CN109320505B - Preparation and application of halogenated butenolide compound with insecticidal activity - Google Patents
Preparation and application of halogenated butenolide compound with insecticidal activity Download PDFInfo
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Abstract
The invention relates to a preparation method and application of halogenated butenolide compounds with insecticidal activity, and relates to nitrogen-containing ring-opening compounds with a formula (A), wherein R is 1 ，R 2 ，R 3 And X are each as defined in the specification. The invention discloses a preparation method and application of a novel pesticide, wherein the compound and derivatives thereof have the following effects on homoptera, lepidoptera and other agricultural and forestry pests: aphids, plant hoppers, whiteflies, leafhoppers, thrips, cotton bollworms, cabbage caterpillars, diamond back moths, prodenia lituras, armyworms and the like have high insecticidal activity.
Description
Technical Field
The invention relates to a novel butenolide neonicotinoid insecticide, and a preparation method and application thereof.
Technical Field
The neonicotinoid insecticide acts on the nicotinic acetylcholine receptors (nAChRs) of insects, and is a classic green pesticide rapidly with the characteristics of high efficiency, low toxicity, broad spectrum, high selectivity, low residue, safety to mammals and various aquatic organisms and the like. Traditional neonicotinoids (Group 4A agonists covering imidacloprid, acetamiprid, clothianidin, dinotefuran, nitenpyram, thiacloprid and thiamethoxam) represented by imidacloprid are registered in more than 120 countries with global sales of more than 20 hundred million dollars and market share occupancy of more than 25% (european patents 247477, 296453, 685477, 235725, 235725, 315826, 192060, 244777, 0386565, 580553 and 1031566, japanese patents 62292765, 8259568, 8291171 and 7242633). However, in recent years the toxicity of traditional neonicotinoid insecticides to bees has been reported in several countries and regions and is recognized as an important cause of the drastic decline in bee numbers and populations. Countries such as canada and france plan to phase out traditional neonicotinoid insecticides such as imidacloprid in all agricultural products for three years since 2017. The development of neonicotinoid insecticides with novel structures and safety against pollinating insects such as bees has been a dilemma and a great challenge for researchers.
Disclosure of Invention
The invention aims to provide a halogenated butenolide compound for efficiently preventing and treating pests and a preparation method thereof.
It is another object of the present invention to provide protection for growing and harvested crops from insect attack and infestation.
In a first aspect, the present invention provides a compound having a structure represented by formula (a):
the compound of (I), wherein R is 1 Selected from: pyridyl, thiazolyl, pyrimidinyl, tetrahydrofuranyl, oxazolyl, or a halide thereof.
The compound of (I), wherein R is 2 ，R 3 Is C 1-6 Alkyl radical, C 3-4 Cycloalkyl or halo C 1-6 An alkyl group.
The compound is characterized in that X is chlorine or bromine.
The pesticide composition comprises:
(a) 1-99.99% by weight of a compound according to any one of claims 1-4;
(b) an agriculturally pharmaceutically acceptable carrier and/or excipient.
The pesticide composition is characterized by being used for killing or preventing pests selected from the following insects: coleopteran, lepidopteran, hemipteran, orthopteran, isopteran, or dipteran insects, preferably isopteran or lepidopteran insects.
Detailed Description
The inventor finds that the mucohalic acid and the alcohol can react to construct a butenolide skeleton structure under an acidic condition and then react with heterocyclic substituted secondary amine to synthesize a novel butenolide neonicotine compound through long-term and intensive research. The compounds have completely novel molecular structures and high activity on aphids and rice planthoppers, and the inventors have completed the invention on the basis of the above.
Process for the preparation of the compounds of the invention
In a particular embodiment of the invention, the compound of formula (a) is synthesized as follows:
insecticidal Activity of the active substances according to the invention
The term "active substance according to the invention" or "active compound according to the invention" means a compound according to the invention which has a high insecticidal activity.
The active substance of the present invention can be used for controlling and exterminating a wide range of agricultural and forestry plant pests, pests of stored cereals, public health pests, pests harmful to animal health, and the like. In the present specification, "pesticide" is a general term for a substance having an effect of controlling all the pests mentioned above. Examples of pests include, but are not limited to: coleopteran insects: elephant of maize (Sitophilus zeamais), Tribophytes castanea (Tribolium castaneum), Iris japonica (Henospiroctona virginitictomaculata), Iris brevifolia (Henospiroctona spiosa), Elaphanoplosis punctiformis (Agriotes fusciplis), Rhynchophorus cantoniensis (Anthragmala cupricius), Rhynchophorus tetragonolobus (Popilia quadrata), Tolypocladium arborvita (Monosepta thermogonophica), Sonchus aspergillum (Monocharus alternatus), Rhus oryzae (Echinococcus squamosus), Ascophyllus (Basiproisaria), Astrocarya stellatus (Anopphora chinensis), Aprionalis (Aprophagi), Abrus communis umbiliciformis (Sciastrum), or Anthemis punctatus (Agiolatus). Lepidopteran insects: gypsy moth (Lymantria dispar), Tenebrio molitor (Malacosoma neosteria testacea), yellow poplar wild borer (Diaphania persicifolia), Bombycis diamondback moth (Clania variegata), yellow piercing moth (Cnidocampana fia fiangens), Dendrolimus punctatus (Dendrolimus punctatus), ancient moth (Orgyia gonostigma), Populus alba moth (Paranthrene tabaniformis), Spodoptera litura (Spodoptera litura), Chilo supressalis (Chilo supressalis), corn borer (Ostrinia nubilalis), pink moth (Ephemia cauella), cotton leaf roller moth (Adoxophyora nana), chestnut curly roll (pyperda sponalia), yellow cutworm (Ostrinia nubilalis), white tiger (Agrocybe Ostrinia), Plutella (Plutella xylostella), Plutella xylostella (Plutella xylostella, Plutella xylostella, Plutella xylostella (Plutella xylostella) or Plutella xylostella. Homopteran insects: leafhopper nigricans (Nephotettix cincticeps), Nilaparvata lugens (Nilaparvata lugens), Tokay mealybugs (Pseudococcus comstocki), Cedar kummer (Unnassia yanonensis), Myzus persicae (Myzus persicae), Aphis gossypii (Aphis gossypidii), Aphis Raphanus (Lipaphis erysimi pseudobasicae), Nephophora pyrifera (Stephaniae nashi), or Bemisia tabaci (Bemisia tabaci). Orthoptera insects: german cockroach (Blattella germanica), american cockroach (Periplaneta americana), mole cricket africana (Gryllotalpa africana), or locusta migratoria asiana (Locus migratoria). Insects of the order isoptera: invasion of Solenopsis invicta (Solenopsis invicta), or domestic termite (Coptotermes formosanus). Insects of the order diptera: houseflies (Musca domestica), Aedes aegypti (Aedes aegypti), seed flies (Delia platura), Culex (Culex sp.), or Anopheles sinensis (Anopheles sinensis).
The compounds of the invention are particularly useful against pests with piercing-sucking and rasping mouthparts such as: the agricultural and forestry pests such as aphids, leafhoppers, plant hoppers, thrips, whiteflies and the like have high efficiency.
Pesticide compositions containing active substances according to the invention
The active substances according to the invention can be prepared in a customary manner to give pesticide compositions. The active compounds can be formulated in the customary formulations, for example solutions, emulsions, suspensions, powders, foams, pastes, granules; aerosols, natural and synthetic materials impregnated with active substances, microcapsules in polymers, coating compositions for seeds, and formulations for use with combustion devices-blocks, such as smoking cartridges, smoking pots and smoking trays, and ULV Cold mist (Cold mist) and hot mist (Warm mist) formulations.
These formulations can be produced by known methods, for example by mixing the active compounds with extenders, that is, liquid or liquefied gas or solid diluents or carriers, and optionally surfactants, that is, emulsifiers and/or dispersants and/or foam formers. Organic solvents may also be used as adjuvants, for example when water is used as extender.
Liquid solvents are basically suitable as diluents or carriers, for example: aromatic hydrocarbons such as xylene, toluene or alkylnaphthalene; chlorinated aromatic or chlorinated aliphatic hydrocarbons, such as chlorobenzene, vinyl chloride or dichloromethane; aliphatic hydrocarbons, such as cyclohexane or paraffins, for example mineral oil fractions; alcohols, such as ethanol or ethylene glycol and their ethers and lipids; ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone; or less commonly polar solvents such as dimethylformamide and dimethylsulfoxide, and water. The diluent or carrier of the liquefied gas means a liquid which will become a gas at normal temperature and pressure, for example, aerosol propellants such as halogenated hydrocarbons as well as butane, propane, nitrogen and carbon dioxide.
The solid carrier can be selected from the group consisting of naturally occurring minerals, such as kaolin, clay, talc, quartz, activated clay, montmorillonite, or diatomaceous earth, and synthetic minerals, such as highly dispersed silicic acid, alumina, and silicates. Solid carriers for granules are ground and classified natural marble, such as calcite, marble, pumice, sepiolite and dolomite, as well as synthetic granules of inorganic and organic meals, and granules of organic materials, such as sawdust, coconut shells, corn cobs and tobacco stalks, etc.
Nonionic and anionic emulsifying trains may be used as emulsifiers and/or foam formers. Such as polyoxyethylene-fatty acid esters, polyoxyethylene-fatty alcohol ethers, such as alkylaryl polyethylene glycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and albumin hydrolysates. Dispersants include, for example, lignin sulfite waste liquor and methyl cellulose.
Furthermore, the active compounds according to the invention can also be formulated with synergists in a mixture in their commercial preparations in the use forms prepared from these preparations. Synergists are compounds which increase the action of the active compound, and, owing to the activity of the active compound itself, it is also not necessary to add a synergist.
These formulations generally contain from 0.001 to 99.99% by weight, preferably from 0.01 to 99.9% by weight, more preferably from 0.05 to 90% by weight, of the active compounds according to the invention, based on the pesticide composition. The concentration of the active compound in the dosage form prepared from commercial preparations for use can vary within wide limits. The concentration of active compound in the dosage form to be used may be from 0.0000001 to 100% (g/v), preferably between 0.0001 and 1%.
Examples
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The experimental procedures, in which specific conditions are not noted in the following examples, are generally carried out under conventional conditions or conditions recommended by the manufacturers. Unless otherwise indicated, percentages and parts are by weight.
Example 1 Synthesis of A series of chloro butenolide Neonicotinoids (1) Synthesis of intermediate 3, 4-dichloro-5-methoxy-2 (5H) -furanone
Adding 2.0g (11.9mmol) of mucochloric acid and 30mL of methanol into a 100mL flask, adding 0.5mL of concentrated sulfuric acid, magnetically stirring and refluxing at constant temperature of 70 ℃, tracking the reaction by TLC, adding 1.3g of anhydrous potassium carbonate after the reaction is finished, stirring for 0.5h, carrying out suction filtration, carrying out reduced pressure spin drying to obtain a crude product, and carrying out column chromatography separation on the crude product (V petroleum ether: V dichloromethane is 1:1) to obtain a light yellow oily liquid with the yield of 60%. 1 H NMR(400MHz,CDCl 3 )δ(ppm):5.79(s,1H,O-CH-O),3.61(s,3H,O-CH 3 )。
Synthesis of intermediate 3, 4-dichloro-5-ethoxy-2 (5H) -furanone: 1 H NMR(400MHz,CDCl 3 )δ(ppm):5.84(s,1H,O-CH-O),3.88(ddq,J＝42.6,9.4,7.1Hz,2H,O-CH 2 -),1.35(t,J＝7.1Hz,3H,O-CH 3 ).
synthesis of intermediate 3, 4-dichloro-5-fluoroethoxy-2 (5H) -furanone: 1 H NMR(400MHz,CDCl 3 )δ(ppm):5.92(s,1H,O-CH-O),4.70(m,2H,O-CH 2 -),4.06(m,2H,F-CH 2 -).
(2) synthesis of target Compound
3-chloro-4- ((3-methylamino-6-chloro) methylpyridine) -5-methoxy-2 (5H) -furanone (A01)
0.45g (2.5mmol) of intermediate 5-methoxy-3, 4-dichloro-2 (5H) -furanone and 0.58g (3.75mmol) of intermediate 3- (methylamino) methyl-6-chloropyridine are respectively added into a 100mL flask, 3mL of newly distilled DMF is used for dissolving, 0.35g of anhydrous potassium carbonate is added into a mixed solution after dissolving, stirring is carried out at normal temperature, TLC tracking reaction is carried out, 50mL of ice water is added into a crude product after the reaction is finished, solid is immediately separated out, vacuum filtration is carried out, the solid obtained by the vacuum filtration is dissolved by 30mL of dichloromethane, then diluted hydrochloric acid, saturated sodium bicarbonate solution and clean water are respectively used for washing, drying is carried out after anhydrous sodium sulfate is used, the vacuum filtration is carried out, spin drying is carried out, column chromatography separation V (ethyl acetate): 1, light yellow oily liquid is obtained, and the yield is 63%.
1 H NMR(400MHz,CDCl 3 )δ(ppm):8.34(d,J＝2.3Hz,1H,Py-H),7.65(dd,J＝8.2,2.5Hz,1H,Py-H),7.41(d,J＝8.2Hz,1H,Py-H),5.75(s,1H,O-CH-O),4.88–4.65(m,2H,Py-CH 2 -N),3.56(s,3H,N-CH 3 ),3.11(s,3H,O-CH 3 ). 13 C NMR(100MHz,CDCl 3 )δ167.70,155.15,151.40,148.73,137.99,130.59,124.82,97.97,87.69,55.74,52.33,38.15。
3-chloro-4- ((3-ethylamino-6-chloro) methylpyridine) -5-methoxy-2 (5H) -furanone (A02)
1 H NMR(400MHz,CDCl 3 )δ(ppm):8.32(d,J＝2.2Hz,1H,Py-H),7.63(dd,J＝8.4,2.0Hz,1H,Py-H),7.39(d,J＝8.2Hz,1H,Py-H),5.73(s,1H,O-CH-O),4.88–4.51(m,2H,Py-CH 2 -N),3.55(s,3H,CH 3 -O),3.51–3.44(m,2H,N-CH 2 -),1.25(t,J＝7.0Hz,3H,CH 3 -)。
3-chloro-4- ((3-propylamino-6-chloro) methylpyridine) -5-methoxy-2 (5H) -furanone (A03)
1 H NMR(400MHz,CDCl 3 )δ(ppm):8.31(d,J＝2.4Hz,1H,Py-H),7.61(dd,J＝8.3,2.5Hz,1H,Py-H),7.39(d,J＝8.2Hz,1H,Py-H),5.71(s,1H,O-CH-O),4.85–4.58(m,2H,Py-CH 2 -N),3.54(s,3H,O-CH 3 ),3.45–3.30(m,2H,N-CH 2 -),1.67(q,J＝7.6Hz,2H,-CH 2 -),0.93(t,J＝7.4Hz,3H,CH 3 -)。
3-chloro-4- ((3-isopropylamino-6-chloro) methylpyridine) -5-methoxy-2 (5H) -furanone (A04)
1 H NMR(400MHz,CDCl 3 )δ(ppm):8.39(d,J＝2.4Hz,1H,Py-H),7.82(dd,J＝8.3,2.3Hz,1H,Py-H),7.33(s,1H,Py-H),6.85(s,1H,O-CH-O),4.56(s,2H,Py-CH 2 -N),3.84(s,3H,CH 3 -O),3.54(d,J＝33.3Hz,2H,N-CH 2 -),1.18(d,J＝6.7Hz,6H,-CH 3 -N-CH 3 -)。
3-chloro-4- ((3-cyclopropylamino-6-chloro) methylpyridine) -5-methoxy-2 (5H) -furanone (A05)
1 H NMR(400MHz,CDCl 3 )δ(ppm):8.36(d,J＝2.4Hz,1H,Py-H),7.62(dd,J＝8.2,2.3Hz,1H,Py-H),7.39(d,J＝8.2Hz,1H,Py-H),5.89(s,1H,O-CH-O),5.21(d,J＝16.0Hz,1H,Py-CH-N),4.46(s,1H,Py-CH-N),3.56(s,3H,O-CH 3 ),2.90(ddd,J＝6.9,4.9,2.2Hz,1H,N-CH-),1.00(m,4H,-CH 2 -CH 2 -)。
3-chloro-4- ((3-butylamino-6-chloro) methylpyridine) -5-methoxy-2 (5H) -furanone (A06) 1 H NMR(400MHz,CDCl 3 )δ(ppm):8.31(d,J＝2.4Hz,1H,Py-H),7.61(dd,J＝8.3,2.4Hz,1H,Py-H),7.39(d,J＝7.4Hz,1H,Py-H),5.71(s,1H,O-CH-O),4.58(d,J＝38.9Hz,2H,Py-CH 2 -N),3.54(s,3H,CH 3 -O),3.46–3.31(m,2H,-CH 2 -N),1.71–1.57(m,2H,-CH 2 -),1.40–1.31(m,2H,-CH 2 -),0.95(d,J＝7.3Hz,3H,CH 3 -)。
3-chloro-4- ((3-methylamino-6-chloro) methylpyridine) -5-ethoxy-2 (5H) -furanone (A07) 1 H NMR(400MHz,CDCl 3 )δ(ppm):8.34(d,J＝2.4Hz,1H,Py-H),7.65(dd,J＝8.3,2.4Hz,1H,Py-H),7.41(d,J＝8.2Hz,1H,Py-H),5.79(s,1H,O-CH-O),4.76(s,2H,O-CH 2 -),3.95(dd,J＝9.4,7.1Hz,1H,Py-CH 2 -),3.73(dq,J＝9.3,7.0Hz,1H,Py-CH 2 -),3.12(s,3H,N-CH 3 -),1.26(t,J＝7.0Hz,3H,CH 3 -). 3-chloro-4- ((3-ethylamino-6-chloro) methylpyridine) -5-ethoxy-2 (5H) -furanone (A08)
1 H NMR(400MHz,CDCl 3 )δ(ppm):8.33(d,J＝2.4Hz,1H,Py-H),7.65(dd,J＝8.3,2.2Hz,1H,Py-H),7.39(d,J＝8.2Hz,1H,Py-H),5.78(s,1H,O-CH-O),4.70(d,J＝3.3Hz,2H,O-CH 2 -),3.95(dd,J＝9.4,7.1Hz,1H,Py-CH 2 ),3.71(m,1H,Py-CH 2 ),3.51(m,2H,N-CH 2 ),1.28(m,6H,CH 3 -,CH 3 -)。
3-chloro-4- ((3-propylamino-6-chloro) methylpyridine) -5-ethoxy-2 (5H) -furanone (A09)
1 H NMR(400MHz,CDCl 3 )δ(ppm):8.32(d,J＝2.5Hz,1H,Py-H),7.64(dd,J＝8.2,2.5Hz,1H，Py-H),7.39(d,J＝8.2Hz,1H,Py-H),5.77(s,1H,O-CH-O),4.81–4.58(m,2H,Py-CH 2 -H),3.95(dd,J＝9.4,7.1Hz,1H,O-CH 2 -),3.35(d,J＝8.1Hz,1H,O-CH 2 -),1.68(d,J＝7.7Hz,2H,N-CH 2 -),1.30–1.14(m,3H,CH 3 -),0.92(t,J＝7.4Hz,3H,CH 3 -)。
3-chloro-4- ((3-isopropylamino-6-chloro) methylpyridine) -5-ethoxy-2 (5H) -furanone (A10)
1 H NMR(400MHz,CDCl 3 )δ(ppm):8.41(m,1H,Py-H),7.82(dd,J＝8.3,2.5Hz,1H,Py-H),7.32(s,1H,Py-H),6.83(s,1H,O-CH-O),4.56(s,2H,Py-CH 2 -N),4.31(q,J＝7.1Hz,2H,O-CH 2 ),4.11(m,1H,N-CH-),1.35(q,J＝6.9Hz,3H,CH 3 -),1.17(s,6H,CH 3 -,CH 3 )。
3-chloro-4- ((3-cyclopropylamino-6-chloro) methylpyridine) -5-ethoxy-2 (5H) -furanone (A11)
1 H NMR(400MHz,CDCl 3 )δ(ppm):8.32(dd,J＝2.6,0.8Hz,1H,Py-H),7.63(dd,J＝8.3,2.5Hz,1H,Py-H),7.35(dd,J＝8.3,0.7Hz,1H,Py-H),5.95(s,1H,O-CH-O),5.15(d,J＝16.1Hz,1H,Py-CH 2 -),4.46(d,J＝16.1Hz,1H,Py-CH 2 -),3.95–3.84(m,1H,O-CH 2 -),3.72(dq,J＝9.4,7.1Hz,1H,O-CH 2 -),2.94–2.87(m,1H,N-CH 2 ),1.25–1.18(m,4H,-CH 2 -CH 2 -),1.00–0.67(m,3H,CH 3 -)。
3-chloro-4- ((3-butylamino-6-chloro) methylpyridine) -5-ethoxy-2 (5H) -furanone (A12) 1 H NMR(400MHz,CDCl 3 )δ(ppm):8.32(d,J＝2.4Hz,1H,Py-H),7.63(d,J＝2.1Hz,1H,Py-H),7.39(d,J＝8.2Hz,1H,Py-H),5.76(s,1H,O-CH-O),4.82–4.57(m,2H,Py-CH 2 -),4.00–3.88(m,1H,O-CH 2 -),3.70(dd,J＝9.3,7.1Hz,1H,O-CH 2 -),3.51–3.30(m,1H,N-CH-),1.66(dd,J＝15.6,8.2Hz,3H,CH 3 -),1.29–1.18(m,4H,-CH 2 -CH 2 -),0.95(t,J＝7.4Hz,3H,CH 3 -)。
3-chloro-4- ((3-methylamino-6-chloro) methylpyridine) -5-fluoroethoxy-2 (5H) -furanone (A13)
1 H NMR(400MHz,CDCl 3 )δ(ppm):8.34(d,J＝2.5Hz,1H,Py-H),7.64(dd,J＝8.2,2.5Hz,1H,Py-H),7.40(d,J＝8.2Hz,1H,Py-H),5.88(s,1H,O-CH-O),4.79(s,2H,Py-CH 2 -),4.66(m,1H,F-CH 2 ),4.53(m,1H,F-CH 2 ),4.12(m,2H,O-CH 2 -),3.15(s,3H,N-CH 3 -)。
3-chloro-4- ((3-ethylamino-6-chloro) methylpyridine) -5-fluoroethoxy-2 (5H) -furanone (A14)
1 H NMR(400MHz,CDCl 3 )δ(ppm):8.32(d,J＝2.4Hz,1H,Py-H),7.64(dd,J＝8.3,2.4Hz,1H,Py-H),7.38(d,J＝8.2Hz,1H,Py-H),5.85(s,1H,O-CH-O),4.74(q,J＝16.4Hz,2H,Py-CH 2 -N),4.67–4.60(m,1H,F-CH 2 ),4.57–4.47(m,1H,F-CH 2 ),4.13(d,J＝7.2Hz,1H,O-CH 2 -),4.00(q,J＝2.2,1.6Hz,1H,O-CH 2 -),3.61–3.45(m,2H,N-CH 2 ),1.27(td,J＝7.1,3.5Hz,3H,CH 3 -). 3-chloro-4- ((3-propylamino-6-chloro) methylpyridine) -5-fluoroethoxy-2 (5H) -furanone (A15)
1 H NMR(400MHz,CDCl 3 )δ(ppm):8.32(d,J＝2.5Hz,1H,Py-H),7.63(dd,J＝8.3,2.4Hz,1H,Py-H),7.39(d,J＝8.3Hz,1H,Py-H),5.83(s,1H,O-CH-O),4.82(d,J＝16.4Hz,1H,F-CH 2 -),4.73–4.58(m,2H,Py-CH 2 -N),4.51(td,J＝3.8,1.9Hz,1H,F-CH 2 ),4.10(m,2H,O-CH 2 ),3.41(m,2H,N-CH 2 ),1.69(q,J＝7.4Hz,2H,-CH 2 -),0.93(t,J＝7.4Hz,3H,CH 3 -)。
3-chloro-4- ((3-cyclopropylamino-6-chloro) methylpyridine) -5-fluoroethoxy-2 (5H) -furanone (A16)
1 H NMR(400MHz,CDCl 3 )δ(ppm):8.36(d,J＝2.5Hz,1H,Py-H),7.64(dd,J＝8.3,2.5Hz,1H,Py-H),7.38(d,J＝8.2Hz,1H,Py-H),6.03(s,1H,O-CH-O),5.20(d,J＝16.1Hz,1H,F-CH 2 -),4.62(m,1H,F-CH 2 -),4.51(m,2H,Py-CH 2 -N),4.12(m,1H,O-CH 2 -),4.01(m,1H,O-CH 2 -),3.95(m,1H,N-CH-),1.01(m,4H,-CH 2 -CH 2 -)。
Example 2 Synthesis of B-series Bromobutylidene Neonicotinoid Compounds (1) Synthesis of intermediate 3, 4-dibromo-5-methoxy-2 (5H) -furanone
Adding 3.0g (11.7mmol) of mucobromic acid and 30mL of methanol into a 100mL flask, adding 0.5mL of concentrated sulfuric acid, magnetically stirring and refluxing at constant temperature of 70 ℃, tracking the reaction by TLC, adding 1.2g of anhydrous potassium carbonate after the reaction is finished, stirring for 0.5h, performing suction filtration, performing reduced pressure spin drying to obtain a crude product, and performing column chromatography separation on the crude product (V petroleum ether: V dichloromethane is 1:1) to obtain a white solid with the yield of 92%. 1 H NMR(400MHz,CDCl 3 )δ(ppm):5.80(s,1H,O-CH-O),3.60(s,3H,O-CH 3 ).
Synthesis of intermediate 3, 4-dibromo-5-ethoxy-2 (5H) -furanone: 1 H NMR(400MHz,CDCl 3 )δ(ppm):5.84(s,1H,O-CH-O),4.05–3.73(m,2H,O-CH 2 ),1.35(t,J＝7.1Hz,3H,CH 3 -).
synthesis of intermediate 3, 4-dibromo-5-fluoroethoxy-2 (5H) -furanone: 1 H NMR(400MHz,CDCl 3 )δ(ppm):5.92(s,1H,O-CH-O),4.70(m,2H,F-CH 2 -),4.10(m,2H,O-CH 2 -).
(2) synthesis of target Compound
3-bromo-4- ((3-methylamino-6-chloro) methylpyridine) -5-methoxy-2 (5H) -furanone (B01)
0.50g (1.85mol) of intermediate 5-methoxy-3, 4-dibromo-2 (5H) -furanone and 0.44g (2.78mmol) of intermediate 3- (methylamino) methyl-6-chloropyridine were added to a 100mL flask, and dissolved in 3mL of freshly distilled DMF, 0.30g of anhydrous potassium carbonate was added to the mixture after dissolution, followed by stirring at room temperature, TLC followed reaction, 50mL of ice water was added to the crude product after the reaction was completed, and a solid was immediately precipitated, followed by suction filtration under reduced pressure, and the solid obtained by suction filtration was dissolved in 30mL of dichloromethane, and then washed with dilute hydrochloric acid, a saturated sodium bicarbonate solution, and water, followed by drying over anhydrous sodium sulfate, suction filtration, spin-drying, and separation of V (petroleum ether) by column chromatography, wherein V (ethyl acetate): 1, gives a pale yellow solid, and the yield was 83%. 1 H NMR(400MHz,CDCl 3 )δ(ppm):8.44(m,1H,Py-H),7.69–7.61(m,1H,Py-H),7.40(d,J＝8.2Hz,1H,Py-H),5.77(s,1H,O-CH-O),4.97–4.66(m,2H,Py-CH 2 -N),3.55(s,3H,O-CH 3 -),3.12(s,3H,N-CH 3 )。
3-bromo-4- ((3-ethylamino-6-chloro) methylpyridine) -5-methoxy-2 (5H) -furanone (B02) 1 H NMR(400MHz,CDCl 3 )δ(ppm):8.32(s,1H,Py-H),7.63(d,J＝7.7Hz,1H,Py-H),7.39(d,J＝8.1Hz,1H,Py-H),5.76(s,1H,O-CH-O),4.66(m,2H,Py-CH 2 -N),3.54(s,3H,O-CH 3 ),3.51(d,J＝8.1Hz,2H,N-CH 2 -),1.25(t,J＝6.8Hz,3H,CH 3 -). 3-bromo-4- ((3-propylamino-6-chloro) methylpyridine) -5-methoxy-2 (5H) -furanone (B03) 1 H NMR(400MHz,CDCl 3 )δ(ppm):8.31(d,J＝2.4Hz,1H,Py-H),7.61(dd,J＝8.2,2.5Hz,1H,Py-H),7.39(d,J＝8.2Hz,1H,Py-H),5.74(s,1H,O-CH-O),4.85(d,J＝16.4Hz,1H,Py-CH 2 -N),4.61(m,1H,Py-CH 2 -N),3.54(s,3H,O-CH 3 ),3.39(qq,J＝12.2,6.2,4.4Hz,2H,N-CH 2 ),1.68(p,J＝7.5Hz,2H,-CH 2 -),0.93(t,J＝7.3Hz,3H,CH 3 -)。
3-bromo-4- ((3-isopropylamino-6-chloro) methylpyridine) -5-methoxy-2 (5H) -furanone (B04)
1 H NMR(400MHz,CDCl 3 )δ(ppm):8.38(d,J＝2.5Hz,1H,Py-H),7.80(dd,J＝8.3,2.4Hz,1H,Py-H),7.31(d,J＝8.3Hz,1H,Py-H),7.06(s,1H,O-CH-O),4.55(s,2H,Py-CH 2 -N),4.10(m,1H,N-CH-),3.84(s,3H,O-CH 3 ),1.32–1.18(m,4H,-CH 2 -CH 2 -). 3-bromo-4- ((3-cyclopropylamino-6-chloro) methylpyridine) -5-methoxy-2 (5H) -furanone (B05)
1 H NMR(400MHz,CDCl 3 )δ(ppm):8.35(d,J＝2.5Hz,1H,Py-H),7.62(dd,J＝8.3,2.5Hz,1H,Py-H),7.38(d,J＝8.2Hz,1H,Py-H),5.91(s,1H,O-CH-O),5.32(d,J＝16.1Hz,1H,Py-CH 2 -N),4.44(d,J＝16.0Hz,1H,Py-CH 2 -N),3.56(s,3H,O-CH 3 ),2.89(m,1H,N-CH-),0.92(m,4H,-CH 2 -CH 2 -)。
3-bromo-4- ((3-butylamino-6-chloro) methylpyridine) -5-methoxy-2 (5H) -furanone (B06) 1 H NMR(400MHz,CDCl 3 )δ(ppm):8.30(d,J＝2.4Hz,1H,Py-H),7.61(dd,J＝8.3,2.6Hz,1H,Py-H),7.38(d,J＝8.2Hz,1H,Py-H),5.73(s,1H,O-CH-O),4.86(d,J＝16.5Hz,1H,Py-CH 2 -N),4.61(m,1H,Py-CH 2 -N),3.53(s,3H,O-CH 3 ),3.42(td,J＝13.2,11.9,6.1Hz,2H,N-CH 2 -),1.63(qd,J＝8.5,8.0,6.4Hz,2H,-CH 2 -),1.34(m,2H,-CH 2 -),0.94(t,J＝7.4Hz,3H,CH 3 -). 3-bromo-4- ((3-methylamino-6-chloro) methylpyridine) -5-ethoxy-2 (5H) -furanone (B07) 1 H NMR(400MHz,CDCl 3 )δ(ppm):8.34(d,J＝2.4Hz,1H,Py-H),7.65(dd,J＝8.3,2.2Hz,1H,Py-H),7.41(d,J＝8.2Hz,1H,Py-H),5.82(s,1H,O-CH-O),4.81(s,2H,Py-CH 2 -N),3.90(m,1H,O-CH 2 -),3.74(dq,J＝9.3,7.0Hz,1H,O-CH 2 -),3.13(s,3H,N-CH 3 ),1.26(t,J＝7.0Hz,3H,CH 3 -)。
3-bromo-4- ((3-ethylamino-6-chloro) methylpyridine) -5-ethoxy-2 (5H) -furanone (B08) 1 H NMR(400MHz,CDCl 3 )δ(ppm):8.33(d,J＝2.4Hz,1H,Py-H),7.65(dd,J＝8.3,2.4Hz,1H,Py-H),7.39(d,J＝8.3Hz,1H,Py-H),5.80(s,1H,O-CH-O),4.77(m,2H,Py-CH 2 -),3.95(dq,J＝9.4,7.1Hz,1H,O-CH 2 -),3.74(q,J＝7.0Hz,1H,O-CH 2 -),3.58(dd,J＝14.7,7.2Hz,1H,N-CH 2 -),3.45(dq,J＝14.2,7.0Hz,1H,N-CH 2 -),1.29–1.23(m,6H,CH 3 -,CH 3 -)。
3-bromo-4- ((3-propylamino-6-chloro) methylpyridine) -5-ethoxy-2 (5H) -furanone (B09)
1 H NMR(400MHz,CDCl 3 )δ(ppm):8.35(m,1H,Py-H),7.67–7.62(m,1H,Py-H),7.39(dd,J＝8.2,0.6Hz,1H,Py-H),5.79(s,1H,O-CH-O),4.77(m,2H,Py-CH 2 -N),3.94(dq,J＝9.4,7.1Hz,1H,O-CH 2 -),3.70(dq,J＝9.4,7.1Hz,1H,O-CH 2 -),3.33(m,2H,N-CH 2 -),1.66(m,2H,-CH 2 -),1.23(t,J＝7.1Hz,3H,CH 3 -),0.92(t,J＝7.2Hz,3H,CH 3 -).。
3-bromo-4- ((3-isopropylamino-6-chloro) methylpyridine) -5-ethoxy-2 (5H) -furanone (B10)
1 H NMR(400MHz,CDCl 3 )δ(ppm):8.37(d,J＝2.5Hz,1H,Py-H),7.79(dd,J＝8.3,2.5Hz,1H,Py-H),7.30(d,J＝8.4Hz,1H,Py-H),7.04(s,1H,O-CH-O),4.55(s,2H,Py-CH 2 -N),4.30(q,J＝7.2Hz,2H,O-CH 2 -),4.14(m,1H,N-CH-),1.34(q,J＝7.1Hz,3H,CH 3 -),1.18(d,J＝6.7Hz,6H,CH 3 -,CH 3 -)。
3-bromo-4- ((3-cyclopropylamino-6-chloro) methylpyridine) -5-ethoxy-2 (5H) -furanone (B11)
1 H NMR(400MHz,CDCl 3 )δ(ppm):8.34(d,J＝2.5Hz,1H,Py-H),7.64(dd,J＝8.3,2.5Hz,1H,Py-H),7.37(d,J＝8.2Hz,1H,Py-H),5.97(s,1H,O-CH-O),5.29(d,J＝16.1Hz,1H,Py-CH 2 -N),4.46(d,J＝16.1Hz,1H,Py-CH 2 -N),3.95(m,1H,O-CH 2 -),3.77(m,1H,O-CH 2 -),2.93(m,1H,N-CH-),1.27(m,3H,CH 3 -),0.987(m,2H,-CH 2 -),0.81(m,2H,-CH 2 -)。
3-bromo-4- ((3-butylamino-6-chloro) methylpyridine) -5-ethoxy-2 (5H) -furanone (B12) 1 H NMR(400MHz,CDCl 3 )δ(ppm):8.31(m,1H,Py-H),7.63(dd,J＝8.3,2.5Hz,1H,Py-H),7.43(m,1H,Py-H),5.78(s,1H,O-CH-O),4.77(m,2H,Py-CH 2 -N),3.94(dd,J＝9.4,7.1Hz,1H,O-CH 2 -),3.73(m,1H,O-CH 2 -),3.45(m,2H,N-CH 2 -),1.65(m,2H,-CH 2 -),1.31(m,5H,-CH 2 -,CH 3 -),0.95(t,J＝7.3Hz,3H,CH 3 -). 3-bromo-4- ((3-methylamino-6-chloro) methylpyridine) -5-fluoroethoxy-2 (5H) -furanone (B13)
1 H NMR(400MHz,CDCl 3 )δ(ppm):8.34(d,J＝2.4Hz,1H,Py-H),7.65(dd,J＝8.3,2.3Hz,1H,Py-H),7.41(d,J＝8.2Hz,1H,Py-H),5.90(s,1H,O-CH-O),4.84(s,2H,Py-CH 2 -N),4.70–4.62(m,1H,F-CH 2 ),4.53(dd,J＝5.1,2.2Hz,1H,F-CH 2 ),4.18–3.93(m,2H,O-CH 2 ),3.16(s,3H,N-CH 3 )。
3-bromo-4- ((3-ethylamino-6-chloro) methylpyridine) -5-fluoroethoxy-2 (5H) -furanone (B14)
1 H NMR(400MHz,CDCl 3 )δ(ppm):8.35(m,1H,Py-H),7.63(dd,J＝8.3,2.0Hz,1H,Py-H),7.39(d,J＝8.2Hz,1H,Py-H),5.87(s,1H,O-CH-O),4.88–4.69(m,2H,Py-CH 2 -N),4.67–4.58(m,1H,F-CH 2 -),4.52(p,J＝3.0,2.5Hz,1H,F-CH 2- ),4.21–4.06(m,1H,O-CH 2 ),4.04–3.92(m,1H,O-CH 2 -),3.54(dt,J＝14.7,7.3Hz,2H,N-CH 2 -),1.30–1.26(m,3H,CH 3 -)。
3-bromo-4- ((3-propylamino-6-chloro) methylpyridine) -5-fluoroethoxy-2 (5H) -furanone (B15)
1 H NMR(400MHz,CDCl 3 )δ(ppm):8.31(d,J＝2.5Hz,1H,Py-H),7.62(dd,J＝8.3,2.5Hz,1H,Py-H),7.39(d,J＝8.2Hz,1H,Py-H),5.85(s,1H,O-CH-O),4.87(d,J＝16.5Hz,1H,Py-CH 2 -N),4.67(d,J＝16.4Hz,1H,Py-CH 2 -N),4.64–4.59(m,1H,F-CH 2 ),4.51(d,J＝1.1Hz,1H,F-CH 2 ),4.08(s,1H,O-CH 2 ),3.99(d,J＝2.6Hz,1H,O-CH 2 ),3.44(q,J＝6.6,5.9Hz,2H,N-CH 2 ),1.68(d,J＝3.2Hz,2H,CH 2 ),0.93(t,J＝7.3Hz,3H,CH 3 ). 3-bromo-4- ((3-isopropylamino-6-chloro) methylpyridine) -5-fluoroethoxy-2 (5H) -furanone (B16)
1 H NMR(400MHz,CDCl 3 )δ(ppm):8.37(d,J＝2.4Hz,1H,Py-H),7.76(dd,J＝8.3,2.3Hz,1H,Py-H),7.12(s,1H,Py-H),4.70(m,1H,O-CH-O),4.62–4.58(m,1H,F-CH 2 -),4.55(s,2H,Py-CH 2 -N),4.53–4.49(m,1H,F-CH 2 -),4.48–4.44(m,1H,O-CH 2 -),4.13(q,J＝6.6Hz,1H,O-CH 2 -),1.19(dd,J＝6.8,4.8Hz,6H,CH 3 -,CH 3 -)。
3-bromo-4- ((3-cyclopropylamino-6-chloro) methylpyridine) -5-fluoroethoxy-2 (5H) -furanone (B17)
1 H NMR(400MHz,CDCl 3 )δ(ppm):8.35(d,J＝2.5Hz,1H,Py-H),7.63(dd,J＝8.3,2.6Hz,1H,Py-H),7.37(d,J＝8.2Hz,1H,Py-H),6.05(s,1H,O-CH-O),5.30(d,J＝16.1Hz,1H,Py-CH 2 -N),4.64(dd,J＝5.3,2.7Hz,1H,F-CH 2 -),4.54–4.52(m,1H,Py-CH 2 -N),4.47(s,1H,F-CH 2 -),4.17–4.04(m,1H,O-CH 2 -),3.99–3.94(m,1H,O-CH 2 -),3.01–2.94(m,1H,N-CH 2 -),1.37–1.26(m,1H,-CH 2 -),1.00(d,J＝7.5Hz,1H,CH 2 -),0.90–0.83(m,2H,-CH 2 -)。
3-bromo-4- ((3-butylamino-6-chloro) methylpyridine) -5-fluoroethoxy-2 (5H) -furanone (B18)
1 H NMR(400MHz,CDCl 3 )δ(ppm):8.34–8.29(m,1H,Py-H),7.62(dd,J＝8.3,2.6Hz,1H,Py-H),7.39(dd,J＝8.3,0.7Hz,1H,Py-H),5.85(s,1H,O-CH-O),4.87(d,J＝16.5Hz,1H,Py-CH 2 -N),4.70–4.63(m,1H,Py-CH 2 -N),4.61(s,1H,F-CH 2 -),4.51(d,J＝1.0Hz,1H,F-CH 2 -),4.19–4.05(m,1H,O-CH 2 -),3.99(d,J＝2.7Hz,1H,O-CH 2 -),3.53–3.43(m,2H,N-CH 2 -),1.69–1.60(m,2H,-CH 2 -),1.35–1.29(m,2H,-CH 2 -),0.94(t,J＝7.3Hz,3H,CH 3 -)。
Example 3 insecticidal Activity testing of Compounds of the invention
(1) Spraying method for testing biological activity of rice planthopper
3-4 seedlings of 2-leaf 1-cored rice (about 3.5cm in length) were fixed in a 6cm petri dish with quartz sand, and three-instar metaphase nymphs of rice planthoppers were anesthetized with carbon dioxide. And (3) treating the rice seedlings under a Potter spray tower, and taking the water-spitting water of the highest-concentration organic solvent as a blank control. After spraying, the glass is covered by a transparent glass cup, the glass cup is placed at the temperature of 23-28 ℃ and is illuminated for 15 hours, and the result is investigated after two days. If the test insects are touched by a brush pen, the death of the insects is judged if the test insects are weak in growth, slow in movement and obviously poor in feeding performance.
(2) Aphid bioactivity test-spraying method
Placing a proper amount of aphids with the same size on a broad bean seedling plant with the height of 2-3cm, placing the broad bean seedling under a Potter spray tower for treatment after 24 hours in an insect breeding room, and taking the temperature spitting water of the highest concentration organic solvent as a blank control. Culturing in observation room at 20-23 deg.C, and observing result after 2 days. If the test insects are touched by a brush pen, the death of the insects is judged if the test insects are weak in growth, slow in movement and obviously poor in feeding performance.
TABLE 1 biological Activity of the synthetic Compounds
EXAMPLE 4 preparation of insecticide compositions containing Compounds of the invention
(a) Oily suspensions
Preparing the following components in proportion: 25% (by weight, the same applies hereinafter) of any one of the compounds A1-A16 or B1-B18; 5% polyoxyethylene sorbitol hexaoleate; 70% of higher aliphatic hydrocarbon oil. The components were ground together in a sand mill until the solid particles fell below about 5 microns. The resulting viscous suspension can be used as such, but also after emulsification in water.
(b) Aqueous suspension
Preparing the following components in proportion: 25% of any one of compound A1-A16 or B1-B18; 3% hydrated attapulgite (hydrate attapulgit); 10% calcium lignosulfonate; 0.5% sodium dihydrogen phosphate; 61.5% water. The components are ground together in a ball mill until the solid particles fall below about 10 microns. The aqueous suspension can be used as such.
(c) Bait agent
Preparing the following components in proportion: 0.1-10% of any one of compound A1-A16 or B1-B18; 80% wheat flour; 19.9-10% of molasses. These components are thoroughly mixed to form a bait shape as desired. Edible baits can be dispersed to a locus infested by sanitary pests, for example a domestic or industrial locus, such as a kitchen, hospital or store or outdoor area, to control pests by oral ingestion.
All documents referred to herein are incorporated by reference into this application as if each were individually incorporated by reference. Furthermore, it should be understood that various changes and modifications of the present invention can be made by those skilled in the art after reading the above teachings of the present invention, and these equivalents also fall within the scope of the present invention as defined by the appended claims.
Claims (4)
1.A compound having a structure represented by formula (A):
wherein R is 1 Is a pyridyl halide, R 2 Is C 1-6 Alkyl or C 3-4 Cycloalkyl radical, R 3 Is halo C 1-6 Alkyl, X is chlorine or bromine.
2. A pesticide composition comprising:
(a) 1-99.99% by weight of a compound of claim 1;
(b) an agriculturally pharmaceutically acceptable excipient.
3. The pesticidal composition of claim 2, wherein the pesticidal composition is used to kill: insects of the order homoptera.
4. A method of combating pests which comprises applying a compound as claimed in claim 1 or a pesticidal composition as claimed in any one of claims 2 to 3 to a plant suffering from pests or to the environment surrounding said plant.
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