CN111978243B - Synthesis and application of oxalic acid monoester derivative - Google Patents
Synthesis and application of oxalic acid monoester derivative Download PDFInfo
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- CN111978243B CN111978243B CN201910455070.9A CN201910455070A CN111978243B CN 111978243 B CN111978243 B CN 111978243B CN 201910455070 A CN201910455070 A CN 201910455070A CN 111978243 B CN111978243 B CN 111978243B
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- cucumber
- oxalic acid
- acid monoester
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/61—Halogen atoms or nitro radicals
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
- A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
Abstract
The invention relates to synthesis and application of oxalic acid monoester-containing compounds shown as a general formula (I), and the compounds represent a broad-spectrum efficient insecticidal bactericide structural type. The oxalic acid monoester derivative is used as a novel insecticidal bactericide, and can well prevent and control aphids, diamond back moths and beet armyworms; can also be well used for preventing and treating cucumber brown spot, cucumber bacterial angular leaf spot, cucumber fusarium wilt, cucumber downy mildew, cucumber powdery mildew, tomato bacterial spot and rice sheath blight. The meaning of R in the formula is shown in the specification.
Description
One, the technical field
The invention relates to oxalic acid monoester derivatives and application thereof as an insecticide and a bactericide, belonging to the technical field of pesticides.
Second, background art
Neonicotinoid insecticides are another major class of insecticides important after organophosphates, carbamates and pyrethroids. It acts on insect central nervous system, is highly effective and selectively safe to mammals, and has no cross resistance with traditional pesticide. In the mid-80's of the 20 th century, the first neonicotinoid insecticide, imidacloprid, was developed by japan pesticide and bayer corporation and commercialized in 1991. Because imidacloprid has the characteristics of novel action mode, high efficiency, broad spectrum, good selectivity, environmental friendliness and the like, some large pesticide companies in the world focus attention on the research of nicotine analogues successively, and become a great hotspot for pesticide development. Through the research on the functional group transformation and the structure-activity relationship of the compound, a series of super-efficient neonicotinoid insecticides with novel heterocyclic structures are developed successively. Currently, there are 7 neonicotinoid insecticides that have been commercialized: imidacloprid (imidacloprid), thiamethoxam (thiamethoxam), thiacloprid (thiacloprid), dinotefuran (dinotefuran), acetamiprid (acetamiprid), nitenpyram (nitenpyram) and clothianidin (clothianidin). We note that the compound reported by Japanese scientists introduces an ester group into an imidacloprid molecule, and the other compound is a compound which uses two carbonyl groups to connect two imidacloprid molecules together and has better biological activity.
Third, the invention
The invention aims to provide oxalic acid monoester derivatives and application thereof, wherein the compounds have excellent insecticidal and bactericidal activities.
The invention relates to preparation and application of oxalic acid monoester derivatives shown in a general formula (I):
wherein R is 1-6 carbon saturated alkyl, unsaturated alkyl, cycloalkyl, or alkyl substituted by one or more same or different halogen atoms.
The oxalic acid monoester derivative can be prepared by the following method: the intermediate 3 is prepared by reacting the corresponding alcohol raw material 1 with oxalyl chloride. The corresponding substituted intermediate 3 reacts with a compound 4 to prepare the oxalic acid monoester derivative with the target general formula (I).
Compounds 1, 2 and 4 are commercially available or prepared according to known methods.
The invention is further illustrated by the compounds listed in Table 2, but is not limited thereto.
The compound of the general formula (I) has excellent insecticidal and bactericidal activity, and can be used as an insecticide for preventing and controlling lepidoptera, coleoptera, homoptera, diptera and orthoptera pests; as a bactericide, the bactericidal composition can be used for preventing and treating cucumber brown spot, cucumber bacterial angular leaf spot, cucumber fusarium wilt, cucumber downy mildew, cucumber powdery mildew, tomato bacterial spot and rice sheath blight.
The compound of the general formula (I) can be directly used, can be added with an agriculturally acceptable carrier for use, and can also be compounded with other types of pesticide bactericides for use.
Fourth, detailed description of the invention
The invention is further illustrated by the following examples:
the first embodiment is as follows: synthesis of intermediate oxalic acid monoester
Under ice bath, slowly dropping corresponding alcohol (0.1mol) into oxalyl chloride (0.2mol), keeping the temperature at 0 ℃, reacting at room temperature for 2h after dropping, then distilling, firstly distilling off excessive oxalyl chloride, and then distilling under normal pressure or reduced pressure to obtain the target product. The boiling point data and yields are shown in Table 1.
TABLE 1 materialization data for intermediates 3a-3l
The second embodiment: synthesis of Compounds of general formula (I)
Nitenpyram (10mmol) is dissolved in 30mL dry DMF, sodium hydride (0.011mol) is added under ice bath, and the mixture is stirred at room temperature for 1h until no gas is discharged. Then, the corresponding chlorooxalate 3(0.011mol) was added dropwise, the reaction was carried out at room temperature for 5 hours, and then the reaction mixture was poured into 50mL of ice water, extracted with dichloromethane (3X 40mL), and the organic layer was washed with water (3X 40mL), anhydrous Na 2 SO 4 Drying, filtering, concentrating the filtrate, subjecting the residue to silica gel chromatographic column chromatography under reduced pressure, and eluting with mixed solvent of ethyl acetate and petroleum ether to obtain compound of formula (I), wherein the specific compound is shown in Table 2.
TABLE 2 List of oxalic acid monoester derivatives (I)
Example three: biological activity assay
The derivatives (Ia-Il) provided by the invention are used for testing, and the evaluation of the biological activity of pests is verified:
any of the derivatives (Ia to Il) provided by the present invention is dissolved in a solvent, water and a surfactant, mixed to a homogeneous aqueous phase, and diluted with water to any desired concentration at the time of use, and the test subjects and test methods are as follows:
1) evaluation of biological Activity against aphids: the insects tested were the aphid Aphis craccivora, a normal population raised on laboratory broad bean leaves. Weighing 20mg of medicine, adding 0.5mL of DMF for dissolving, adding one drop of Tween-20 emulsifier and 100mL of distilled water, and stirring uniformly to prepare 200mg of kg -1 The liquid medicine is used for dilution. Soaking the leaves of broad beans with aphids (about 60) in the medicament for 5 seconds, taking out, lightly spin-drying, sucking off the excess medicament with filter paper, then inserting the broad bean branches into wet sponge, covering the branches with glass covers, sealing with gauze, checking the mortality rate in 24 or 48 hours, counting and correcting the mortality rate, and repeating each compound for 3 times. Adding an emulsifier and a solvent into distilled water only by contrast, and uniformly stirring;
2) evaluation of biological Activity of Plutella xylostella: the tested insects were diamondback moth 2-instar larvae (Plutella xylostella (L.)), a normal population normally raised indoors; dipping the cabbage leaves in the prepared solution for 2-3 seconds by using a leaf dipping method and using tweezers to throw off residual liquid; 1 tablet at a time, 3 tablets per sample; after the liquid medicine is dried, putting the liquid medicine into a straight test tube with the length of 10cm, inoculating 2-year-old plutella xylostella larvae, and covering the tube opening with gauze; placing the test treatment in a standard treatment chamber, and observing test results after 24 hours, 48 hours and 72 hours;
3) evaluation of biological Activity of beet armyworm: the tested insects are 3-instar larvae of spodoptera exigua Hubner (Laphygma exigua Hubner), which are normal groups normally raised indoors; dipping the cabbage leaves in the prepared solution for 2-3 seconds by using a leaf dipping method and using tweezers to throw off residual liquid; 1 tablet at a time, 3 tablets per sample; after the liquid medicine is dried, putting the liquid medicine into a culture dish with the diameter of 7cm, inoculating 3-instar larvae of spodoptera exigua, putting test treatment into a standard treatment chamber, and observing test results after 24 hours, 48 hours and 72 hours;
some of the test results of the above tests are shown in table 3.
TABLE 3 biological Activity test results of Compounds on aphids, Plutella xylostella and beet armyworm
Mortality rating in table: the grade A is 100-90%; the grade B is 90-70%; the grade C is 70-50%; the grade D is 50-0%.
Example four: micro-screening test for preventing and treating vegetable diseases
Selecting 2 cucumber seedlings at the cotyledon stage, carrying out spray inoculation on cucumber brown spot, powdery mildew and downy mildew by adopting spore suspension, carrying out spray inoculation on cucumber bacterial angular leaf spot and tomato bacterial spot by adopting bacterial suspension, carrying out seed soaking inoculation on cucumber blight by adopting a radicle seed soaking inoculation method, and carrying out hypha spray inoculation on rice sheath blight. Uniformly spraying the test agent and the control agent on the cucumber cotyledon in the morning of a sunny day, inoculating pathogenic bacteria after 2 hours, and performing moisture-keeping culture. After the disease is fully developed in contrast, the disease condition is investigated according to the grading standard, and the disease index and the prevention effect are calculated. Table 4 shows the test results of the compounds.
TABLE 4 results of in vivo microscreen test (500mg kg) for preventing and treating vegetable diseases with compounds -1 )
Claims (3)
1. An oxalic acid monoester derivative is characterized by having a structure shown as the following general formula (I):
in the formula, R is C1-C6 saturated alkyl, allyl, cyclohexyl, benzyl, 2-methoxyethyl and 2,2, 2-trifluoroethyl.
2. The use of oxalic acid monoester derivatives according to claim 1, characterized in that it is used as an insecticide for the control of lepidoptera, coleopteran, homopteran, dipteran and orthopteran pests.
3. The use of oxalic acid monoester derivatives according to claim 1, characterized in that it is used as fungicide for preventing and curing cucumber powdery mildew, cucumber bacterial angular leaf spot, cucumber fusarium wilt, cucumber brown spot, cucumber downy mildew, tomato bacterial spot disease, rice sheath blight.
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| CN201910455070.9A CN111978243B (en) | 2019-05-24 | 2019-05-24 | Synthesis and application of oxalic acid monoester derivative |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001056358A2 (en) * | 2000-01-28 | 2001-08-09 | Rohm And Haas Company | Enhanced propertied pesticides |
| CN1326442A (en) * | 1998-11-17 | 2001-12-12 | 诺瓦提斯公司 | Pesticides |
| CN1907023A (en) * | 2006-08-04 | 2007-02-07 | 华南农业大学 | Coupling compounds of bios and pesticides, their preparation process and use as pesticides |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1326442A (en) * | 1998-11-17 | 2001-12-12 | 诺瓦提斯公司 | Pesticides |
| WO2001056358A2 (en) * | 2000-01-28 | 2001-08-09 | Rohm And Haas Company | Enhanced propertied pesticides |
| CN1907023A (en) * | 2006-08-04 | 2007-02-07 | 华南农业大学 | Coupling compounds of bios and pesticides, their preparation process and use as pesticides |
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