A carboxylic acid oxime ester compound, a preparation method and application thereof

Abstract

The application provides a carboxylic acid oxime ester compound and a preparation method and application thereof, and belongs to the technical field of pesticide synthesis. The carboxylic acid oxime ester compound provided by the application has any one of structures shown in formula I, formula II and formula III; the carboxylic acid oxime ester compound has good killing effect on golden apple snails and is almost non-toxic to non-target organisms, and has environmental friendliness. The results of examples show that the carboxylic acid oxime ester compounds with structures shown in X-1 to X-14 all have certain snail killing activity. Among them, the killing activity of compound X-1 on golden apple snails is close to that of traditional snail killing drug niclosamide, that is, under the condition of 2 mg / L drug concentration, the snail mortality is greater than or equal to 87.5% after 72 h. In terms of ichthyotoxicity, X-1 is safe to fish at a concentration of 16 mg / L, and the mortality rate of fish under the condition of 1 mg / L niclosamide concentration is 100%. The ichthyotoxicity of the carboxylic acid oxime ester compound of the application is greatly reduced compared with that of niclosamide, and the carboxylic acid oxime ester compound shows good aquatic organism safety.

Description

Technical Field

[0001] This invention belongs to the field of pesticide synthesis technology, specifically relating to a carboxylic acid oxime ester compound, its preparation method, and its application. Background Technology

[0002] The golden apple snail, also known as the apple snail or the giant bottle snail, is a large freshwater snail native to the Amazon basin of South America. Due to its strong adaptability and rapid reproduction rate, it competes with native aquatic organisms for living space.

[0003] With the widespread use of chemical molluscicides, golden apple snails have shown a certain degree of resistance, and some populations have become less sensitive to conventional agents, leading to diminishing control effectiveness. Niclosamide, a chemical molluscicide introduced in 1972, is widely used to kill golden apple snails, Oncomelania snails, and other species, and has excellent killing effects; however, niclosamide is highly toxic to non-target aquatic animals, especially fish. Summary of the Invention

[0004] The purpose of this invention is to provide a carboxylic acid oxime ester compound, its preparation method and application. The carboxylic acid oxime ester compound provided by this invention has a good killing effect on golden apple snails and is almost non-toxic to non-target organisms, and is environmentally friendly.

[0005] To achieve the objectives of this invention, the following technical solutions are provided: A carboxylic acid oxime ester compound having the structure shown in any one of Formula I, Formula II, and Formula III: Formula I; Formula II; Formula III; In Formula I, R1, R2, R4, and R5 are independently -H or halogen groups; R3 in Formula I is one of -H, halogen groups, alkoxy groups, cyano groups, and substituted alkyl groups. In Equation II, R6 is -H; In Formula III, R7 is a halogen group.

[0006] Preferably, in Formula I, the halogen group in R1 is -Br or -Cl, the halogen group in R2 is -Cl, the halogen group in R4 is -Cl, and the halogen group in R5 is -Cl; the halogen group in R3 is -Br, -Cl, or -F, the alkoxy group is a C1~C3 alkoxy group, the substituted alkyl group is a halo-C1~C3 alkyl group, and the halo-substituted group is fluorinated; In Formula III, the halogen group in R7 is -Cl.

[0007] Preferably, it has the structure shown in any one of X-1 to X-14: X-1, X-2, X-3, X-4 X-5 X-6 X-7 X-8 X-9 X-10 X-11 X-12 X-13 X-14.

[0008] This invention also provides a method for preparing the carboxylic acid oxime ester compounds described above, comprising the following steps: 2,6-Dichlorobenzaldehyde oxime, aryl-substituted acyl chloride, polar organic solvent and basic catalyst are mixed and subjected to acylation reaction to obtain the carboxylic acid oxime ester compound; The aryl-substituted acyl chloride has the structure shown in any one of formulas a to c; Formula a Formula b Equation c, R1 to R7 are as defined in the above technical solution.

[0009] Preferably, the molar ratio of the 2,6-dichlorobenzaldehyde oxime to the aryl-substituted acyl chloride is 1:1 to 1.1.

[0010] Preferably, the alkaline catalyst is an organic amine.

[0011] Preferably, the molar ratio of the 2,6-dichlorobenzaldehyde oxime to the alkaline catalyst is 1:4×10. -4 ~8×10 -4 .

[0012] Preferably, the polar organic solvent is dichloromethane.

[0013] Preferably, the acylation reaction is carried out at a temperature of 25-40°C for 4-6 hours.

[0014] The present invention also provides the application of the carboxylic acid oxime ester compounds described in the above technical solutions or the carboxylic acid oxime ester compounds prepared by the preparation methods described in the above technical solutions as active ingredients in molluscicides.

[0015] This invention provides a carboxylic acid oxime ester compound having the structure shown in any one of Formula I, Formula II, and Formula III. The carboxylic acid oxime ester compound provided by this invention exhibits good killing effect on *Pomacea canaliculata* and is almost non-toxic to non-target organisms, demonstrating environmental friendliness. The results of the examples show that the carboxylic acid oxime ester compounds with structures X-1 to X-14 provided by this invention all possess certain molluscicide activity. Specifically, X-1, after immersion for 72 hours, shows killing activity against *Pomacea canaliculata* close to that of the traditional molluscicide niclosamide, i.e., at a drug concentration of 2 mg / L, the snail mortality rate is ≥87.5% after 72 hours. Regarding fish toxicity, X-1 is safe for fish at a concentration of 16 mg / L, while niclosamide still has a 100% lethality rate for fish at 1 mg / L. This carboxylic acid oxime ester compound shows a significant reduction in fish toxicity compared to niclosamide, demonstrating good safety for aquatic organisms. Attached Figure Description

[0016] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0017] Figures 1-3 The proton NMR spectrum, carbon NMR spectrum, and high-resolution mass spectrometry of compound X-1 obtained in Example 1 of this invention are shown below. Figures 4-6 The proton NMR spectrum, carbon NMR spectrum, and high-resolution mass spectrometry of compound X-2 obtained in Example 2 of this invention are shown below. Figures 7-9 The proton NMR spectrum, carbon NMR spectrum, and high-resolution mass spectrometry of compound X-3 obtained in Example 3 of this invention are shown. Figures 10-12 The proton NMR spectrum, carbon NMR spectrum, and high-resolution mass spectrometry of compound X-4 obtained in Example 4 of this invention are shown. Figures 13-15 The proton NMR spectrum, carbon NMR spectrum, and high-resolution mass spectrometry of compound X-5 obtained in Example 5 of this invention are shown. Figures 16-18 The proton NMR spectrum, carbon NMR spectrum, and high-resolution mass spectrometry of compound X-6 obtained in Example 6 of this invention are shown. Figures 19-21 The proton NMR spectrum, carbon NMR spectrum, and high-resolution mass spectrometry of compound X-7 obtained in Example 7 of this invention are shown. Figures 22-24 The proton NMR spectrum, carbon NMR spectrum, and high-resolution mass spectrometry of compound X-8 obtained in Example 8 of this invention are shown. Figures 25-27The proton NMR spectrum, carbon NMR spectrum, and high-resolution mass spectrometry of compound X-9 obtained in Example 9 of this invention are shown. Figures 28-30 The proton NMR spectrum, carbon NMR spectrum, and high-resolution mass spectrometry of compound X-10 obtained in Example 10 of this invention are shown. Figures 31-33 The proton NMR spectrum, carbon NMR spectrum, and high-resolution mass spectrometry of compound X-11 obtained in Example 11 of this invention are shown below. Figures 34-36 The proton NMR spectrum, carbon NMR spectrum, and high-resolution mass spectrometry of compound X-12 obtained in Example 12 of this invention are shown below. Figures 37-39 The proton NMR spectrum, carbon NMR spectrum, and high-resolution mass spectrometry of compound X-13 obtained in Example 13 of this invention are shown. Figures 40-42 The images show the proton NMR spectrum, carbon NMR spectrum, and high-resolution mass spectrometry of compound X-14 obtained in Example 14 of this invention. Detailed Implementation

[0018] This invention provides a carboxylic acid oxime ester compound having the structure shown in any one of Formula I, Formula II, and Formula III: Formula I; Formula II; Formula III; In Formula I, R1, R2, R4, and R5 are independently -H or halogen groups; R3 in Formula I is one of -H, halogen groups, alkoxy groups, cyano groups, and substituted alkyl groups. In Equation II, R6 is -H; In Formula III, R7 is a halogen.

[0019] In this invention, in Formula I, R1 is -H, -Br, or -Cl; R2 is -H or -Cl; R3 is -H, -Br, -Cl, -F, -CN, -OCH3, or -CF3; R4 is -H or -Cl; and R5 is -H or -Cl. In Formula II, R6 is -H; and in Formula III, R7 is -Cl. The carboxylic acid oxime ester compounds provided by this invention have good killing effects on golden apple snails and are almost non-toxic to non-target organisms, thus exhibiting environmental friendliness.

[0020] This invention provides a method for preparing the carboxylic acid oxime ester compounds described above, comprising the following steps: 2,6-Dichlorobenzaldehyde oxime, aryl-substituted acyl chloride, polar organic solvent, and basic catalyst are mixed and subjected to an acylation reaction to obtain carboxylic acid oxime esters having structures shown in Formulas I to III; wherein the aryl-substituted acyl chloride has a structure shown in any one of Formulas a to c.

[0021] In this invention, unless otherwise specified, all raw materials used in the preparation are commercially available products well known to those skilled in the art or prepared using conventional methods in the art.

[0022] In this invention, the alkaline catalyst is an organic amine, which may be triethylamine in a specific embodiment; the polar organic solvent is dichloromethane.

[0023] In this invention, the molar ratio of 2,6-dichlorobenzaldehyde oxime to the aryl-substituted acyl chloride is 1:1 to 1.1; the molar ratio of 2,6-dichlorobenzaldehyde oxime to the basic catalyst is 1:4 × 10⁻⁶. -4 ~8×10 -4 In a specific embodiment, it can be 1:5×10 -4 Or 1:6×10 -4 The preferred molar ratio of the 2,6-dichlorobenzaldehyde oxime to the volume ratio of the polar organic solvent is 1 mmol: 5~10 mL.

[0024] In this invention, the mixing specifically involves mixing 2,6-dichlorobenzaldehyde oxime, an aryl-substituted acyl chloride, and a polar organic solvent, followed by the dropwise addition of an alkaline catalyst. This invention does not impose any particular limitation on the rate of addition.

[0025] In this invention, the temperature of the acylation reaction is room temperature, which can be 25~40℃ in specific embodiments; the time of the acylation reaction is 4~6 h, which can be 4h, 5h or 6h in embodiments of this invention; the time of the acylation reaction is calculated from the time the alkaline catalyst is added.

[0026] After the acylation reaction is completed, the present invention further includes: quenching the acylation reaction with water and performing post-treatment on the obtained product. In the present invention, the post-treatment includes: extracting the obtained acylation reaction product with dichloromethane, washing the organic phase with distilled water, and successively drying, concentrating under reduced pressure, and recrystallizing to obtain the carboxylic acid oxime ester compound.

[0027] In this invention, the dichloromethane extraction is performed three times, with each extraction using 10 mL of solvent; the washing is performed three times; the drying is done using anhydrous sodium sulfate; and the recrystallization is performed using ethanol. This invention does not impose any particular requirements on the post-treatment methods; methods well-known in the art can be used.

[0028] This invention also provides the application of the carboxylic acid oxime ester compounds described in the above-described technical solutions or the carboxylic acid oxime ester compounds prepared by the preparation methods described in the above-described technical solutions as active ingredients in molluscicides. The carboxylic acid oxime compounds provided by this invention exhibit good killing effects against golden apple snails and are virtually non-toxic to non-target organisms, demonstrating environmental friendliness. The results of the examples show that the carboxylic acid oxime compounds with structures X-1 to X-14 provided by this invention all possess certain molluscicide activity. Specifically, X-1, after immersion for 72 hours, shows killing activity against golden apple snails close to that of the traditional molluscicide niclosamide; that is, at a drug concentration of 2 mg / L, the snail mortality rate is ≥87.5% after 72 hours. Regarding fish toxicity, X-1 is safe for fish (such as carp and grass carp) at a concentration of 16 mg / L, while niclosamide still has a 100% lethality rate for fish at 1 mg / L. The carboxylic acid oxime compounds show a significant reduction in fish toxicity compared to niclosamide, demonstrating good safety for aquatic organisms.

[0029] To further illustrate the present invention, the carboxylic acid oxime ester compounds, their preparation methods, and applications provided by the present invention are described in detail below with reference to the accompanying drawings and embodiments, but these should not be construed as limiting the scope of protection of the present invention.

[0030] Example 1 Carboxylic acid oxime esters were prepared according to the chemical reaction equation shown in Formula 1, wherein R1 is -H, R2 is -Cl, R3 is -H, R4 is -H, and R5 is -H.

[0031] At room temperature, 2,6-dichlorobenzaldehyde oxime (1 mmol, 190 mg) and 3-chlorobenzoyl chloride (1 mmol, 175 mg) were dissolved in 10 mL of dichloromethane in a 50 mL single-necked flask, and one drop of triethylamine (approximately 4 × 10⁻⁶ mg) was added dropwise. -4 The mixture was stirred at room temperature for 6 h (mmol). After the reaction was completed, the mixture was quenched with 5 mL of water and extracted three times with dichloromethane (10 mL solvent each time). The organic phase was washed three times with distilled water, dried with anhydrous sodium sulfate, concentrated under reduced pressure to obtain crude product, and recrystallized from ethanol to obtain white powdery solid carboxylic acid oxime ester compound X-1 with a purity >95%. Yield 91.3%.

[0032] Formula 1.

[0033] The structure of the obtained product was characterized, and the proton NMR spectrum, carbon NMR spectrum, and high-resolution mass spectrometry were obtained as follows: Figures 1-3 As shown, the structural characterization data are as follows: 1 H NMR(400 MHz, CDCl3) δ 8.82(s, 1H), 8.14(t, J =1.9 Hz, 1H), 8.05(dt, J =7.8, 1.3 Hz, 1H), 7.61(ddd,J =8.0,2.2,1.2 Hz), 7.49 — 7.41 (m, 4H); 13 C NMR (101MHz, CDCl3) δ 162.36, 153.27, 135.59, 134.79, 133.89, 133.67, 131.75, 130.02,130.00, 129.84, 128.87, 128.17, 128.05, 127.17; HR-MS (ESI), m / z: [M+Na] + calcd for C 14 H8O2NCl3Na + , 349.9513; found, 349.9509.

[0034] Based on the above data and spectral analysis, the obtained product is the target product, a carboxylic acid oxime ester compound X-1, whose structure is shown in the above X-1 diagram.

[0035] Example 2 The preparation steps are the same as in Example 1, except that R1 is -H, R2 is -H, R3 is -Cl, R4 is -H, and R5 is -H, to obtain carboxylic acid oxime ester compound X-2 with a purity >95% and a yield of 98.0%.

[0036] The structure of the obtained product was characterized, and the proton NMR spectrum, carbon NMR spectrum, and high-resolution mass spectrometry were obtained as follows: Figures 4-6 As shown, the structural characterization data are as follows: 1 H NMR (400 MHz, CDCl3) δ8.82(s, 1H), 8.13(d, J =8.6 Hz,2H), 7.53 —7.43 (m, 5H); 13 C NMR (101 MHz, CDCl3) δ153.06, 140.18, 138.55, 135.61, 133.81,131.68, 131.28, 129.03, 128.86, 128.15, 127.27, 126.72; HR-MS (ESI), m / z : [M+Na] + calcd for C 14 H8O2NCl3Na + , 349.9513; found, 349.9514.

[0037] Example 3 The preparation steps were the same as in Example 1, except that R1 was -H, R2 was -Cl, R3 was -Cl, R4 was -H, and R5 was -H, to obtain carboxylic acid oxime ester compound X-3 with a purity >95% and a yield of 98.0%.

[0038] The structure of the obtained product was characterized, and the proton NMR spectrum, carbon NMR spectrum, and high-resolution mass spectrometry were obtained as follows: Figures 7-9 As shown, the structural characterization data are as follows: 1 H NMR (400 MHz, CDCl3) δ8.83(s, 1H), 8.26(s, 1H), 8.01(d, J =8.5 Hz, 1H), 7.62(td, J =16.1,8.4 Hz,2H), 7.36(d, J =7.8 Hz, 1H), 7.28 (s, 1H); 13 C NMR (101MHz, CDCl3) δ 161.77, 153.45, 150.54, 138.53, 135.62, 133.85, 133.29, 131.81,131.70, 130.85, 128.95, 128.90, 128.16, 127.07; HR-MS (ESI), m / z: [M+Na] + calcdfor C 14 H7O2NCl4Na + , 383.9123; found, 383.9119.

[0039] Example 4 The preparation steps were the same as in Example 1, except that R1 was -Cl, R2 was -H, R3 was -H, R4 was -H, and R5 was -Cl, yielding carboxylic acid oxime ester compound X-4 with a purity >95% and a yield of 74.3%.

[0040] The structure of the obtained product was characterized, and the proton NMR spectrum, carbon NMR spectrum, and high-resolution mass spectrometry were obtained as follows: Figures 10-12 As shown, the structural characterization data are as follows: 1 H NMR (400 MHz, CDCl3) δ8.42(s, 1H), 7.46(dd, J =7.3,4.8 Hz,1H), 7.41—7.39 (m, 3H),7.29—7.23 (m, 2H); 13C NMR (101 MHz, CDCl3) δ165.30, 153.36,145.91, 138.51, 137.24, 135.71, 135.00, 133.89, 131.84, 130.47, 130.01,128.90, 128.26, 127.86; HR-MS (ESI), m / z: [M+Na] + calcd for C 14 H7O2NCl4Na + ,383.9123; found, 383.9129.

[0041] Example 5 The preparation steps were the same as in Example 1, except that R1 was -H, R2 was -Cl, R3 was -H, R4 was -Cl, and R5 was -H, yielding carboxylic acid oxime ester compound X-5 with a purity >95% and a yield of 74.3%.

[0042] The structure of the obtained product was characterized, and the proton NMR spectrum, carbon NMR spectrum, and high-resolution mass spectrometry were obtained as follows: Figures 13-15 As shown, the structural characterization data are as follows: 1 H NMR (400 MHz, CDCl3) δ8.84(s, 1H), 8.05(d, J =2.0 Hz, 1H), 7.99(d, J =1.9 Hz, 1H), 7.63(dt, J =5.7,2.0 Hz,1H), 7.48 — 7.45 (m, 3H); 13 C NMR (101 MHz, CDCl3)δ 161.35, 153.66, 138.55, 135.61, 135.50, 133.83, 133.69, 133.50,131.86, 131.11, 128.91, 128.60, 128.23, 128.16, 126.97; HR-MS (ESI), m / z: [M+Na] + calcd for C 14 H7O2NCl4Na + , 383.9123; found, 383.9132.

[0043] Example 6 The preparation steps are the same as in Example 1, except that R1 is -H, R2 is -H, R3 is -Br, R4 is -H, and R5 is -H, to obtain carboxylic acid oxime ester compound X-6 with a purity >95% and a yield of 89.0%.

[0044] The structure of the obtained product was characterized, and the proton NMR spectrum, carbon NMR spectrum, and high-resolution mass spectrometry were obtained as follows: Figures 16-18 As shown, the structural characterization data are as follows: 1 H NMR (400 MHz, CDCl3) δ8.80(s, 1H), 8.02(d, J =8.6 Hz, 2H), 7.64(d, J =7.3 Hz,2H), 7.48 — 7.40 (m, 3H); 13 C NMR (101 MHz, CDCl3) δ 162.85, 153.11,138.47, 135.57, 133.91, 132.01, 131.72, 131.35, 128.86, 128.17, 127.20,127.15; HR-MS (ESI), m / z : [M+Na] + calcd for C 14 H8O2NCl2BrNa + , 395.8987; found,395.8988.

[0045] Example 7 The preparation steps are the same as in Example 1, except that R1 is -Br, R2 is -H, R3 is -H, R4 is -H, and R5 is -H, to obtain carboxylic acid oxime ester compound X-7 with a purity >95% and a yield of 81.5%.

[0046] The structure of the obtained product was characterized, and the proton NMR spectrum, carbon NMR spectrum, and high-resolution mass spectrometry were obtained as follows: Figures 19-21 As shown, the structural characterization data are as follows: 1 H NMR (400 MHz, CDCl3) δ8.80(s, 1H), 8.13(s, 1H), 8.00(dd, J =6.7, 2.6 Hz, 1H), 7.87 (dd, J =7.3, 2.2 Hz, 1H), 7.71(dd, J =7.2,2.0 Hz,1H), 7.44 — 7.40 (m,3H); 13C NMR (101 MHz, CDCl3)δ 153.35, 150.46, 138.47, 135.61, 134.84, 134.48,133.95, 133.54, 133.11, 131.76, 131.48, 128.91, 128.19, 128.02, 127.33; HR-MS(ESI), m / z: [M+Na] + calcd for C 14 H8O2NCl2BrNa + , 395.8987; found, 395.8990.

[0047] Example 8 The preparation steps were the same as in Example 1, except that R1 was -Br, R2 was -H, R3 was -F, R4 was -H, and R5 was -H, yielding carboxylic acid oxime ester compound X-8 with a purity >95% and a yield of 81.5%.

[0048] The structure of the obtained product was characterized, and the proton NMR spectrum, carbon NMR spectrum, and high-resolution mass spectrometry were obtained as follows: Figures 22-24 As shown, the structural characterization data are as follows: 1 H NMR (400 MHz, CDCl3) δ8.81(s, 1H), 8.20(dd, J =8.7,5.6 Hz,2H), 7.51— 7.41 (m, 3H), 7.20(t, J =8.6 Hz, 2H); 13 C NMR (101 MHz, CDCl3) δ 167.39,164.86, 162.60, 152.93, 138.51, 135.58, 133.87, 132.58, 132.48, 131.67,128.85, 128.16, 127.29, 116.00, 115.78; HR-MS (ESI), m / z: [M+Na] + calcd forC 14 H8O2NCl2FNa + , 333.9808; found, 333.9817.

[0049] Example 9 The preparation steps were the same as in Example 1, except that R1 was -H, R2 was -H, R3 was -H, R4 was -H, and R5 was -H, yielding carboxylic acid oxime ester compound X-9 with a purity >95% and a yield of 91.1%.

[0050] The structure of the obtained product was characterized, and the proton NMR spectrum, carbon NMR spectrum, and high-resolution mass spectrometry were obtained as follows: Figures 25-27 As shown, the structural characterization data are as follows: 1 H NMR (400 MHz, CDCl3) δ8.82(s, 1H), 8.17(d, J =6.8 Hz,2H), 7.48- 7.44(m, 5H); 13 C NMR (101 MHz, CDCl3) δ 163.54, 152.83, 138.49, 135.57, 133.92,133.65, 131.63, 129.88, 128.84, 128.63, 128.19, 127.39, 114.40, 113.37; HR-MS(ESI), m / z: [M+Na] + calcd for C 14 H9O2NCl2Na + , 315.9903; found, 315.9912.

[0051] Example 10 The preparation steps were the same as in Example 1, except that R1 was -H, R2 was -H, R3 was -CN, R4 was -H, and R5 was -H, yielding carboxylic acid oxime ester compound X-10 with a purity >95% and a yield of 87.7%.

[0052] The structure of the obtained product was characterized, and the proton NMR spectrum, carbon NMR spectrum, and high-resolution mass spectrometry were obtained as follows: Figures 28-30 As shown, the structural characterization data are as follows: 1 H NMR (400 MHz, CDCl3) δ8.85(s, 1H), 8.28(dt, J =8.5, 1.6 Hz, 2H), 7.84(dt, J =8.4,1.5 Hz,2H), 7.48 — 7.44 (m, 3H); 13C NMR (101 MHz, CDCl3) δ161.99,153.72, 138.52, 135.62, 133.87, 132.44, 132.23, 131.91, 130.39, 128.94,128.17, 126.94, 117.80, 117.05, 114.45, 113.36; HR-MS (ESI), m / z: [M+Na] + calcd for C 14 H8O2N2Cl2Na + , 340.9855; found, 340.9864.

[0053] Example 11 The preparation steps were the same as in Example 1, except that R1 was -H, R2 was -H, R3 was -OMe, R4 was -H, and R5 was -H, to obtain the carboxylic acid oxime ester compound X-11 with a purity >95% and a yield of 78.4%.

[0054] The structure of the obtained product was characterized, and the proton NMR spectrum, carbon NMR spectrum, and high-resolution mass spectrometry were obtained as follows: Figures 31-33 As shown, the structural characterization data are as follows: 1 H NMR (400 MHz, CDCl3) δ8.78(s, 1H), 8.12(dt, J =8.9,2.8 Hz,2H), 7.44— 7.39 (m, 3H), 6.98(dt, J =8.9,2.9 Hz,2H), 3.90(s, 3H); 13 C NMR (101 MHz, CDCl3) δ163.91, 163.30, 152.38, 138.47, 135.55, 133.92, 132.01, 131.52,129.78, 128.80, 128.18, 127.53, 120.37, 113.92, 55.53; HR-MS (ESI), m / z: [M+Na] + calcd for C 15 H 12 O3NCl2Na + , 324.0189; found, 324.0197.

[0055] Example 12 The preparation steps were the same as in Example 1, except that R1 was -H, R2 was -H, R3 was -CF3, R4 was -H, and R5 was -H, yielding carboxylic acid oxime ester compound X-12 with a purity >95% and a yield of 94.7%.

[0056] The structure of the obtained product was characterized, and the proton NMR spectrum, carbon NMR spectrum, and high-resolution mass spectrometry were obtained as follows: Figures 34-36 As shown, the structural characterization data are as follows: 1 H NMR (400 MHz, CDCl3) δ8.45(s, 1H), 8.30(d, J =8.1 Hz, 2H), 7.79(d, J =8.2 Hz,2H), 7.45 — 7.42 (m, 2H), 7.35(dd, J =9.1, 7.1 Hz, 1H); 13 C NMR (101 MHz, CDCl3) δ162.37, 153.47, 135.62, 135.20, 134.87, 131.80, 131.62, 130.30,128.90, 128.16, 127.09, 125.68, 125.64, 124.88, 122.17; HR-MS (ESI), m / z [M+Na] + calcd for C 15 H8O2Cl2F3NNa + , 383.9776; found, 383.9783.

[0057] Example 13 Carboxylic acid oxime compounds were prepared according to the chemical reaction equation shown in Equation 2, where R6 is -H; at room temperature, 2,6-dichlorobenzaldehyde oxime (1 mmol, 190 mg) and 2-furanoyl chloride (1 mmol, 131 mg) were dissolved in 10 mL of dichloromethane in a 50 mL single-necked flask, and one drop of triethylamine (approximately 4 × 10⁻⁶ mg) was added dropwise. -4 The mixture was stirred at room temperature for 6 h (mmol). After the reaction was completed, the mixture was quenched with 5 mL of water and extracted three times with dichloromethane (10 mL each time). The organic phase was washed three times with distilled water and then dried with anhydrous sodium sulfate. The crude product was concentrated under reduced pressure and recrystallized with ethanol to obtain carboxylic acid oxime ester compound X-13 with a purity >95% and a yield of 85.9%.

[0058] Equation 2.

[0059] The structure of the obtained product was characterized, and the proton NMR spectrum, carbon NMR spectrum, and high-resolution mass spectrometry were obtained as follows: Figures 37-39 As shown, the structural characterization data are as follows: 1 H NMR(400 MHz, CDCl3) δ 8.78(s, 1H), 8.40(s, 1H), 7.69(d, J =1.9 Hz,1H),7.43 — 7.39 (m, 3H), 6.61(dd, J =3.6, 1.8 Hz, 1H); 13 C NMR (101 MHz, CDCl3) δ153.02, 147.24, 146.11, 142.50, 135.56, 131.69, 130.41, 128.81, 128.17,127.24, 119.56, 112.22; HR-MS (ESI), m / z : [M+Na] + calcd for C 12 H7O3NCl2Na + ,305.9695; found, 305.9703.

[0060] Example 14 Carboxylic acid oxime compounds were prepared according to the chemical reaction equation shown in Equation 3, where R7 is -Cl; at room temperature, 2,6-dichlorobenzaldehyde oxime (1 mmol, 190 mg) and 5-chloro-2-acylthiophene (1 mmol, 181 mg) were dissolved in 10 mL of dichloromethane in a 50 mL single-necked flask, and one drop of triethylamine (approximately 4 × 10⁻⁶ mg) was added dropwise. -4 The mixture was stirred at room temperature for 6 h (mmol). After the reaction was completed, the mixture was quenched with 5 mL of water and extracted three times with dichloromethane (10 mL of solvent each time). The organic phase was washed three times with distilled water and then dried with anhydrous sodium sulfate. The crude product was concentrated under reduced pressure and recrystallized with ethanol to obtain carboxylic acid oxime ester compound X-14 with a purity >95% and a yield of 83.6%.

[0061] Formula 3.

[0062] The structure of the obtained product was characterized, and the proton NMR spectrum, carbon NMR spectrum, and high-resolution mass spectrometry were obtained as follows: Figures 40-42 As shown, the structural characterization data are as follows: 1 H NMR (400 MHz, CDCl3) δ 8.76 (s, 1H), 7.70 (d, J=3.9 Hz,1H), 7.48 - 7.45(m, 3H), 7.00(d, J =4.0 Hz, 1H); 13 C NMR (101 MHz, CDCl3) δ152.96, 138.50, 135.57,134.34, 133.90, 131.75, 128.86, 128.18, 127.57, 127.10, 114.42, 113.37; HR-MS(ESI), m / z: [M+Na] + calcd for C 12 H6O2NCl3SNa + , 355.9077; found, 355.9088.

[0063] Test Example 1 Preliminary laboratory molluscicidal properties of molluscicides Experimental subject: Pomacea canaliculata, a snail with good activity, taken from Yangzonghai Wetland in Kunming, Yunnan Province.

[0064] Experimental method: The experiment was conducted by immersion method, and a control group was set up with niclosamide as positive control and dimethyl sulfoxide (DMSO) as negative control.

[0065] After being rinsed clean with tap water, golden apple snails were kept in dechlorinated tap water. Snails of uniform size, with no obvious damage to their shells and strong vitality were selected for the experiment. 12 mg, 30 mg, and 60 mg of molluscicide (X-1~X-14) were accurately weighed using an analytical balance. DMSO (3 mL) was added to each snail to ensure complete dissolution. Then, Tween 20 (1 mL) and water (6 L) were added and mixed thoroughly to obtain solutions of 2 mg / L, 5 mg / L, and 10 mg / L. Eight snails were placed at the center of the bottom for each concentration group, and one experiment was conducted for each concentration group.

[0066] Method for positive control group test of niclosamide: Accurately weigh 12 mg, 30 mg and 60 mg of niclosamide using an analytical balance, add 3 mL of DMSO to dissolve them completely, then add 1 mL of Tween 20 and 6 L of water and mix well to obtain 2 mg / L, 5 mg / L and 10 mg / L drug solutions. Place 8 snails in the center of the bottom for each concentration group, and set up 1 experiment for each concentration group.

[0067] DMSO negative control group test method (Control group): Add DMSO (3 mL), then add Tween 20 (1 mL) and water (6 L), mix well, and place 8 snails in the center of the bottom to set up one experiment.

[0068] The snails were covered with plastic mesh to prevent them from escaping. The number of dead snails was recorded after soaking for 24 h, 48 h, and 72 h, and the mortality rate after 72 h was calculated. The specific data are shown in Table 1.

[0069] Table 1. Record of molluscicidal activity of carboxylic acid oxime esters X-1~X-14

[0070] Test Example 2 Healthy carp and grass carp were selected as experimental subjects, with a weight ranging from 1.34 g ± 0.37 g to 1.42 g ± 0.21 g and an average length ranging from 3.60 cm ± 0.25 cm to 4.36 cm ± 0.25 cm. Before conducting the fish toxicity test, 6 L aquariums were filled with water and exposed to sunlight for two days to remove chlorine. Newly purchased fish were placed in the prepared dechlorinated water for at least one week of acclimatization training. The water was changed every two days to keep it clean, and appropriate feed (special goldfish feed) was provided to ensure the accuracy and reliability of the experimental data. A clearly defined water group was established as a negative control for each group, and a commercially available molluscicide, niclosamide, was used as a positive control. In the test system containing DMSO (3 mL), the concentrations of the compounds used for fish toxicity testing were 2 mg / L, 5 mg / L, 10 mg / L, and 16 mg / L. Tween 20 (1 mL) and water (6 L) were added and mixed thoroughly. Then, 10 active carp or grass carp were placed in a 6 L aquarium for a fish toxicity test. During this period, fish mortality rates were carefully recorded at 24 h, 48 h, and 72 h. Dead fish were immediately removed from the tank and disposed of to prevent water contamination, thus ensuring the smooth conduct of the experiment. The 72 h test data are shown in Table 2.

[0071] Table 2. Fish toxicity test records of carboxylic acid oxime ester compound X-1 over 72 hours.

[0072] As shown in Tables 1 and 2, the carboxylic acid oxime compounds provided by this invention all have certain molluscicidal activity. Compound X-1, after immersion for 72 hours, exhibits similar molluscicidal activity against golden apple snails to niclosamide. Specifically, at a drug concentration of 2 mg / L, the snail mortality rate after 72 hours is more than 87.5% of that of niclosamide, and its fish toxicity is significantly lower than that of niclosamide. This series of molluscicidal compounds has the advantages of simple synthesis process and high yield, and has certain commercial application potential in the field of chemical molluscicides.

[0073] Although the above embodiments have provided a detailed description of the present invention, they are only some embodiments of the present invention, and not all embodiments. People can obtain other embodiments based on these embodiments without creative effort, and these embodiments all fall within the protection scope of the present invention.

Claims

1. A carboxylic acid oxime ester compound, characterized in that, It has the structure shown in any one of Equations I, II, and III: Formula I; Formula II; Formula III; In Formula I, R1, R2, R4, and R5 are independently -H or halogen groups; R3 in Formula I is one of -H, halogen groups, alkoxy groups, cyano groups, and substituted alkyl groups. In Equation II, R6 is -H; In Formula III, R7 is a halogen group.

2. The carboxylic acid oxime ester compound according to claim 1, characterized in that, In Formula I, the halogen group in R1 is -Br or -Cl, the halogen group in R2 is -Cl, the halogen group in R4 is -Cl, and the halogen group in R5 is -Cl; the halogen group in R3 is -Br, -Cl, or -F, the alkoxy group is a C1~C3 alkoxy group, the substituted alkyl group is a halo-C1~C3 alkyl group, and the halo-substituted group is fluorinated; In Formula III, the halogen group in R7 is -Cl.

3. The carboxylic acid oxime ester compound according to claim 1 or 2, characterized in that, It has the structure shown in any one of X-1 to X-14: X-1、 X-2、 X-3、 X-4、 X-5、 X-6、 X-7、 X-8、 X-9、 X-10、 X-11、 X-12、 X-13、 X-14。 4. A method for preparing the carboxylic acid oxime ester compound according to any one of claims 1 to 3, characterized in that, Includes the following steps: 2,6-Dichlorobenzaldehyde oxime, aryl-substituted acyl chloride, polar organic solvent and basic catalyst are mixed and subjected to acylation reaction to obtain the carboxylic acid oxime ester compound; The aryl-substituted acyl chloride has the structure shown in any one of formulas a to c; Formula a Formula b Equation c, Wherein R1 to R7 are as defined in claim 1.

5. The preparation method according to claim 4, characterized in that, The molar ratio of the 2,6-dichlorobenzaldehyde oxime to the aryl-substituted acyl chloride is 1:1 to 1.

1.

6. The preparation method according to claim 4, characterized in that, The alkaline catalyst is an organic amine.

7. The preparation method according to claim 4, characterized in that, The molar ratio of 2,6-dichlorobenzaldehyde oxime and the alkaline catalyst is 1:4×10. -4 ~8×10 -4 .

8. The preparation method according to claim 4, characterized in that, The polar organic solvent is dichloromethane.

9. The preparation method according to claim 4 or 5, characterized in that, The acylation reaction is carried out at a temperature of 25-40°C for 4-6 hours.

10. The use of the carboxylic acid oxime ester compound according to any one of claims 1 to 3 or the carboxylic acid oxime ester compound prepared by the preparation method according to any one of claims 4 to 9 as the active ingredient of a molluscicide.

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