Novel pyrazole propionamide derivative as well as preparation method and application thereof

Abstract

The invention provides a novel pyrazole amide derivative as well as a preparation method and application thereof, and relates to 1-oxypropionamide-pyrazole-3-carboxylic ester derivatives which have a chemical structural general formula as shown in V in the specification. The invention discloses a structural general formula and a synthesis method of the compound, as well as a biological activity of the compound for controlling agricultural, gardening and forestry weeds and a determination method of the compound, and also provides application of the compounds in the fields of agriculture, gardening and forestry.

Description

Technical Field

[0001] The technical scheme of the present invention relates to pyrazole propionamide compounds, specifically to 1-oxypropionamide-pyrazole-3-carboxylate derivatives. Background Art

[0002] Weeds are one of the factors that affect crop production. They compete with crops for survival resources, resulting in an average global crop yield reduction of more than 30% (Horvath, DP Trends. Plant. Sci. 2023, 28: 567-582). At present, chemical herbicides are the most effective and direct solution for comprehensive weed control, but the large-scale repeated use of a single herbicide has led to an increasingly serious problem of weed resistance. Therefore, it is necessary to create new herbicides to meet market demand.

[0003] The discovery of new targets and the development of inhibitors are of great significance to improving the competitiveness of my country's pesticide market and alleviating the problem of weed resistance. Transketolase, which is commonly found in the pentose phosphate pathway and Calvin cycle in plants, can catalyze the reversible transfer of two carbon atom units between the phosphate ketose donor and the phosphate aldose acceptor, and plays an important role in plant photosynthesis. It has now been used as a potential herbicide target for herbicide creation research.

[0004] Pyrazole heterocyclic compounds have the characteristics of diverse structures and wide range of biological activities (Lu Shichao. Pesticides, 2020, 59(06): 397-406), and are widely developed in pesticide products such as insecticides, fungicides, and herbicides. For example, herbicides containing pyrazole structures include Benzofenap, Pyrazoxyfen, Pyrazosulfuron-ethyl, Metazachlor, etc. Also frequently appearing in the herbicide structure is the O-propionamide structure, and herbicides containing this structure show high activity and high selectivity. For example, typical herbicide products include Tiafenacil, Metamifop, Clomeprop, and Naproanilide. Therefore, the rational design of pyrazole structures and O-propionamides with herbicidal activity is expected to discover new herbicide molecules.

[0005] In order to discover a transketolase inhibitor skeleton with herbicidal activity, the present invention rationally combines the -O-CH(CH3)-C(O)N- group in the oxadiazine structure with the pyrazole structure, designs and synthesizes a new type of 1-oxypropionamide-pyrazole-3-carboxylate derivatives with simple substituents, and systematically screens and evaluates their biological activities, in order to provide more candidate compounds with high activity and low resistance risk for the creation and research of new target herbicides. Summary of the invention

[0006] The technical problem to be solved by the present invention is to provide a method for synthesizing a new type of 1-oxypropionamide-pyrazole-3-carboxylate derivatives, and a method for determining their biological activity in controlling agricultural, horticultural and forestry weeds, and to provide applications of these compounds in the agricultural, horticultural and forestry fields.

[0007] The technical solution adopted by the present invention to solve the technical problem is: the chemical structure of the 1-oxypropionamide-pyrazole-3-carboxylate compound with herbicidal activity in the agricultural field, the horticultural field, and the forestry field is shown in Formula V:

[0008] V:

[0009] Wherein, X is O or NH;

[0010] R1 is selected from the group consisting of methyl, ethyl, butyl, pentyl, phenyl, benzyl, propargyl, 4-isopropylphenyl, 4-trifluoromethylphenyl, 2,4-dichlorophenyl, 3,4-difluorophenyl, 3-fluoro-4-trifluoromethylphenyl, 2,3,4-trifluoromethylphenyl, 2,3,4,5,6-pentafluoromethylphenyl, 3,4-methylenedioxyphenyl, 6-methoxypyridin-3-yl, 2,6-dichloropyridin-3-yl, 4-methoxy-6-methylpyrimidin-2-yl, 4,6-dimethoxypyrimidin-2-yl, 4-(3-oxomorpholino)phenyl, 2-(o-tolyloxy)phenyl, 4-(4-methoxyphenoxy)phenyl, 4-((5-(trifluoromethyl)pyridin-2-yl)oxy)phenyl, 2-carboxylic acid methyl ester-5-phenylthiophen-2-yl;

[0011] R 2 Selected from: methyl, tert-butyl, phenyl, 2-fluorophenyl, 2,4-dichlorophenyl.

[0012] The synthesis method of the 1-oxypropionamide-pyrazole-3-carboxylate derivative V of the present invention is as follows:

[0013]

[0014] Wherein, X is O or NH;

[0015] R 1Selected from: methyl, ethyl, butyl, pentyl, phenyl, benzyl, propargyl, 4-isopropylphenyl, 4-trifluoromethylphenyl, 2,4-dichlorophenyl, 3,4-difluorophenyl, 3-fluoro-4-trifluoromethylphenyl, 2,3,4-trifluoromethylphenyl, 2,3,4,5,6-pentafluoromethylphenyl, 3,4-methylenedioxyphenyl, 6-methoxypyridin-3-yl, 2,6-dichloropyridin-3-yl, 4-methoxy-6-methylpyrimidin-2-yl, 4,6-dimethoxypyrimidin-2-yl, 4-(3-oxomorpholino)phenyl, 2-(o-tolyloxy)phenyl, 4-(4-methoxyphenoxy)phenyl, 4-((5-(trifluoromethyl)pyridin-2-yl)oxy)phenyl, 2-carboxylic acid methyl ester-5-phenylthiophen-2-yl;

[0016] R 2 Selected from: methyl, tert-butyl, phenyl, 2-fluorophenyl, 2,4-dichlorophenyl.

[0017] The specific method for the synthesis of the 1-oxypropionamide-pyrazole-3-carboxylate derivative V of the present invention and the determination of the biological activity is divided into the following steps:

[0018] A. Preparation of Compound II:

[0019] In a 50 ml single-necked round-bottom flask, 4.58 mmol of R 1 The substituted alcohol or amine was dissolved in 20 ml of dichloromethane, 5.04 mmol of triethylamine was slowly added dropwise, and the reaction was carried out at room temperature for 5 minutes, and then 4.58 mmol of compound I was slowly added dropwise, and the reaction was carried out at room temperature for 3 hours, and the reaction progress was monitored by TLC. After the reaction was completed, the mixed solution was washed 3 times with saturated brine, the aqueous phase was separated, the organic layer was retained, the aqueous layer was stripped twice, the organic layers were combined, and the compound II was purified by 100-200 mesh silica gel column chromatography, the eluent was petroleum ether: ethyl acetate, the volume ratio was 8:1, and the yield was 40.54-94.87%; the amount of compound II prepared and the volume of the reaction container were enlarged or reduced in the corresponding proportion.

[0020] B. Preparation of Compound IV:

[0021] a. When R 2 When it is methyl, the preparation of compound IV:

[0022] In a 200 ml single-necked round-bottom flask, 42.22 mmol of compound III and 44.33 mmol of methylhydrazine sulfate were added, 12 ml of toluene and 12 ml of glacial acetic acid were added to dissolve, and then 105.55 mmol of sodium acetate was added. The mixture was stirred at 100° C. for 1.5 hours. After the reaction was complete, the solvent was removed under reduced pressure. The residue was purified by 100-200 mesh silica gel column chromatography to obtain compound IV. The eluent was dichloromethane:ethyl acetate in a volume ratio of 10:1, and the yield was 37.88%; the amount of compound IV prepared and the volume of the reaction container were enlarged or reduced in corresponding proportions.

[0023] b. When R 2 When it is phenyl, the preparation of compound IV:

[0024] 1.85 mmol of compound III was added to a 50 ml single-mouth round-bottom flask, 16 ml of methanol was added to dissolve, and then 1.85 mmol of phenylhydrazine was added to react at room temperature for 16 hours. After completion, the solvent was evaporated, 6 ml of xylene was added, and the mixture was stirred at 130°C for 2 hours. After the reaction was complete, the organic layer was washed with 2 mol / L dilute hydrochloric acid, dried over anhydrous sodium sulfate, and the solvent was evaporated to obtain compound IV with a yield of 62.00%; the amount of compound IV prepared and the volume of the reaction container were enlarged or reduced in a corresponding proportion.

[0025] c. When R 2 Preparation of compound IV when is other substituent:

[0026] In a 100 ml single-necked round-bottom flask, add 11.24 mmol of compound III, add 20 ml of methanol to dissolve, and then slowly add 34.80 mmol of R 2 Replace hydrazine, stir at 0°C for 5 hours. After the reaction is completed, filter and recrystallize the solid, and redissolve it in 4 ml of methanol, add 40 μl of triethylamine, stir at 70°C for 1 hour, remove the solvent under reduced pressure after the reaction is complete, and purify the residue by 100-200 mesh silica gel column chromatography to obtain compound IV, the eluent is petroleum ether: ethyl acetate, the volume ratio is 6:1, and the yield is 46.67-62.50%; the amount of compound IV prepared and the volume of the reaction container are enlarged or reduced in the corresponding proportion.

[0027] C. Preparation of Compound V:

[0028] 0.79 mmol of compound IV was added to a 10 ml microwave tube, 0.5 ml of N,N-dimethylformamide was added to dissolve, 1.58 mmol of sodium hydride with a content of 60% was slowly added, and then 0.95 mmol of compound II was added, and the mixture was stirred at room temperature for 3 hours. After the reaction was completed, the mixed solution was washed 3 times with saturated brine, the aqueous phase was separated, the organic layer was retained, the aqueous layer was back-extracted twice, the organic layers were combined, and the compound V was purified by 100-200 mesh silica gel column chromatography, the eluent was petroleum ether: ethyl acetate, the volume ratio was 8:1, and the yield was 7-80%; the amount of compound IV prepared and the volume of the reaction container were increased or decreased in the corresponding proportion.

[0029] D. Determination of the herbicidal activity of the pyrazole propionamide derivative V of the present invention:

[0030] a. Small cup method herbicidal activity test:

[0031] Take 20 mg of compound V and dissolve it in 1 ml of N,N-dimethylformamide to prepare a mother solution with a concentration of 20,000 mg / L, and then dilute it to 200 mg / L with distilled water containing 0.1% Tween 80 emulsifier. The final content of DMF in the test solution is less than 1%. Germinate the seeds of the test weeds two days in advance, then use tweezers to pick the seeds with consistent germination effects and place them evenly in a 50 ml small beaker, 9 seeds per cup, and repeat each treatment 3 times. Finally, 1 ml of the agent with a concentration of 200 mg / L is evenly added to the beaker and cultured for one week at a temperature of 25°C, a humidity of 75%, and a light day-night ratio of 16:8. Measure the root length and stem length of the weeds, and calculate the root length inhibition rate and stem length inhibition rate by comparing with the blank control weeds. The test weeds are species of most typical weeds actually occurring in the fields in my country's agricultural production. Their codes and names are as follows: DS: Digitaria sanguinalis, AR: Amaranthus retroflexus, SV: Setaria viridis, EC: Echinochloa crusgalli, DS: Descurainia sophia, PO: Portulaca oleracea, LP: Lolium perenne, CE: Cichorium endivia, Cichorium endivia.

[0032]

[0033]

[0034] b. Leaf spray herbicidal activity test:

[0035] Take 20 mg of compound V and dissolve it in 1 ml of N,N-dimethylformamide to prepare a mother solution with a concentration of 20,000 mg / L, and then dilute it to 150 g / hectare with distilled water containing 0.1% Tween 80 emulsifier. The final content of DMF in the test solution is less than 1%. Mix the nutrient soil and vermiculite in a volume ratio of 1:1, put the prepared mixed soil into the flower pot, and use the bottom of the pot to make the soil completely wet. Use tweezers to take 9 seeds of the spare test plants and place them evenly in the flower pot in turn, and cover the soil to the mouth of the pot. Cultivate in a greenhouse at 25°C, add water in time to keep it moist, and when the test plants grow to the two-leaf and one-heart stage, use a walking spray tower (3WP-2000) to spray the medicine uniformly, and repeat each treatment 3 times. The treated weeds are placed in the greenhouse for cultivation, and water is added in time during the period to ensure that the soil is moist. After 14 days, weigh the fresh weight of the aboveground part of the weeds and calculate the fresh weight inhibition rate. The test weeds are species of most typical weeds actually occurring in the fields in my country's agricultural production. Their codes and names are as follows: DS: Digitaria sanguinalis, its Latin name is: AR: Amaranthus retroflexus, its Latin name is: Amaranthus retroflexus.

[0036]

[0037] E. The inhibitory activity of the pyrazole propionamide derivative V of the present invention on Setaria viridis transketolase (SvTKL):

[0038] The transketolase protein (SvTKL) of Setaria viridis was expressed and purified by prokaryotic expression. The specific test method of the pyrazole propionamide derivative V of the present invention on the SvTKL enzyme activity is as follows: First, a 1.5 mg / ml SvTKL concentration was treated with a gradient concentration compound (v:v=99:1) at 30°C, and after 10 minutes, a magnesium chloride aqueous solution (1.80×10 4 mg / L, 20 μL), TPP coenzyme (1.10×10 4 mg / L, 20 μL) and phenol red (99.2 mg / L, 20 μL), and then incubated at 37°C for 5 minutes. After the incubation, the mixture (160 μL) was transferred to a 96-well plate. Then, 1.80×10 5 mg / L d-glyceraldehyde (20 μL) and 5.40×10 4 mg / L β-hydroxyacetic acid lithium salt hydrate (20 μL), mixed for 60 seconds, and then the corresponding enzyme activity inhibition rate was calculated according to the absorbance measured at 650 nm. SPSS19.0 software was used to calculate IC 50 value.

[0039] The beneficial effects of the present invention are: the pyrazole propionamide derivative V is optimized first, and the herbicidal activity of the pyrazole propionamide derivative V is screened and the SvTKL inhibitory activity is tested.

[0040] The present invention further specifically illustrates the synthesis, biological activity and application of pyrazole propionamide derivative V through specific preparation and biological activity determination examples. The examples are only used to specifically illustrate the present invention but not to limit the present invention. In particular, the biological activity is only an example but not to limit the present invention. The specific implementation methods are as follows:

[0041] Example 1: Preparation of Compound II:

[0042] In a 50 ml single-necked round-bottom flask, 4.58 mmol of R 1 The substituted alcohol or amine was dissolved in 20 ml of dichloromethane, 5.04 mmol of triethylamine was slowly added dropwise, and the reaction was carried out at room temperature for 5 minutes, and then 4.58 mmol of compound I was slowly added dropwise, and the reaction was carried out at room temperature for 3 hours, and the reaction progress was monitored by TLC. After the reaction was completed, the mixed solution was washed 3 times with saturated brine, the aqueous phase was separated, the organic layer was retained, the aqueous layer was stripped twice, the organic layers were combined, and the compound II was purified by 100-200 mesh silica gel column chromatography, the eluent was petroleum ether: ethyl acetate, the volume ratio was 8:1, and the yield was 40.54-94.87%; the amount of compound II prepared and the volume of the reaction container were enlarged or reduced in the corresponding proportion.

[0043] Example 2: Preparation of Compound IV:

[0044] a. When R 2 When it is methyl, the preparation of compound IV:

[0045] In a 200 ml single-necked round-bottom flask, 42.22 mmol of compound III and 44.33 mmol of methylhydrazine sulfate were added, 12 ml of toluene and 12 ml of glacial acetic acid were added to dissolve, and then 105.55 mmol of sodium acetate was added. The mixture was stirred at 100° C. for 1.5 hours. After the reaction was complete, the solvent was removed under reduced pressure. The residue was purified by 100-200 mesh silica gel column chromatography to obtain compound IV. The eluent was dichloromethane:ethyl acetate in a volume ratio of 10:1, and the yield was 37.88%; the amount of compound IV prepared and the volume of the reaction container were enlarged or reduced in corresponding proportions.

[0046] b. When R 2 When it is phenyl, the preparation of compound IV:

[0047] 1.85 mmol of compound III was added to a 50 ml single-mouth round-bottom flask, 16 ml of methanol was added to dissolve, and then 1.85 mmol of phenylhydrazine was added to react at room temperature for 16 hours. After completion, the solvent was evaporated, 6 ml of xylene was added, and stirred at 130°C for 2 hours. After the reaction was complete, the organic layer was washed with 2 mol / L dilute hydrochloric acid, dried over anhydrous sodium sulfate, and the solvent was evaporated to obtain compound IV with a yield of 62.00%; the amount of compound IV prepared and the volume of the reaction container were enlarged or reduced in a corresponding proportion.

[0048] c. When R 2 Preparation of compound IV when is other substituent:

[0049] In a 100 ml single-necked round-bottom flask, add 11.24 mmol of compound III, add 20 ml of methanol to dissolve, and then slowly add 34.80 mmol of R 2 Replace hydrazine, stir at 0°C for 5 hours. After the reaction is completed, filter and recrystallize the solid, and redissolve it in 4 ml of methanol, add 40 μl of triethylamine, stir at 70°C for 1 hour, remove the solvent under reduced pressure after the reaction is complete, and purify the residue by 100-200 mesh silica gel column chromatography to obtain compound IV, the eluent is petroleum ether: ethyl acetate, the volume ratio is 6:1, and the yield is 46.67-62.50%; the amount of compound IV prepared and the volume of the reaction container are enlarged or reduced in the corresponding proportion.

[0050] Example 3: Preparation of Compound V:

[0051] 0.79 mmol of compound IV was added to a 10 ml microwave tube, 0.5 ml of N,N-dimethylformamide was added to dissolve, 1.58 mmol of sodium hydride with a content of 60% was slowly added, and then 0.95 mmol of compound II was added, and the mixture was stirred at room temperature for 3 hours. After the reaction was completed, the mixed solution was washed 3 times with saturated brine, the aqueous phase was separated, the organic layer was retained, the aqueous layer was back-extracted twice, the organic layers were combined, and the compound V was purified by 100-200 mesh silica gel column chromatography, the eluent was petroleum ether: ethyl acetate, the volume ratio was 8:1, and the yield was 7-80%; the amount of compound IV prepared and the volume of the reaction container were increased or decreased in the corresponding proportion.

[0052] Example 4: Preparation of compound S33:

[0053]

[0054] 0.79 mmol of compound IV was added to a 10 ml microwave tube, 0.5 ml of N,N-dimethylformamide was added to dissolve, 1.58 mmol of sodium cyanide with a content of 60% was slowly added, and then 0.95 mmol of compound II was added, and stirred at room temperature for 3 hours. After the reaction was completed, the mixed solution was washed 3 times with saturated brine, the aqueous phase was separated, the organic layer was retained, the aqueous layer was back-extracted twice, the organic layers were combined, and purified by 100-200 mesh silica gel column chromatography, the eluent was petroleum ether: ethyl acetate, the volume ratio was 8:1, and the yield was 46%; the physicochemical parameters and structural parameters of compound V are shown in Table 1.

[0055] Example 5: Results of determination of herbicidal activity of the pyrazole propionamide derivative V of the present invention:

[0056] The codes and names of the common weeds tested in the present invention are as follows: DS: Digitaria sanguinalis, AR: Amaranthus retroflexus, SV: Setaria viridis, EC: Echinochloa crusgalli, DS: Descurainia sophia, PO: Portulaca oleracea, LP: Perennial ryegrass, Lolium perenne, CE: Chicory, Cichorium endivia. These weeds are very representative and can represent most of the weeds occurring in the field during agricultural production. The test methods selected were the small cup method and the stem and leaf spray method.

[0057] The results of the herbicidal activity test using the small cup method are shown in Table 2. Table 2 shows that at 200 mg / L, all the pyrazole propionamide compounds synthesized by the present invention have different degrees of herbicidal activity. For the root length of Amaranthus retroflexus, the inhibition rates of compounds S2, S13, S23, S28, S31, S32, and S36 are above 60%, which are better than the control agents nicosulfuron, mesotrione, atrazine, and oxadiazine. Among them, compound S28 has the best effect, which is more than 10% higher than the control agent; for the stem length of Amaranthus retroflexus, the inhibition effects of compounds S2, S13, S23, and S28 are more than 10% higher than the control agent atrazine; for the root length of Crabgrass, compounds S23, S24, S36 have an inhibition rate of more than 60%, which is better than the control agent nicosulfuron, mesotrione, atrazine, and oxadiazine. Among them, compound S28 has the best effect, which is more than 10% higher than the control agent; for the stem length of Amaranthus retroflexus, the inhibition effects of compounds S2, S13, S23, and S28 are more than 10% higher than the control agent atrazine; for the root length of Crabgrass, compounds S23, S24, S36 have an inhibition rate of more than 60%. The inhibition rates of S25, S28, S30, S31, S32, S33, and S36 were above 65%, which were better than the control agents nicosulfuron, mesotrione, and atrazine, among which compound S23 had the best inhibition effect, which was more than 30% higher than the control agent; for the stem length of Digitaria, the inhibition rates of compounds S24, S30, and S33 were above 40%, which were better than the control agents nicosulfuron, mesotrione, and atrazine, among which compound S33 had the best inhibition effect, which was more than 20% higher than the control agent. In summary, in the small cup method test, compounds S2, S13, S23, and S28 had good growth inhibition activity on Amaranthus retroflexus, and compounds S24, S30, and S33 had good growth inhibition activity on Digitaria.

[0058] The herbicidal activity test results of the stem and leaf spray method are shown in Table 3. Table 3 shows that at 150 g / hectare, all the pyrazole propionamide compounds synthesized by the present invention have different degrees of herbicidal activity. For Amaranthus retroflexus, compounds S12, S13, S14, S16, S23, and S33 have good inhibitory effects, with an inhibition rate of more than 63%, which is better than the control agent oxadiazine; for Digitaria, compounds S23, S24, S26, and S33 have good inhibitory effects, with an inhibition rate of more than 60%. In summary, it can be seen that in the stem and leaf spray method, the inhibition rates of compounds S23 and S33 on Digitaria and Amaranthus retroflexus are both above 60%, and have good herbicidal activity.

[0059] The broad-spectrum test results of the pyrazole propionamide derivative V of the present invention are shown in Table 4, which shows that at 200 mg / L, all compounds have different degrees of herbicidal activity against Setaria, Echinochloa crusgalli, Artemisia selengensis, Portulaca oleracea, Perennial ryegrass, and Chicory. For the root length of Setaria, the inhibition rates of compounds S23 and S33 are above 60%, which is close to the control agent atrazine; for the root length of Echinochloa crusgalli, the inhibition rates of compounds S23 and S33 are above 60%, which is close to the control agents nicosulfuron and mesotrione; for Artemisia selengensis, the inhibition rates of compound S23 on its root length and stem length are 68% and 84%, respectively, which are better than the control agents nicosulfuron, mesotrione, atrazine, and oxadiazine; for Portulaca oleracea, the inhibition rates of compound S23 on its root length and stem length are 68% and 84%, respectively, which are better than the control agents nicosulfuron, mesotrione, atrazine, and oxadiazine. For root length, the inhibition rates of compounds S23 and S33 were over 60%, which were better than those of the control agents nicosulfuron, mesotrione, and oxadiazine; for perennial ryegrass, the inhibition rates of compound S33 on its root length and stem length were 78% and 69%, respectively, which were better than those of the control agent mesotrione; for chicory, the inhibition rates of compound S33 on its root length and stem length were 78% and 66%, respectively, which were better than those of the control agents nicosulfuron, mesotrione, atrazine, and oxadiazine.

[0060] Example 6: SvTKL inhibitory activity of the pyrazole propionamide derivative V of the present invention:

[0061] The results of the SvTKL inhibitory activity of the pyrazole propionamide derivatives V of the present invention are shown in Table 5. Table 5 shows that the IC values ​​of compounds S23 and S33 are 50 The values ​​were 0.508 mg / L and 0.269 mg / L, respectively, which were close to the control drug p-hydroxyphenylpyruvic acid 0.167 mg / L. The results showed that the pyrazole propionamide derivative V of the present invention is an inhibitor of transketolase and is worthy of further study.

[0062] Example 7: Use of the pyrazole propionamide derivative V of the present invention in combination with an agriculturally acceptable adjuvant and any one or more of the following commercial herbicides in the preparation of a compound herbicide:

[0063] The commercial herbicide is selected from nicosulfuron, bensulfuron-methyl, monosulfuron, sulfamethoxam, penoxsulam, alachlor, acetochlor, butachlor, isopropyl metolachlor, 2-methyl-4-chloro, fluralin, mesotrione, mesotrione, benzachlor, pendimethalin, atrazine, promethazine, cyanazine, ametryn, metribuzin, nitropropene, oxyfluorfen, trifluorfen, lactofen, fluazifop-butyl, pyraclostrobin, isopropylpyraclostrobin, imazapic, imazapic, imazapic, imazapic, imazaquin, methyl imazapic, pyrimidine, pyrimidine, bispyribac, pyrimidine, pyrimidine, betamethoxam, betamethoxam, avena cava, diamine, cypermethrin, pyrimidine ... Fluchloral, oxazolidinone, quizalofop-p-butyl, thiazolinone, fluroxypyr, dithiopyr, fluridone, thiamethoxam, flufenacet, paraquat, glyphosate, sedge barnyardgrass, flufenac, fluazifop-butyl, fluthiamethoxam-butyl, flufenacet-butyl, pyrazoline, pyraclostrobin, pyraclostrobin, benzothiazolin, isoxathiocarb, isoxathiocarb, bromoxynil, etc.; the total mass percentage of the pyrazole propionamide derivative V of the present invention in the obtained composite herbicide is 1%-90%, and the ratio of the pyrazole propionamide derivative V of the present invention to the commercial herbicide is 1%:99% to 99%:1% by mass; the formulation suitable for the composite herbicide is selected from any one of the following formulations: wettable powder, microcapsule suspension, dispersible liquid formulation agent, dispersible solid preparation, seed treatment emulsion, water emulsion, large granule, microemulsion, oil suspension, water-soluble granule, soluble concentrate, water-dispersible granule, poisonous valley, aerosol, slow-release block, capsule granule, dry seed powder, emulsifiable concentrate, electrostatic spray, oil-in-water emulsion, water-in-oil emulsion, smoke can, fine granule, smoke candle, smoke tube, smoke stick, seed treatment suspension, smoke tablet, smoke pill, gasifier, drifting powder, ointment, hot fog agent, solid / liquid mixed agent, liquid / liquid mixed agent, cold fog agent, solid / solid mixed agent, lacquer, seed treatment liquid, microgranule, oil-dispersible powder, concentrated glue agent, pouring agent, smear, suspension emulsion, film-forming oil agent, soluble powder, seed treatment water-soluble powder agent, ultra-low volume suspension, tracking powder, ultra-low volume liquid, steam release agent, wet seed dressing water dispersible powder; the plants suitable for the compound herbicide are selected from rice, wheat, barley, oats, corn, sorghum, sweet potato, potato, cassava, soybean, snow pea, broad bean, pea, mung bean, red bean, cotton, sericulture, peanut, rape, sesame, sunflower, beet, sugarcane, coffee, cocoa, ginseng, fritillaria, rubber, coconut, oil palm, sisal, tobacco, tomato, pepper, radish, cucumber, cabbage, celery, mustard, beet, rape, onion, garlic, watermelon, melon, cantaloupe, papaya, apple, citrus, peach, tea, wild vegetables, bamboo shoots, hops, pepper, banana, papaya, orchid, bonsai;The compound herbicide is suitable for controlling weeds selected from: Gramineae weeds: Digitaria, Setaria, Goosegrass, Echinochloa, Leptochloa, Chlorophytum, Wild Oats, Teff, Golden Setaria, Long-awned Coptis, Alopecuroides, etc.; Broadleaf weeds: Amaranthus retroflexus, Purslane, Chenopodium album, Artemisia selengensis, Amaranthus, Xanthium sibiricum, Ambrosia, Amaranthus, Abutilon, Kochia, Solanum nigrum, Willowleaf Prickly, Chickweed, Waterthorn Needle, Rumex, Cupressus, Field Bindweed, Cuscuta, etc.; Cyperaceae weeds: Cyperus rotundus, Cyperus heterosexualus, Cyperus watergrass, Salsola, Onion, etc.;

[0064]

[0065]

[0066]

[0067]

[0068]

[0069] Table 2 Herbicidal activity of the pyrazole propionamide derivatives V of the present invention by the small cup method

[0070]

[0071] Table 3 Herbicidal activity of pyrazole propionamide derivatives V of the present invention by foliar spraying

[0072]

[0073] Table 4 Broad spectrum test of pyrazole propionamide derivative V of the present invention

[0074]

[0075] Table 5 Inhibitory effect of pyrazole propionamide derivatives V of the present invention on SvTKL

[0076]

Claims

1. A class of 1-oxypropionamide-pyrazole-3-carboxylate derivatives, characterized in that It has a general chemical structure as shown in Formula V: Ⅴ： Wherein, X is O or NH; R 1 Selected from: methyl, ethyl, butyl, pentyl, phenyl, benzyl, propargyl, 4-isopropylphenyl, 4-trifluoromethylphenyl, 2,4-dichlorophenyl, 3,4-difluorophenyl, 3-fluoro-4-trifluoromethylphenyl, 2,3,4-trifluoromethylphenyl, 2,3,4,5,6-pentafluoromethylphenyl, 3,4-methylenedioxyphenyl, 6-methoxypyridin-3-yl, 2,6-dichloropyridin-3-yl, 4-methoxy-6-methylpyrimidin-2-yl, 4,6-dimethoxypyrimidin-2-yl, 4-(3-oxomorpholino)phenyl, 2-(o-tolyloxy)phenyl, 4-(4-methoxyphenoxy)phenyl, 4-((5-(trifluoromethyl)pyridin-2-yl)oxy)phenyl, 2-carboxylic acid methyl ester-5-phenylthiophen-2-yl; R 2 Selected from: methyl, tert-butyl, phenyl, 2-fluorophenyl, 2,4-dichlorophenyl.

2. The method for synthesizing the 1-oxypropionamide-pyrazole-3-carboxylate derivative V according to claim 1, wherein the specific synthetic route is as follows: in, X is O or NH; R 1 Selected from: methyl, ethyl, butyl, pentyl, phenyl, benzyl, propargyl, 4-isopropylphenyl, 4-trifluoromethylphenyl, 2,4-dichlorophenyl, 3,4-difluorophenyl, 3-fluoro-4-trifluoromethylphenyl, 2,3,4-trifluoromethylphenyl, 2,3,4,5,6-pentafluoromethylphenyl, 3,4-methylenedioxyphenyl, 6-methoxypyridin-3-yl, 2,6-dichloropyridin-3-yl, 4-methoxy-6-methylpyrimidin-2-yl, 4,6-dimethoxypyrimidin-2-yl, 4-(3-oxomorpholino)phenyl, 2-(o-tolyloxy)phenyl, 4-(4-methoxyphenoxy)phenyl, 4-((5-(trifluoromethyl)pyridin-2-yl)oxy)phenyl, 2-carboxylic acid methyl ester-5-phenylthiophen-2-yl; R 2 Selected from: Methyl, tert-butyl, phenyl, 2-fluorophenyl, 2,4-dichlorophenyl. The specific method for synthesizing the 1-oxypropionamide-pyrazole-3-carboxylate derivatives according to claim 1 is divided into the following steps: A. Preparation of Compound II: In a 50 ml single-necked round-bottom flask, 4.58 mmol of R 1 The substituted alcohol or amine was dissolved in 20 ml of dichloromethane, 5.04 mmol of triethylamine was slowly added dropwise, and the reaction was carried out at room temperature for 5 minutes, and then 4.58 mmol of compound I was slowly added dropwise, and the reaction was carried out at room temperature for 3 hours, and the reaction progress was monitored by TLC. After the reaction was completed, the mixed solution was washed 3 times with saturated brine, the aqueous phase was separated, the organic layer was retained, the aqueous layer was stripped twice, the organic layers were combined, and the compound II was purified by 100-200 mesh silica gel column chromatography, the eluent was petroleum ether: ethyl acetate, the volume ratio was 8:1, and the yield was 40.54-94.87%; the amount of compound II prepared and the volume of the reaction container were enlarged or reduced in the corresponding proportion. B. Preparation of Compound IV: a. When R 2 When it is methyl, the preparation of compound IV: In a 200 ml single-necked round-bottom flask, 42.22 mmol of compound III and 44.33 mmol of methylhydrazine sulfate were added, 12 ml of toluene and 12 ml of glacial acetic acid were added to dissolve, and then 105.55 mmol of sodium acetate was added. The mixture was stirred at 100° C. for 1.5 hours. After the reaction was complete, the solvent was removed under reduced pressure. The residue was purified by 100-200 mesh silica gel column chromatography to obtain compound IV. The eluent was dichloromethane:ethyl acetate in a volume ratio of 10:1, and the yield was 37.88%; the amount of compound IV prepared and the volume of the reaction container were enlarged or reduced in corresponding proportions. b. When R 2 When it is phenyl, the preparation of compound IV: 1.85 mmol of compound III was added to a 50 ml single-mouth round-bottom flask, 16 ml of methanol was added to dissolve, and then 1.85 mmol of phenylhydrazine was added to react at room temperature for 16 hours. After completion, the solvent was evaporated, 6 ml of xylene was added, and the mixture was stirred at 130°C for 2 hours. After the reaction was complete, the organic layer was washed with 2 mol / L dilute hydrochloric acid, dried over anhydrous sodium sulfate, and the solvent was evaporated to obtain compound IV with a yield of 62.00%; the amount of compound IV prepared and the volume of the reaction container were enlarged or reduced in a corresponding proportion. c. When R 2 Preparation of compound IV when is other substituent: In a 100 ml single-necked round-bottom flask, add 11.24 mmol of compound III, add 20 ml of methanol to dissolve, and then slowly add 34.80 mmol of R 2 Replace hydrazine and stir at 0°C for 5 hours. After the reaction is completed, filter and recrystallize the solid and redissolve it in 4 ml of methanol. Add 40 μl of triethylamine and stir at 70°C for 1 hour. After the reaction is complete, remove the solvent under reduced pressure. The residue is purified by 100-200 mesh silica gel column chromatography to obtain compound IV. The eluent is petroleum ether: ethyl acetate, the volume ratio is 6:1, and the yield is 46.67-62.50%; the amount of compound IV prepared and the volume of the reaction container are enlarged or reduced in the corresponding proportion. C. Preparation of compound V: 0.79 mmol of compound IV was added to a 10 ml microwave tube, 0.5 ml of N,N-dimethylformamide was added to dissolve, 1.58 mmol of sodium cyanide with a content of 60% was slowly added, and then 0.95 mmol of compound II was added, and the mixture was stirred at room temperature for 3 hours. After the reaction was completed, the mixed solution was washed 3 times with saturated brine, the aqueous phase was separated, the organic layer was retained, the aqueous layer was back-extracted twice, the organic layers were combined, and the compound V was purified by 100-200 mesh silica gel column chromatography, the eluent was petroleum ether: ethyl acetate, the volume ratio was 8:1, and the yield was 7-80%; the amount of compound IV prepared and the volume of the reaction container were increased or decreased in the corresponding proportion.

3. Use of the 1-oxypropionamide-pyrazole-3-carboxylate derivative V according to claim 1 and an agriculturally acceptable adjuvant in the preparation of a herbicide.

4. The 1-oxypropionamide-pyrazole-3-carboxylate derivative V of claim 1 is used in combination with any one or more of the following commercial herbicides to prepare a composite herbicide composition for controlling agricultural, forestry and gardening weeds: The commercial herbicide is selected from nicosulfuron, bensulfuron-methyl, monosulfuron, sulfamethoxam, penoxsulam, alachlor, acetochlor, butachlor, isopropyl metolachlor, 2-methyl-4-chloro, fluralin, mesotrione, mesotrione, benzachlor, pendimethalin, atrazine, promethazine, cyanazine, ametryn, metribuzin, nitropropene, oxyfluorfen, trifluorfen, lactofen, fluazifop-butyl, pyraclostrobin, isopropylpyraclostrobin, imazapic, imazapic, imazapic, imazapic, imazaquin, methyl imazapic, pyrimidine sulfamethoxam, pyrimidine sulfamethoxam, pyrimidine sulfamethoxam, pyrimidine sulfamethoxam, pyrimidine sulfamethoxam, pyrimidine sulfamethoxam, betaine, betaine, avena cava, diamine, cypermethrin, cypermethrin, pyrimidine sulfamethoxam ... Azofenac, quizalofop-p-butyl, thiazopyr, fluroxypyr, dithiopyr, fluridone, thiamethoxam, flufenacet, paraquat, glyphosate, sedge barnyardgrass, flufenac, fluazifop-butyl, fluthiamethoxam, flufenacet-butyl, flumethoxam-butyl, pyrazoline, pyraclostrobin, pyraclostrobin, benzaclostrobin, isoxathiocarb, isoxathiocarb, bromoxynil, etc.; the total mass percentage of the 1-oxypropionamide-pyrazole-3-carboxylate derivative V in the obtained compound herbicide is 1%-90%, and the ratio of the 1-oxypropionamide-pyrazole-3-carboxylate derivative V to the commercial herbicide is 1%:99% to 99%:1% by mass; the formulation suitable for the compound herbicide is selected from any one of the following formulations: wettable powder, micro-powder, Capsule suspension, dispersible liquid preparation, dispersible solid preparation, seed treatment emulsion, water emulsion, large granule, microemulsion, oil suspension, water-soluble granule, soluble concentrate, water-dispersible granule, poisonous valley, aerosol, slow-release block, capsule granule, dry seed powder, emulsifiable concentrate, electrostatic spray, oil-in-water emulsion, water-in-oil emulsion, smoke can, fine granule, smoke candle, smoke tube, smoke stick, seed treatment suspension, smoke tablet, smoke pill, gasifier, drifting powder, ointment, hot fog agent, solid / liquid mixed agent, liquid / liquid mixed agent, cold fog agent, solid / solid mixed agent, lacquer, seed treatment liquid, microgranule, oil-dispersible powder, concentrated glue, pouring agent, smear, suspension emulsion, film-forming oil, soluble powder, seed Water-soluble powder, ultra-low volume suspension, tracking powder, ultra-low volume liquid, steam release agent, wet seed dressing water dispersible powder; the compound herbicide is suitable for plants selected from rice, wheat, barley, oats, corn, sorghum, sweet potato, potato, cassava, soybean, snow pea, broad bean, pea, mung bean, adzuki bean, cotton, sericulture, peanut, rape, sesame, sunflower, beet, sugar cane, coffee, cocoa, ginseng, fritillaria, rubber, coconut, oil palm, sisal, tobacco, tomato, pepper, radish, cucumber, cabbage, celery, mustard, beet, rape, onion, garlic, watermelon, melon, cantaloupe, papaya, apple, citrus, peach, tea, wild vegetables, bamboo shoots, hops, pepper, banana, papaya, orchid, bonsai;The compound herbicide is suitable for controlling weeds selected from: Gramineae weeds: Digitaria, Setaria, Goosegrass, Echinochloa, Leptochloa, Chlorophytum, Wild Oats, Teff, Golden Setaria, Long-awned Coptis, Alopecuroides, etc.; Broadleaf weeds: Amaranthus retroflexus, Purslane, Chenopodium album, Artemisia selengensis, Amaranthus, Xanthium sibiricum, Ambrosia, Amaranthus, Abutilon, Kochia, Solanum nigrum, Willowleaf Prickly, Chickweed, Waterthorn Needle, Rumex, Cupressus, Field Bindweed, Cuscuta, etc.; Cyperaceae weeds: Cyperus rotundus, Cyperus heterosexualus, Cyperus watergrass, Salsola, Onion, etc.;

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