a radical intermediate III; finally, the radical intermediate III is further transformed into product 4a.

[0019] Optionally, the molar ratio of substituted styrene / styrene to alcohol is 1:10 - 1:60, the reaction time is 4 - 8 hours, and the reaction temperature is 25 - 30 °C; the reaction is carried out under constant current conditions, and a certain amount of additive needs to be added to the reaction system. After the reaction is completed, product separation is carried out to obtain the β - carbonyl dithiophosphate compounds.

[0020] Furthermore, the reaction is carried out in a reaction vessel equipped with a cathode and an anode. The anode and the cathode are arranged opposite to each other with a distance of 3 - 10 mm. Part or all of the cathode and the anode are placed in the reaction solution of the reaction system, and the area of the opposite surfaces of the anode and the cathode placed in the reaction solution is 64 - 150 mm 2 and a current is applied between the cathode and the anode in the reaction system.

[0021] It should be noted that after the reaction is completed, it is monitored by TLC and separated and purified by column chromatography to obtain β - carbonyl dithiophosphate compounds.

[0022] Even further, 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 ammonium iron(III) sulfate, and the molar concentration of the electrolyte in the solution is 0.006 M - 0.12 M, preferably the reaction electrolyte is tetrabutylammonium tetrafluoroborate; the additive is one of 18 - crown - 6, ferrocene, and N - hydroxyphthalimide, preferably 18 - crown - 6.

[0023] Even further, the electrochemical constant 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 an air atmosphere.

[0024] It should be noted that the present invention discloses a preparation method of β - carbonyl dithiophosphate compounds. Under electrochemical conditions, using styrene, P4S 10Using alcohol as a raw material, tetrabutylammonium tetrafluoroborate as an electrolyte, and a cheap, easily available, and reusable graphite electrode material, the synthesis cost and environmental impact are reduced. The corresponding β-carbonyl dithiophosphates are prepared by reacting for 6 hours in a room-temperature air atmosphere. Compared with the reported preparation methods, the present invention has the advantages of being green, environmentally friendly, safe, efficient, with easily available raw materials, and simple operation.

[0025] The third technical object of the present invention is to provide an application of the β-carbonyl dithiophosphates as described above in pesticides.

[0026] Specifically, as Figure 2 shown, Dimethoate, which is a widely used and highly produced insecticide, is suitable for controlling piercing-sucking mouthpart pests on various crops, such as aphids, leafhoppers, whiteflies, leaf-mining pests, and certain scale insects, etc., and has good control effects. It also has certain control effects on mites. As an insecticide and herbicide, Morphothion can increase grain yield and anti-androgen secretion. Anilofos is a pre-emergence herbicide that has been proven to be effective against barnyard grass, can down-regulate amino acid metabolism, mainly promote carbohydrate metabolism and secondary metabolite biosynthesis in crops, and has the least impact on soil metabolism. Phenthoate is suitable for controlling various pests on crops such as rice, cotton, fruit trees, and vegetables, and can be used to control Chilo suppressalis, Tryporyza incertulas, Nilaparvata lugens, Oulema oryzae, Helicoverpa armigera, aphids, leafhoppers, Pieris rapae, Plutella xylostella, etc.

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

[0028] By adopting an electrochemical method, the present invention does not need to use toxic and harmful reagents and solvents, the electrolyte can be recycled, reducing the synthesis cost and environmental hazards; the reaction device is simple, the electrode material can be reused, and it is easy to realize industrial production; the reaction conditions are mild, without the need for harsh conditions such as high temperature and high pressure; the raw materials used are easily obtained and inexpensive; the reaction is realized by a multi-component one-pot method, with simple operation.

[0029] In summary, the method disclosed in the present invention utilizes the clean reagent "electron", without adding metals, acids or bases, without the need to add any additional oxidants or reductants, with mild conditions, energy conservation and environmental protection, cheap and easily available raw materials, simple operation, safe and reliable, and can be prepared in large quantities with a high product yield. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] In order to more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the following will briefly introduce the drawings required for the description of the embodiments or the prior art. Obviously, the drawings in the following description are only the embodiments of the present invention. For those of ordinary skill in the art, other drawings can be obtained according to the provided drawings without creative efforts.

[0031] Figure 1 It is the synthesis mechanism diagram of the β-carbonyl dithiophosphate compounds of the present invention.

[0032] Figure 2 It is the diagram of the function of the functional group in the β-carbonyl dithiophosphate compounds of the present invention.

[0033] Figure 3 It is the hydrogen spectrum diagram (a), carbon spectrum diagram (b), and phosphorus spectrum diagram (c) of 4a of the present invention

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

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

[0036] Figure 6 It is the hydrogen spectrum diagram (a), carbon spectrum diagram (b), and phosphorus spectrum diagram (c) of compound 4d of the present invention.

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

[0038] Figure 8 It is the hydrogen spectrum diagram (a), carbon spectrum diagram (b), and phosphorus spectrum diagram (c) of compound 4i of the present invention. Detailed implementation manners

[0039] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without making creative efforts shall fall within the protection scope of the present invention.

[0040] The special term "embodiment" here, any embodiment described as "exemplary" does not have to be construed as superior to or better than other embodiments. For the performance index tests in the embodiments of this application, unless otherwise specified, the conventional test methods in the art are adopted. It should be understood that the terms described in this application are only for describing specific embodiments and are not used to limit the content disclosed in this application.

[0041] Unless otherwise specified, the technical and scientific terms used herein have the same meanings as those commonly understood by those of ordinary skill in the technical field to which this application belongs; the test methods and technical means not specifically mentioned in this application are all the experimental methods and technical means commonly adopted by those of ordinary skill in the art.

[0042] In order to better illustrate the content of the present application, numerous specific details are given in the following specific embodiments. Those skilled in the art should understand that the present application can also be implemented without certain specific details. In the embodiments, some methods, means, instruments, equipment, etc. well-known to those skilled in the art are not described in detail in order to highlight the gist of the present application.

[0043] On the premise of no conflict, the technical features disclosed in the embodiments of the present application can be arbitrarily combined, and the obtained technical solutions belong to the content disclosed in the embodiments of the present application.

[0044] The present invention discloses a preparation method of β-carbonyl dithiophosphate compounds.

[0045] To better understand the present invention, the following embodiments are used to further specifically elaborate the present invention, but it should not be construed as a limitation of the present invention. For those skilled in the art, some non-essential improvements and adjustments made according to the above-mentioned invention content are also regarded as falling within the protection scope of the present invention.

[0046] Example 1

[0047]

[0048] In air, a mixture of styrene (0.1 mmol), P4S 10 (66.7 mg, 0.15 mmol) and EtOH (290 μL, 5 mmol) was added to an undivided electro-reaction flask (10 mL), and the flask was equipped with graphite plates as the 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), tetrabutylammonium tetrafluoroborate as the electrolyte (0.2 mmol), and 18-crown-6 (0.1 mmol) as the additive; after the reaction was completed, 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 with a yield of 71%.

[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 (21.6 mg, 71%). 11H NMR (600 MHz, CDCl3) δ 7.98 (dd, J = 8.1, 1.0 Hz, 2H), 7.62 - 7.60 (m, 1H), 7.49 (t, J = 7.9, 2H), 4.37 (d, J = 14.5 Hz, 2H), 4.26 - 4.13 (m, 4H), 1.36 (t, J = 7.1 Hz, 6H). 13 13C NMR (150 MHz, CDCl3) δ 193.1 (d, J = 4.5 Hz), 135.5, 134.0, 129.0, 128.7, 64.5 (d, J = 6.0 Hz), 40.9 (d, J = 3.0 Hz), 16.0 (d, J = 7.5 Hz). 31 31P NMR (243 MHz, CDCl3) δ 93.98 (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 after work-up, the yellow liquid target product 4b (20.2 mg, yield 63%) was obtained.

[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 (20.2 mg, 63%). 1 1H NMR (600 MHz, CDCl3) δ 7.88 (d, J = 8.2 Hz, 2H), 7.28 (d, J = 8.0 Hz, 2H), 4.34 (d, J = 14.3 Hz, 2H), 4.26 - 4.12 (m, 4H), 2.42 (s, 3H), 1.35 (t, J = 7.1 Hz, 6H). 13 13C NMR (150 MHz, CDCl3) δ 192.7 (d, J = 7.5 Hz), 145.0, 133.0, 129.7, 128.8, 64.5 (d, J = 7.5 Hz), 40.8 (d, J = 3.0 Hz), 21.9, 16.0 (d, J = 9.0 Hz). 31 31P NMR (600 MHz, CDCl3) δ 94.04 (s).

[0056] Example 3

[0057]

[0058] The reaction steps and operations were the same as those 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 yellow liquid target product 4c (20.2 mg, yield 60%) was obtained.

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

[0060] S-(2-(4-chlorophenyl)-2-oxoethyl) O,O-diethyldithiophosphate (4c): TLC (Petroleum / EtOAc = 10:1, v / v), R f = 0.41; Yellow oil (20.2 mg, 60%). 1 1H NMR (600 MHz, DMSO-d6) δ 8.00 (d, J = 8.5 Hz, 2H), 7.64 (d, J = 8.5 Hz, 2H), 4.50 (d, J = 15.5 Hz, 2H), 4.14 - 4.05 (m, 4H), 1.26 (t, J = 7.0 Hz, 6H). 13 13C NMR (150 MHz, DMSO-d6) δ 192.4 (d, J = 4.5 Hz), 138.8, 133.8, 130.4, 129.0, 63.9 (d, J = 4.5 Hz), 40.1, 15.5 (d, J = 9.0 Hz). 31 31P NMR (243 MHz, CDCl3) δ 92.39 (s).

[0061] Example 4

[0062]

[0063] The reaction steps and operations were the same as those 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 yellow liquid target product 4d (26.2 mg, yield 68%) was obtained.

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

[0065] S-(2-(4-bromophenyl)-2-oxoethyl) O,O-diethyldithiophosphate (4d): TLC (Petroleum / EtOAc = 10:1, v / v), R f = 0.37; Yellow oil (26.2 mg, 68%). 11H NMR (600 MHz, CDCl3) δ 7.86 - 7.84 (m, 2H), 7.65 - 7.63 (m, 2H), 4.32 (d, J = 14.9 Hz, 2H), 4.25 - 4.12 (m, 4H), 1.35 (t, J = 7.1 Hz, 6H). 13 13C NMR (150 MHz, CDCl3) δ 192.3 (d, J = 6.0 Hz), 134.2, 132.3, 130.2, 129.3, 64.6 (d, J = 6.0 Hz), 40.8 (d, J = 1.5 Hz), 16.0 (d, J = 9.0 Hz). 31 31P NMR (243 MHz, CDCl3) δ 93.92 (s).

[0066] Example 5

[0067]

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

[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 (20.5 mg, 64%). 1 1H NMR (600 MHz, CDCl3) δ 8.04 - 8.00 (m, 2H),

[0072] 7.18 - 7.14 (m, 2H), 4.33 (d, J = 14.8 Hz, 2H), 4.26 - 4.12 (m, 4H), 1.35 (td, J = 7.1, 0.5 Hz, 6H). 13 13C NMR (150 MHz, CDCl3) δ 191.6 (d, J = 6.0 Hz), 166.3 (d, J = 255.0 Hz), 131.9 (d, J = 3.0 Hz), 131.4 (d, J = 10.5 Hz), 116.2 (d, J = 21.0 Hz), 64.6 (d, J = 6.0 Hz), 40.8 (d, J = 3.0 Hz), 15.9 (d, J = 9.0 Hz). 1919F NMR (565 MHz, CDCl3) δ -25.66 (s). 31 31P NMR (243 MHz, CDCl3) δ 94.02 (s).

[0073] Example 6

[0074]

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

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

[0077] O,O-Diethyl S-(2-(naphthalen-2-yl)-2-oxoethyl) dithiophosphate (4f): TLC (Petroleum / EtOAc = 10:1, v / v), R f = 0.38; Yellow oil (10.1 mg, 28%). 1 1H NMR (600 MHz, DMSO-d6) δ 8.74 (s, 1H), 8.16 (d, J = 8.0 Hz, 1H), 8.06 - 8.01 (m, 2H), 7.99 (dd, J = 8.6, 1.7 Hz, 1H), 7.72 - 7.64 (m, 2H), 4.65 (d, J = 15.5 Hz, 2H), 4.18 - 4.07 (m, 4H), 1.27 (t, J = 7.0 Hz, 6H). 13 13C NMR (150 MHz, DMSO-d6) δ 193.1 (d, J = 4.5 Hz), 135.2, 132.4, 132.1, 130.7, 129.7, 129.0, 128.5, 127.7, 127.2, 123.7, 63.9 (d, J = 4.5 Hz), 40.1, 39.9 (d, J = 4.5 Hz) 15.6 (d, J = 9.0 Hz). 31 31P NMR (243 MHz, DMSO-d6) δ 92.60 (s).

[0078] Example 7

[0079]

[0080] The reaction steps and operations are the same as those in Example 1. The difference from Example 1 is that 1 g (0.1 mmol, 14.41 mg) of 5-vinylbenzofuran is added to the reaction system. The reaction is stopped, and after post-treatment, 4 g (12.0 mg, yield 35%) of the yellow liquid target product is obtained.

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

[0082] S-(2-(benzofuran-5-yl)-2-oxoethyl) O,O-diethyldithiophosphate (4 g): TLC (Petroleum / EtOAc = 10:1, v / v), R f = 0.33; Yellow oil (12.0 mg, 35%). 1 1H NMR (600 MHz, DMSO-d6) δ 8.40 (d, J = 1.5 Hz, 1H), 8.15 (d, J = 2.2 Hz, 1H), 7.96 (dd, J = 8.7, 1.7 Hz, 1H), 7.75 (d, J = 8.7 Hz, 1H), 7.13 (d, J = 1.4 Hz, 1H), 4.58 (d, J = 15.1 Hz, 2H), 4.17 - 4.06 (m, 4H), 1.27 (t, J = 7.0 Hz, 6H). 13 13C NMR (150 MHz, DMSO-d6) δ 192.6 (d, J = 3.0 Hz), 157.0, 147.8, 130.6, 127.5, 125.0, 123.1, 111.7, 107.5, 63.8 (d, J = 4.5 Hz), 40.0, 15.5 (d, J = 9.0 Hz). 31 31P NMR (243 MHz, DMSO-d6) δ 92.61 (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 steps and operations are the same as those in Example 1. The difference from Example 1 is that 1 h (0.1 mmol, 16.03 mg) of 5-vinylbenzofuran is added to the reaction system. The reaction is stopped, and after post-treatment, 4 h (13.2 mg, yield 36%) of the yellow liquid target product is obtained.

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

[0087] S-(2-(Benzo[b]thiophen-5-yl)-2-oxoethyl) O,O-diethyl phosphorodithioate (4h): TLC (Petroleum / EtOAc = 10:1, v / v), R f = 0.32; Yellow oil (13.2 mg, 37%). 1 1H NMR (600 MHz, CDCl3) δ 8.46 (s, 1H), 7.97 - 7.93 (m, 2H), 7.55 (d, J = 5.5 Hz, 1H), 7.46 (d, J = 5.4 Hz, 1H), 4.45 (d, J = 14.4 Hz, 1H), 4.27 - 4.14 (m, 2H), 1.36 (t, J = 7.1 Hz, 6H). 13 13C NMR (150 MHz, CDCl3) δ 192.9 (d, J = 6.0 Hz), 145.1 (s), 139.6 (s), 131.9 (s), 128.4 (s), 124.8 (d, J = 3.0 Hz), 123.6 (s), 123.0 (s), 64.6 (d, J = 6.0 Hz), 41.0 (d, J = 3.0 Hz), 16.0 (d, J = 7.5 Hz). 31 31P NMR (243 MHz, DMSO-d6) δ 92.59 (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 steps and operations were the same as those in Example 1, except that: 3b-propanol (5 mmol, 375 μL) was added to the reaction system. The reaction was stopped, and after post-treatment, the yellow liquid target product 4i (19.9 mg, yield 60%) was obtained.

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

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

[0093] R f = 0.42; Yellow oil (19.9 mg, 60%).1 1H NMR (600 MHz, DMSO-d6) δ 7.98 (dd, J = 8.3, 1.1 Hz,

[0094] 2H), 7.70 - 7.67 (m, 1H), 7.58 - 7.55 (m, 2H), 4.51 (d, J = 15.5 Hz, 2H), 4.04 - 3.97 (m, 4H), 1.67 - 1.61 (m, 4H), 0.88 (t, J = 7.4 Hz, 6H). 13 13C NMR (150 MHz, DMSO-d6) δ 193.2 (d, J = 4.5 Hz), 135.1, 133.8, 128.9, 128.4, 69.1 (d, J = 6.0 Hz), 40.0, 22.7 (d, J = 9.0 Hz), 10.0. 31 31P NMR (243 MHz, DMSO-d6) δ 93.18 (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 steps and operations were the same as in Example 1, except that: 3c (5 mmol, 455 μL) of butanol was added to the reaction system. The reaction was stopped, and after post-treatment, the yellow liquid target product 4j (27.0 mg, yield 75%) was obtained.

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

[0099] O,O-Dibutyl S-(2-oxo-2-phenylethyl) dithiophosphate (4j): TLC (Petroleum / EtOAc = 10:1, v / v), R f = 0.51; Yellow oil (27.0 mg, 75%). 1 1H NMR (600 MHz, DMSO-d6) δ 7.98 (dd, J = 7.5 Hz, 2H), 7.69 (t, J = 7.3 Hz, 1H), 7.57 (t, J = 7.6 Hz, 2H), 4.50 (d, J = 15.6 Hz, 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 13C NMR (150 MHz, DMSO-d6) δ

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

[0101] Example 11

[0102]

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

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

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

[0106] R f = 0.52; Yellow oil (27.0 mg, 70%). 1 1H NMR (600 MHz, DMSO-d6) δ 7.98 (m, 2H), 7.68 (t, J =

[0107] 7.4 Hz, 1H), 7.56 (t, J = 7.6 Hz, 2H), 4.50 (d, J = 15.5 Hz, 2H), 4.09 - 3.98 (m, 4H), 1.64 - 1.59 (m, 4H), 1.30 - 1.27 (m, 8H), 0.84 (t, J = 7.0 Hz, 6H). 13 13C NMR (150 MHz, DMSO-d6) δ 193.1 (d, J = 4.2 Hz), 135.1, 133.8, 128.8, 128.4, 67.6 (d, J = 6.0 Hz), 39.9, 28.9 (d, J = 7.5 Hz), 27.2, 21.6, 13.8. 31 31P NMR (243 MHz, CDCl3) δ 94.34 (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 steps and operations were the same as in Example 1. The difference from Example 1 was that isopropanol 3e (5 mmol, 382 μL) was added to the reaction system. The reaction was stopped, and after post-treatment, the yellow liquid target product 4l (20.3 mg, yield 61%) was obtained.

[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 (20.3 mg, 61%). 1 1H NMR (600 MHz, DMSO-d6) δ 7.98 (d, J = 7.1 Hz, 2H), 7.68 (t, J = 7.3 Hz, 1H), 7.56 (t, J = 6.9 Hz, 2H), 4.76 - 4.70 (m, 2H), 4.50 (d, J = 15.4 Hz, 2H), 1.32 - 1.24 (m, 12H). 13 13C NMR (150 MHz, DMSO-d6) δ 193.2 (d, J = 4.5 Hz), 135.2, 133.8, 128.9, 128.4, 73.5 (d, J = 7.5 Hz), 40.2 (d, J = 3.0 Hz), 23.3 (d, J = 3.0 Hz), 23.0 (d, J = 4.5 Hz). 31 31P NMR (243 MHz, DMSO-d6) δ 88.64 (s).

[0113] Example 13

[0114]

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

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

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

[0118] R f = 0.50; Yellow oil (21.3 mg, 65%). 1 H NMR (600 MHz, DMSO-d6) δ 7.97 (d, J = 7.4 Hz, 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 = 7.5 Hz, 4H). 13 C NMR (150 MHz, DMSO-d6) δ 192.7 (d, J = 6.0 Hz), 134.9, 133.6, 128.6, 128.2, 79.7 (t, J = 33.0), 51.9 (t, J = 4.5 Hz), 40.1 (d, J = 1.5 Hz), 5.0 (d, J = 6 Hz), 4.8 (d, J = 4.5 Hz). 31 P NMR (243 MHz, DMSO-d6) δ 94.15 (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 steps and operations were the same as in Example 1, except that: 1-Cyclopropylmethyl 3 g (5 mmol, 399 μL) was added to the reaction system. The reaction was stopped, and after post-treatment, the yellow liquid target product 4n (20.6 mg, yield 58%) was obtained.

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

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

[0125] v / v), R f= 0.51; Yellow oil (20.6 mg, 58%). 1 HNMR (600 MHz, DMSO-d6) δ 7.99 - 7.98 (m, 2H),

[0126] 7.69 (t, J = 7.4 Hz, 1H), 7.58 - 7.55 (m, 2H), 4.53 (d, J = 15.1 Hz, 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 (150 MHz, DMSO-d6) δ 193.2 (d, J = 4.5 Hz), 135.1, 133.8, 128.9, 128.4, 72.4 (d, J = 6.0 Hz), 39.9 (d, J = 3.0 Hz), 10.6 (d, J = 9.0 Hz), 3.4 (d, J = 9.0 Hz). 31 P NMR (243 MHz, DMSO-d6) δ 95.92 (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 steps and operations were the same as in Example 1, except that: cycloheptanol 3h (5 mmol, 575 μL) was added to the reaction system. The reaction was stopped, and the target product 4o, a yellow liquid (17.6 mg, yield 40%), was obtained after post-treatment.

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

[0132] O,O-dicycloheptyl S-(2-oxo-2-phenylethyl)phosphorodithioate (4o): O,O-dicycloheptyl S-(2-oxo-2-phenylethyl)phosphorodithioate (4ad): TLC (Petroleum / EtOAc = 10:1, v / v), R f = 0.49; Yellow oil (17.6 mg, 40%).1 1H NMR (600 MHz, DMSO-d6) δ 7.97 (d, J = 7.7 Hz, 2H), 7.68 (t, J = 7.3 Hz, 1H), 7.56 (t, J = 7.6 Hz, 2H), 4.69 - 4.62 (m, 2H), 4.49 (d, J = 15.7 Hz, 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 13C NMR (150 MHz, DMSO-d6) δ 193.2 (d, J = 4.5 Hz), 135.2, 133.8, 128.9, 128.4, 80.5 (d, J = 7.5 Hz), 40.1 (d, J = 6.0 Hz) 34.8 (d, J = 4.5 Hz), 34.5 (d, J = 4.5 Hz), 27.5 (d, J = 6.0 Hz), 21.7 (d, J = 13.5 Hz). 31 31P NMR (243 MHz, DMSO-d6) δ 90.32 (s). HRMS (ESI) m / z: Calcd for: 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 those in Example 1. The difference from Example 1 was that the reaction was carried out without power supply. The reaction was stopped, and the target product 4 was not obtained after post-treatment.

[0135] It shows that the reaction cannot proceed without power supply.

[0136] Comparative Example 2

[0137] The reaction steps and operations were the same as those in Example 1. The difference from Example 1 was that the reaction was carried out under a N2 atmosphere. The reaction was stopped, and the target product 4 was obtained in only a trace yield after post-treatment.

[0138] It shows that the N2 condition is not conducive to the reaction.

[0139] Comparative Example 3

[0140] The reaction steps and operations were the same as those in Example 1. The difference from Example 1 was that the reaction was carried out without electrolyte. The reaction was stopped, and the target product 4 (12.2 mg, yield 40%) was obtained after post-treatment.

[0141] It shows that the absence of electrolyte is not conducive to the reaction.

[0142] Experimental Example 1

[0143] The reaction steps and operations were the same as those in Example 1, and the difference from Example 1 was that the reaction was carried out under 18 O2 conditions. The reaction was stopped, and the target product 18 O-4a was obtained after post-treatment. It was shown that O2 was the oxygen source for this reaction.

[0144] Experimental Example 2

[0145] The reaction steps and operations were the same as those in Example 1, and the difference from Example 1 was that H2 18 O was added to the reaction system. The reaction was stopped, and after post-treatment and high-resolution characterization, the product 18 O-4a was not detected, indicating that H2O was not the oxygen source for this reaction.

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

Claims

1. A β-carbonyl dithiophosphate compound, characterized in that, The structure of the β-carbonyl dithiophosphate compounds is as follows: Among them, R 1 is a linear alkyl group, branched alkyl group, halogen, alkoxy group, heteroaromatic olefin, R 2 is a linear alkyl group, branched alkyl group, cycloalkyl group.

2. A method for synthesizing the β-carbonyl dithiophosphate compounds as claimed in claim 1, characterized in that Substituent R 1 , R 2 is defined as claimed in claim 1.

3. The synthesis method of the β-carbonyl dithiophosphate compound according to claim 2, characterized in that, Using styrene or substituted styrene as raw materials, under electrocatalytic conditions, with P4S 10 and alcohol to form β-carbonyl dithiophosphate compounds.

4. The synthesis method of the β-carbonyl dithiophosphate compound according to claim 2 or 3, characterized in that, the molar ratio of substituted styrene / styrene to alcohol is 1:10 - 1:60, the reaction time is 4 - 8 hours, and the reaction temperature is 25 - 30°C; the reaction is carried out under a constant current condition, and a certain amount of additive needs to be added to the reaction system. After the reaction is completed, product separation is carried out to obtain the β-carbonyl dithiophosphate compounds.

5. The synthesis method of the β-carbonyl dithiophosphate compound according to claim 4, characterized in that, The reaction is carried out in a reaction vessel provided with a cathode and an anode. The anode and the cathode are arranged opposite to each other with a distance of 3 - 10 mm. Part or all of the cathode and the anode are placed in the reaction solution of the reaction system, and the area of the opposite surfaces of the anode and the cathode placed in the reaction solution is 64 - 150 mm 2 , and a current is applied between the cathode and the anode in the reaction system.

6. The synthesis method of the β-carbonyl dithiophosphate compound according to claim 5, characterized in that, The reaction anode material is one of graphite, nickel, and platinum, and 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 ammonium iron(III) sulfate, and the molar concentration of the electrolyte in the solution is 0.006M - 0.12M; the additive is one of 18-crown-6, ferrocene, and N-hydroxyphthalimide.

7. The synthesis method of the β-carbonyl dithiophosphate compound according to claim 5, characterized in that, The electrochemical constant reaction current is 6 - 11 mA, and the reaction time is 5 - 8 hours; the reaction temperature is room temperature, and the reaction atmosphere is an air atmosphere.

8. The application of the β-carbonyl dithiophosphate compounds as claimed in claim 1 or the β-carbonyl dithiophosphate compounds prepared by the method as claimed in claim 2 in pesticides.

Images