A (E)-2-(hydroxyimino)-2-(methylsulfonyl)-N,N-dimethylacetamide and its preparation method and application

Abstract

The present invention belongs to the technical field of pesticides, and specifically relates to a (E)-2-(hydroxyimino)-2-(methylsulfonyl)-N,N-dimethylacetamide and a preparation method and application thereof. The present invention provides a (E)-2-(hydroxyimino)-2-(methylsulfonyl)-N,N-dimethylacetamide having a structure shown in Formula I. The (E)-2-(hydroxyimino)-2-(methylsulfonyl)-N,N-dimethylacetamide provided by the present invention has good killing activity against plant root-knot nematodes.

Description

Technical Field

[0001] The invention belongs to the technical field of pesticides, and specifically relates to (E)-2-(hydroxyimino)-2-(methylsulfonyl)-N,N-dimethylacetamide and a preparation method and application thereof. Background Art

[0002] Plant parasitic nematodes (hereinafter referred to as "nematodes") are hidden and invisible, have a short life cycle, a large reproduction coefficient, a wide variety of species, a wide distribution and spread, and are difficult to identify. They are one of the main pests in crop planting and directly affect the entire growth period of crops, including beans, cereals, potatoes, beets, sweet potatoes, bananas, coconuts, tobacco, etc., as well as vegetables such as cucumbers, tomatoes, and ginger. Globally, crop yields are lost by more than 12% each year due to nematode infection, and the direct economic losses are as high as $150 billion. With global climate change, planting system reforms, and the rapid development of high-value agriculture, plant nematode diseases in China are showing a serious trend and have risen to the second largest plant disease. Among them, root-knot nematodes and cyst nematodes are the two most serious types of crop pathogenic nematodes. The annual loss caused by nematodes in my country is about $3.5 billion. Due to the endoparasitic nature of nematodes, most of their life cycles are completed in the host plant and protected by the host plant tissues, making them difficult to prevent and control.

[0003] German patent Ger.Offen2119700 discloses the preparation and application of the compound 2-(hydroxyimino)-2-(methylsulfonyl)-N,N-dimethylacetamide, the structure of which is shown in Formula 1:

[0004]

[0005] The patent discloses that the compound of formula 1 can be obtained by oxidizing the corresponding sulfur-containing compound, and the structure of the sulfur-containing compound is shown in formula 2:

[0006]

[0007] The reaction formula is:

[0008]

[0009] The patent discloses that the compound of formula 2 can be prepared from diketene as a raw material through four reactions: amination, oximation, chlorination and methylthiolation.

[0010] This patent discloses the fungicidal activity of the compound of formula 1 and its composition, and specifically studies the ability of the compound of formula 1 to prevent diseases of crops and ornamental plants caused by fungi of the class Algae Fungi, but it has not yet been commercially applied.

[0011] It is worth noting that according to the structural formula of the compound of Formula 1, because it contains a double bond -C=N-, it indicates that there may be two different isomers, Z type and E type, which are not mentioned in the above patent. It is particularly noteworthy that the compound obtained by the above preparation method disclosed in the patent is actually a Z type structure (Formula II) after testing, that is, (Z)-2-(hydroxyimino)-2-(methylsulfonyl)-N,N-dimethylacetamide, and there is no E type structural component. At the same time, the patent also does not study and mention its nematicidal activity and application.

[0012]

[0013] Indoor biological test tests have shown that the compound of formula II has very poor killing activity against plant root-knot nematodes. Summary of the invention

[0014] In order to solve the problems existing in the prior art, the present invention provides a (E)-2-(hydroxyimino)-2-(methylsulfonyl)-N,N-dimethylacetamide and a preparation method and application thereof. The (E)-2-(hydroxyimino)-2-(methylsulfonyl)-N,N-dimethylacetamide provided by the present invention has good killing activity against plant root-knot nematodes.

[0015] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:

[0016] The present invention provides a (E)-2-(hydroxyimino)-2-(methylsulfonyl)-N,N-dimethylacetamide having a structure shown in Formula I:

[0017]

[0018] The present invention also provides a method for preparing the above-mentioned (E)-2-(hydroxyimino)-2-(methylsulfonyl)-N,N-dimethylacetamide, comprising the following steps:

[0019] Mixing (Z)-2-(hydroxyimino)-2-(methylsulfonyl)-N,N-dimethylacetamide, water and an alkaline substance, and performing transposition to obtain a system containing a salt of (E)-2-(hydroxyimino)-2-(methylsulfonyl)-N,N-dimethylacetamide;

[0020] The system containing the salt of (E)-2-(hydroxyimino)-2-(methylsulfonyl)-N,N-dimethylacetamide is neutralized with an acid to obtain the (E)-2-(hydroxyimino)-2-(methylsulfonyl)-N,N-dimethylacetamide.

[0021] Preferably, the alkaline substance includes one or more of sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium oxide, potassium oxide, calcium oxide, sodium carbonate, potassium carbonate, ammonia and derivatives thereof.

[0022] Preferably, the temperature of the transposition is 0 to 100° C., and after the (Z)-2-(hydroxyimino)-2-(methylsulfonyl)-N,N-dimethylacetamide, water and alkaline substance are mixed, the pH value of the system is 7 to 14.

[0023] Preferably, after neutralization with acid, the neutralization system is further cooled, solid-liquid separated and dried in sequence.

[0024] The present invention also provides the use of the above-mentioned (E)-2-(hydroxyimino)-2-(methylsulfonyl)-N,N-dimethylacetamide in the preparation of a plant root-knot nematode killer.

[0025] Preferably, the plant root-knot nematode killer comprises an active component and an adjuvant; the active component is the (E)-2-(hydroxyimino)-2-(methylsulfonyl)-N,N-dimethylacetamide described in claim 1; and the adjuvant comprises one or more of a binder, a stabilizer, a carrier and a solvent.

[0026] Preferably, the binder includes paraffin and / or polyvinyl alcohol; the carrier includes one or more of quartz sand, attapulgite and clay particles; the solvent includes one or more of water, alcohols, esters, aromatic hydrocarbons and ethers; the stabilizer includes one or more of phosphoric acid, oxalic acid, tartaric acid and citric acid.

[0027] Preferably, the mass percentage of the active component in the plant root-knot nematode killer is 0.1-95%.

[0028] Preferably, the plant root-knot nematode killer agent is in the form of one or more of granules, dusts, wettable powders, emulsifiable concentrates, microcapsule suspensions, dispersible oil suspensions, dry suspensions, concentrated emulsions and sustained-release agents.

[0029] The present invention provides a (E)-2-(hydroxyimino)-2-(methylsulfonyl)-N,N-dimethylacetamide having a structure shown in Formula I. The (E)-2-(hydroxyimino)-2-(methylsulfonyl)-N,N-dimethylacetamide provided by the present invention has good killing activity against plant root-knot nematodes. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] Figure 1 is the liquid chromatogram of (Z)-2-(hydroxyimino)-2-(methylsulfonyl)-N,N-dimethylacetamide before transposition;

[0031] Figure 2 This is the single crystal XRD structure diagram of (Z)-2-(hydroxyimino)-2-(methylsulfonyl)-N,N-dimethylacetamide before conversion;

[0032] Figure 3 is the liquid chromatogram of (E)-2-(hydroxyimino)-2-(methylsulfonyl)-N,N-dimethylacetamide after transposition;

[0033] Figure 4 The single crystal of (E)-2-(hydroxyimino)-2-(methylsulfonyl)-N,N-dimethylacetamide Structural diagram. DETAILED DESCRIPTION

[0034] The present invention provides a (E)-2-(hydroxyimino)-2-(methylsulfonyl)-N,N-dimethylacetamide having a structure shown in Formula I:

[0035]

[0036] The present invention also provides a method for preparing the (E)-2-(hydroxyimino)-2-(methylsulfonyl)-N,N-dimethylacetamide, comprising the following steps:

[0037] Mixing (Z)-2-(hydroxyimino)-2-(methylsulfonyl)-N,N-dimethylacetamide, water and an alkaline substance, and performing transposition to obtain a system containing a salt of (E)-2-(hydroxyimino)-2-(methylsulfonyl)-N,N-dimethylacetamide;

[0038] The system containing the salt of (E)-2-(hydroxyimino)-2-(methylsulfonyl)-N,N-dimethylacetamide is neutralized with an acid to obtain the (E)-2-(hydroxyimino)-2-(methylsulfonyl)-N,N-dimethylacetamide.

[0039] In the present invention, the alkaline substance preferably includes one or more of sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium oxide, potassium oxide, calcium oxide, sodium carbonate, potassium carbonate, ammonia and derivatives thereof, more preferably sodium hydroxide.

[0040] In the present invention, the temperature of the transposition is preferably 0-100°C, more preferably 25-50°C, and the time of the transposition is preferably >10 min, more preferably 20-30 min. In the present invention, the transposition is preferably performed under stirring.

[0041] In the present invention, after (Z)-2-(hydroxyimino)-2-(methylsulfonyl)-N,N-dimethylacetamide, water and alkaline substances are mixed, the pH value of the system is preferably 7-14, more preferably 7-9.

[0042] In the present invention, the acid preferably includes an inorganic acid and / or an organic acid, and is preferably hydrochloric acid. In the present invention, after neutralization with an acid, preferably cooling, solid-liquid separation and drying are also included. In the present invention, the cooling is preferably cooled to 0°C, and the solid-liquid separation is preferably performed by filtration.

[0043] In the present invention, the preparation formula of the (E)-2-(hydroxyimino)-2-(methylsulfonyl)-N,N-dimethylacetamide is:

[0044]

[0045] The present invention also provides the use of the (E)-2-(hydroxyimino)-2-(methylsulfonyl)-N,N-dimethylacetamide described in the above technical solution in the preparation of a plant root-knot nematode killer.

[0046] In the present invention, the plant root-knot nematode killer preferably includes an active component and an adjuvant; the active component is preferably (E)-2-(hydroxyimino)-2-(methylsulfonyl)-N,N-dimethylacetamide; the adjuvant preferably includes one or more of a binder, a stabilizer, a carrier and a solvent.

[0047] In the present invention, the binder preferably includes paraffin and / or polyvinyl alcohol; the carrier preferably includes one or more of quartz sand, attapulgite and clay particles, more preferably quartz sand. In the present invention, the solvent preferably includes one or more of water, alcohols, esters, aromatic hydrocarbons and ethers, more preferably water. In the present invention, the stabilizer preferably includes one or more of phosphoric acid, oxalic acid, tartaric acid and citric acid.

[0048] In the present invention, the mass percentage of the active component in the plant root-knot nematode killer is preferably 0.1 to 95%, and more preferably 30 to 50%.

[0049] In the present invention, the dosage form of the plant root-knot nematode killer is preferably one or more of granules, dusts, wettable powders, emulsifiable concentrates, microcapsule suspensions, dispersible oil suspensions, dry suspensions, concentrated emulsions and sustained-release agents.

[0050] In the present invention, when the plant root-knot nematode killer is used to kill plant root-knot nematodes, the field application method preferably includes hole application, furrow application, broadcast application, mixing with poisoned soil or root irrigation.

[0051] The technical solutions provided by the present invention are described in detail below in conjunction with the embodiments, but they should not be construed as limiting the protection scope of the present invention.

[0052] Example 1

[0053] In a 250 mL three-necked round-bottom flask with stirring, 39.07 g of (Z)-2-(hydroxyimino)-2-(methylsulfonyl)-N,N-dimethylacetamide (mass content: 99.3%, molar weight: 0.2 mol) and 100 mL of water were added. Under stirring, 29.3 g of NaOH solution (mass concentration of NaOH: 30%, molar weight: 0.22 mol) was slowly added dropwise to make the pH of the system reach about 8. The mixture was stirred at room temperature for 20 min. Samples were taken and the Z-configuration raw materials were completely converted by liquid chromatography. 26.74 g of hydrochloric acid (mass concentration of HCl: 30%, molar weight: 0.22 mol) was added for neutralization. Then, the temperature was lowered to 0°C, filtered and dried to obtain 33 g of white crystals, wherein the content of (E)-2-(hydroxyimino)-2-(methylsulfonyl)-N,N-dimethylacetamide was 99%. The mother liquor was decompressed and dehydrated to recover the dissolved part to obtain 5 g of white crystals, wherein the content of (E)-2-(hydroxyimino)-2-(methylsulfonyl)-N,N-dimethylacetamide was 80.5%.

[0054] After calculation, the total mass of (E)-2-(hydroxyimino)-2-(methylsulfonyl)-N,N-dimethylacetamide was 36.7 g, and the total yield was 94.6%.

[0055] The present invention has carried out relevant tests on raw materials and products, and the test results are shown in Figures 1 to 4 ,from Figure 1 and Figure 3 The available information is shown in Tables 1 and 2 respectively.

[0056] Table 1 Liquid chromatography analysis results of (Z)-2-(hydroxyimino)-2-(methylsulfonyl)-N,N-dimethylacetamide

[0057] Peak Retention time Peak height Peak area content 1 4.298 5338.955 31491.100 0.7000 2 5.523 615494.063 4467339.500 99.3000 total 620833.017 4498830.600 100.0000

[0058] Table 2 Liquid chromatography analysis results of (Z)-2-(hydroxyimino)-2-(methylsulfonyl)-N,N-dimethylacetamide

[0059] Peak Retention time Peak height Peak area content 1 5.528 6167.696 44073.645 0.9801 2 6.915 513539.344 4452562.500 99.0199 total 519707.040 4496636.145 100.0000

[0060] from Figures 1 to 4 As shown in Tables 1 and 2, (Z)-2-(hydroxyimino)-2-(methylsulfonyl)-N,N-dimethylacetamide was successfully transformed into (E)-2-(hydroxyimino)-2-(methylsulfonyl)-N,N-dimethylacetamide.

[0061] Test example:

[0062] Indoor bioassay test

[0063] The test was conducted in accordance with NY / T 1833.1-2009 "Guidelines for Indoor Bioassay Tests of Pesticides - Nematicides" Part 1: Insect Immersion Method for Inhibition of Plant Pathogenic Nematodes. The test agents are shown in Table 3, and the test results are shown in Tables 4 to 6.

[0064] Table 3 Indoor activity test agent specifications

[0065]

[0066] Table 4 Toxicity results of the agents to southern root-knot nematode J2 (24h)

[0067]

[0068]

[0069] Table 5 Toxicity results of two pesticides to southern root-knot nematode J2 (48h)

[0070]

[0071] Table 6 Toxicity results of two pesticides to southern root-knot nematode J2 (72h)

[0072]

[0073] As shown in Tables 3 to 6, the LC values ​​of the E-type compound ((E)-2-(hydroxyimino)-2-(methylsulfonyl)-N,N-dimethylacetamide) after treating the southern root-knot nematode J22 for 4h, 48h, and 72h. 50 The values ​​were 17.31 mg / L, 13.04 mg / L and 9.09 mg / L respectively, which were all lower than the LC of the selected control agent II, i.e. (Z)-2-(hydroxyimino)-2-(methylsulfonyl)-N,N-dimethylacetamide. 50 The values ​​were 355.37 mg / L, 328.75 mg / L and 247.03 mg / L, indicating that the E-type compound has excellent indoor nematode activity, which is much higher than that of the Z-type compound, and the difference in activity between the two is more than 20 times. The LC values ​​of the E-type compound after treating the southern root-knot nematode J2 for 24h, 48h and 72h 90 The values ​​were 71.42 mg / L, 58.00 mg / L and 40.63 mg / L respectively, all of which were lower than the LC of the selected control agent Z-type compound. 90 The values ​​were 8036.20 mg / L, 7133.18 mg / L and 5265.87 mg / L, which also showed that type E compounds had excellent indoor nematicidal activity, which was much higher than type Z compounds, and the difference in activity between the two was more than 110 times.

[0074] Although the above embodiment describes the present invention in detail, it is only a part of the embodiments of the present invention, not all of the embodiments. Other embodiments can be obtained based on this embodiment without creativity, and these embodiments all fall within the protection scope of the present invention.

Claims

1. A (E)-2-(hydroxyimino)-2-(methylsulfonyl)-N,N-dimethylacetamide, characterized in that: It has the structure shown in formula I:

2. The method for preparing (E)-2-(hydroxyimino)-2-(methylsulfonyl)-N,N-dimethylacetamide according to claim 1, characterized in that: The following steps are involved: Mixing (Z)-2-(hydroxyimino)-2-(methylsulfonyl)-N,N-dimethylacetamide, water and an alkaline substance, and performing transposition to obtain a system containing a salt of (E)-2-(hydroxyimino)-2-(methylsulfonyl)-N,N-dimethylacetamide; neutralizing a system containing a salt of (E)-2-(hydroxyimino)-2-(methylsulfonyl)-N,N-dimethylacetamide with an acid to obtain the (E)-2-(hydroxyimino)-2-(methylsulfonyl)-N,N-dimethylacetamide; The alkaline substance includes one or more of sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium oxide, potassium oxide, calcium oxide, sodium carbonate, potassium carbonate and ammonia.

3. The preparation method according to claim 2, characterized in that: The temperature of the transposition is 0-100° C. After the (Z)-2-(hydroxyimino)-2-(methylsulfonyl)-N,N-dimethylacetamide, water and alkaline substances are mixed, the pH value of the system is 7-14.

4. The preparation method according to claim 2, characterized in that: After neutralization with acid, the neutralization system is sequentially cooled, solid-liquid separated and dried.

5. Use of (E)-2-(hydroxyimino)-2-(methylsulfonyl)-N,N-dimethylacetamide prepared by the preparation method of claim 1 or any one of claims 2 to 4 in the preparation of a plant root-knot nematode killer.

6. The use according to claim 5, characterized in that The plant root-knot nematode killer comprises an active component and an adjuvant; the active component is the (E)-2-(hydroxyimino)-2-(methylsulfonyl)-N,N-dimethylacetamide described in claim 1; the adjuvant comprises one or more of a binder, a stabilizer, a carrier and a solvent.

7. The use according to claim 6, characterized in that The binder includes paraffin and / or polyvinyl alcohol; the carrier includes one or more of quartz sand, attapulgite and clay particles; the solvent includes one or more of water, alcohols, esters, aromatic hydrocarbons and ethers; the stabilizer includes one or more of phosphoric acid, oxalic acid, tartaric acid and citric acid.

8. The use according to claim 6, characterized in that The mass percentage of the active component in the plant root-knot nematode killer is 0.1-95%.

9. The use according to claim 5, characterized in that The dosage form of the plant root-knot nematode killer is one or more of granules, powders, wettable powders, emulsifiable concentrates, microcapsule suspensions, dispersible oil suspensions, dry suspensions, concentrated emulsions and sustained-release agents.

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