CN113149900A - Amide compound and application thereof - Google Patents
Amide compound and application thereof Download PDFInfo
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- CN113149900A CN113149900A CN202011208863.XA CN202011208863A CN113149900A CN 113149900 A CN113149900 A CN 113149900A CN 202011208863 A CN202011208863 A CN 202011208863A CN 113149900 A CN113149900 A CN 113149900A
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- C07—ORGANIC CHEMISTRY
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- 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
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/81—Amides; Imides
- C07D213/82—Amides; Imides in position 3
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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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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
- A01P7/00—Arthropodicides
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
- A01P7/00—Arthropodicides
- A01P7/04—Insecticides
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- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K31/00—Medicinal preparations containing organic active ingredients
- A61K31/33—Heterocyclic compounds
- A61K31/395—Heterocyclic compounds having nitrogen as a ring hetero atom, e.g. guanethidine or rifamycins
- A61K31/435—Heterocyclic compounds having nitrogen as a ring hetero atom, e.g. guanethidine or rifamycins having six-membered rings with one nitrogen as the only ring hetero atom
- A61K31/44—Non condensed pyridines; Hydrogenated derivatives thereof
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
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- C07C237/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups
- C07C237/28—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atom of at least one of the carboxamide groups bound to a carbon atom of a non-condensed six-membered aromatic ring of the carbon skeleton
- C07C237/40—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atom of at least one of the carboxamide groups bound to a carbon atom of a non-condensed six-membered aromatic ring of the carbon skeleton having the nitrogen atom of the carboxamide group bound to a carbon atom of a six-membered aromatic ring
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- C07C255/00—Carboxylic acid nitriles
- C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
- C07C255/32—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring
- C07C255/42—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring the carbon skeleton being further substituted by singly-bound nitrogen atoms, not being further bound to other hetero atoms
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- 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
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/84—Nitriles
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- C07C2601/00—Systems containing only non-condensed rings
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Abstract
The invention discloses an amide compound and application thereof, wherein the structure of the compound is shown as a general formula I:
Description
Technical Field
The invention relates to a compound, in particular to a novel amide compound and application thereof.
Background
Due to the long-term large amount of unreasonable use of existing agents, the problem of resistance of pests to pesticides is becoming more and more serious. On the other hand, the insecticidal effect of the existing insecticide is still unsatisfactory especially on the activity of rice stem borer, and the continuously improved use requirement of the insecticide in reality is difficult to meet. There is still a need in the art to actively develop new insecticides with higher activity to meet the needs of agriculture and other fields.
The compounds shown in the general formula I and the insecticidal activity thereof in the prior art are not reported.
Disclosure of Invention
The purpose of the present invention is to provide an amide compound having excellent insecticidal activity. It can be used for preparing medicaments for controlling pests in agriculture and other fields and for preparing medicaments for controlling animal parasites in the field of veterinary medicaments.
In order to realize the purpose of the invention, the invention provides the following technical scheme:
an amide compound, shown as a general formula I:
in formula I:
R1selected from halogens;
R2selected from halogen, C1-C4Haloalkyl or C1-C4HaloalkoxyA group;
R3selected from CF3Or CF2CF3；
R4Selected from cyano group C1-C4An alkyl group.
In one possible implementation, in formula I,
R1selected from halogens;
R2selected from halogen, C1-C2Haloalkyl or C1-C2A haloalkoxy group;
R3selected from CF3Or CF2CF3；
R4Selected from cyano group C1-C4An alkyl group.
In one possible implementation, in formula I,
R1selected from bromine or iodine;
R2selected from bromo, iodo, trifluoromethyl or difluoromethoxy;
R3selected from CF3Or CF2CF3；
R4Is selected from CH2CN、CH2CH2CN、CH2CH2CH2CN、CH2CH2CH2CH2CN、CH(CH3)CN、CH(CH2CH3)CN、CH(CH2CH2CH3)CN、C(CH3)(CH3) CN or C (CH)3)(CH2CH3)CN。
In one possible implementation, in formula I,
R1selected from bromine or iodine;
R2selected from bromine, iodine or trifluoromethyl;
R3selected from CF3；
R4Is selected from CH2CN、CH2CH2CN、CH2CH2CH2CN or CH2CH2CH2CH2CN。
In one possible implementation, the amide compound is selected from the compounds of Table 1The compounds of Table 1 have the structure as shown in formula I and R1、R2、R3And R4As shown in table 1:
TABLE 1
The compounds of the general formula I according to the invention can be prepared by the following process (where the radicals are as defined above, where LG = Cl, Br or I, unless otherwise stated):
compounds of the formula III and halides R4The compound of formula II is obtained by reacting LG in a suitable solvent at a temperature of from-10 ℃ to the boiling point of the solvent for 0.5 to 48 hours, the reaction being carried out in the presence of a base and a catalyst; the compound of the general formula I can be prepared by reacting the compound of the general formula II with 6-cyano nicotinyl chloride in a suitable solvent at a temperature of between-10 ℃ and the boiling point of the solvent for 0.5 to 48 hours, and the reaction can be carried out in the presence of alkali and a catalyst. Suitable solvents in the above steps may be the same or different and are aromatic hydrocarbons such as benzene, toluene and xylene, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, halogenated hydrocarbons such as chloroform and methylene chloride, esters such as methyl acetate and ethyl acetate, ethers such as tetrahydrofuran, dioxane, diethyl ether and 1, 2-dimethoxyethane, polar solvents such as water, acetonitrile, N-dimethylformamide, N-methylpyrrolidone and dimethylsulfoxide, and mixed solvents thereof. The bases in the above steps may be the same or different and are organic bases such as triethylamine, pyridine, DBU, 4-dimethylaminopyridine and the like, alkali metal hydrides such as sodium hydride, potassium hydride and the like, alkali metal hydroxides such as sodium hydroxide, potassium hydroxide and the like, alkaline earth metal hydroxides such as calcium hydroxide and the like, alkali metal carbonates such as sodium carbonate, potassium carbonate and the like, alkali metal bicarbonates such as sodium bicarbonate and the like, and metal alkoxides such as sodium methoxide, sodium ethoxide, potassium tert-butoxide, sodium tert-butoxide and the like. The catalyst in each step can be the same or different and is potassium iodide, sodium iodide and fluorinePotassium fluoride, sodium fluoride, potassium bromide, sodium bromide, or the like.
The compounds of formula III may be prepared according to known methods, for example by methods reported in WO20110201687, WO2011093415, WO2005021488, WO2005073165, WO2006137395, JP2007099761, WO2008000438, WO2008074427, WO2008107091, WO2010013567, WO2010018714, WO2010090282, WO2010127926, WO2010127928, JP2011063549, WO2012020483, WO2012020484, WO2012077221, WO2012164698, WO 2013050260260261, WO2014069665, WO2014067838, WO2014161848, WO2014161850, WO2015097091 or WO 2015097094; halogen R4LG and the alkali are generally commercially available and can be prepared by a conventional method.
The embodiment of the invention also provides application of the amide compound in preparation of pesticides.
In one possible implementation, the insecticide is used to control one or more of the following insects:
beetles (Coleopteran), such as the green bean (Callosobruchus Chinensis), corn (Sitophilus zeamais), Tribolium Castaneum (Tribolium Castaneum), calabash (epilaeachothamella), kowter (agriotica grossedentata), polychrome beetle (Anomala rubra), potato beetle (leptotamus decemlineata), Diabrotica spp (Diabrotica spp), Monochamus alternatus (Monochamus alternatus), rice root (lissorophus oryzae), brown powder (lycotus brunneus);
lepidopteran (lepidopteran) pests, for example, gypsy moth (Lymantria dispar), Trichoplusia lutea (Malacomonas neustria), Pieris rapae subspecies Japan (Pieris rapae cruvora), Spodoptera litura (Spodoptera litura), cabbage looper (Mamestra brassicae), Chilo supressalis (Chilo supressalis), European corn borer (Ostrinia nubilalis), Kalophaga medinalis (Cadra caudaella), Chyanokakkumura (Adoxophyceae honmai), apple leaf roller (Cydia pomonella), yellow cutworm (Agrotis segetum), Heliotis incertus (Galleria mellonella), cabbage moth (Plutella xylostella), tobacco bud (Heliothis virescens), and Crypthecodinia punctata (Phlebia punctifera);
hemiptera (Hemipterous) pests, for example, leafhopper melanogaster (Nephotettix cincticeps), brown planthopper (Nilaparvata lugens), mealybugs conoidea (Pseudococcus comstocki), arrowhead (Unaspis yanonensis), green peach aphid (Myzus persicas), apple aphid (Aphis pomi), cotton aphid (Aphis gossypii), radish aphid (liparis physmii), cercospora pyricularis (stephanis nashi), green Chinese toona (Nezara spp.), green house whitefly (greenhouse whitefly), and pseudolla spp.;
pests of the order Thysanoptera (Thysanoptera), such as Thrips palmi (Thrips palmi), Thrips occidentalis (Franklinella occidentalis);
orthopteran pests such as mole cricket in africa (Gryllotalpa Africana), Locusta migratoria (Locusta);
pests of the order blattaria (blattaria), such as the german cockroach (blattaria germanica), the american cockroach (Periplaneta americana), the yellow mealworm (rotigotermes speratus), the domesticated termite (coptottermes formosanus);
diptera (Dipterous) pests, for example, houseflies (Musca domestica), Aedes aegypti (Aedesaegypti), Musca grisea (Delia platura), Culex pipiens pallens (Culex pipiens pallens), Anopheles sinensis (Anopheles sinensis), Culex tritaeniorhynchus (Culex tritaeniorhynchus), Liriomyza trifolii (Liriomyza trifolii), etc.
Agricultural harmful mites, such as Tetranychus cinnabarinus (Tetranychus cinnabarinus), Tetranychus urticae (Tetrahychus urticae), Panonychus citri (Panychus citri), Denychus citri (Aculops pelekassi), Tarsonemus spp.
In one possible implementation mode, the pesticide is used for controlling one or more of armyworm, plutella xylostella and chilo suppressalis.
The embodiment of the invention also provides an insecticide preparation, which contains the amide compound as an active component and one or more auxiliary materials.
In one possible implementation, the insecticide formulation is selected from the following dosage forms: solutions, emulsions, wettable powders, granulated wettable powders, suspensions, powders (powder), foams, pastes, tablets, granules, aerosols, natural agents impregnated with active compounds, synthetic agents impregnated with active compounds, microcapsules, seed coatings, formulations equipped with combustion devices which can be smokers and fogs, pots and coils, etc., and ULVs (cold fogging, hot fogging), etc. These insecticide preparations or animal parasite control agents can be prepared by known methods, for example by mixing the active ingredient with extenders, such as liquid diluents or carriers, liquefied gas diluents or carriers, solid diluents or carriers, and optionally with surfactants, i.e. emulsifiers and/or dispersants and/or foaming agents, and the like.
In one possible implementation, the auxiliary material includes one or more of the following: fillers (e.g., liquid diluents or carriers, liquefied gas diluents or carriers, solid diluents or carriers), surfactants (e.g., emulsifiers and/or dispersants and/or foaming agents), binders, colorants;
the liquid diluent or carrier may include, for example, aromatic hydrocarbons (xylene, toluene, alkylnaphthalenes, etc.), chlorinated aromatic or chlorinated aliphatic hydrocarbons (e.g., chlorobenzene, vinyl chloride, methylene chloride, etc.), aliphatic hydrocarbons (e.g., cyclohexane or paraffin (e.g., mineral oil fractions)), alcohols (e.g., butanol, ethylene glycol, and ethers or esters thereof, etc.), ketones (e.g., acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), strongly polar solvents (e.g., dimethylformamide, dimethyl sulfoxide), water, and the like. When water is used as the filler, for example, an organic solvent may be used as a co-solvent;
liquefied gas diluents or carriers can include those that exist in gaseous form at atmospheric pressure and temperature, e.g., propane, nitrogen, carbon dioxide, and aerosol propellants such as halogenated hydrocarbons;
solid diluents may include crushed natural minerals (e.g., kaolin, clay, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, etc.) as well as crushed synthetic minerals (e.g., finely divided silicic acid, alumina, silicates, etc.), and the like;
emulsifiers and/or foaming agents may include nonionic and anionic emulsifiers [ e.g., polyoxyethylene fatty acid esters, polyoxyethylene fatty acid alcohol ethers (such as alkylaryl polyglycol ethers), alkyl sulfonates, alkyl sulfates and aryl sulfonates ], and albumin hydrolysates, among others;
dispersants may include lignosulfite waste liquors and methylcellulose;
the binder may include carboxymethyl cellulose, natural or synthetic polymers (e.g., gum arabic, polyvinyl alcohol, polyvinyl acetate, and the like).
The colorant may include inorganic pigments (e.g., iron oxide, titanium oxide, prussian blue, etc.), organic dyes such as alizarin dyes, azo dyes, or metal phthalocyanine dyes; and trace elements such as salts of iron, manganese, boron, copper, cobalt, molybdenum or zinc.
Furthermore, the amides of the invention may be present as a mixture with a synergist, which does not have to be active per se. More precisely, it is a compound which enhances the activity of the active compound.
In one possible implementation, the above amide-based compound is contained in the pesticide preparation in an amount of 0.1 to 99% by weight, alternatively 0.5 to 90% by weight.
Also provided in embodiments of the present invention is an insecticidal composition comprising a mixture of the above amide compounds and other active compounds (e.g., insecticides, baits, disinfectants, acaricides, nematicides, fungicides, growth regulators, herbicides, etc.). The mixture can be provided in the form of raw material medicine, or can be provided in the form of a commercially available preparation or a use form prepared from the preparation.
The embodiment of the invention also provides a method for controlling agricultural or forestry pests, which comprises the following steps: applying an effective amount of a material to a pest or its growth medium in need of control, the material being selected from one or more of the following: the amide compound, the insecticide preparation, and the insecticide composition.
The embodiment of the invention also provides application of the amide compound in preparing an animal parasite control agent. In the veterinary field, i.e. veterinary science, the amides of the invention can be used effectively against a wide variety of harmful animal parasites, in particular endoparasites and ectoparasites.
In one possible implementation, the animal parasite comprises one or more of the following:
from the order of the Anoplura (Anopluria), for example the genera Haematopinus spp, pediculosus spp (Linogaphus spp.), pediculosis spp (Pediculus spp.), Phtirus spp and pediculosis spp (Solenoptes spp.); in particular, representative examples are acanthamoeba (Linogathus setosus), bovines californica (Solenopotes capsulatus);
mallophaga (Mallopha, bamboos visuli (linogluchus), ovine palaemons (linogluchus), linogluchus oviformis, podophyllus pepulis (linogluchus pedalis), caprine palaemons (linogluchus stenopsis), donkey blood lice (Haematopinus asini macrocarpulus), bovine blood lice (Haematopinus eurytenus), porcine blood lice (Haematopinus suis), head lice (pee humanus capitis), body lice (pee humanus coproporus), grape root aphid (phyllera vasta), crab lice (phyllus purpura) and blunt sub-orders (ambyceria) and sub-orders of microcentrences (ischioptera), such as trichoderma, louse, and louse, such as trichoderma, louse, and leptopodium sp; in particular, representative examples are cow hair lice (Bovicola bovis), wool lice (Bovicola ovis), angora goat feather lice (Bovicola limcata), cow animal lice (Damalina bovis), dog hair lice (trichodices canis), cat feather lice (Felicola subclautus), goat hair lice (Bovicola caprae), lepentron ovis, bite lice (wereckiella equi);
diptera (Diptera) and its subclasses Petera (Nematococcus) and Brachydicta (Brachydictana), e.g. the genera Aedes (Aedes spp.), Anopheles (Anopheles spp.), Culex (Culex spp.), Kupffer (Culex spp.), Schistogna (Simulium spp.), Eumulus (Eulimulus spp.), phlebotomis (Phlebomes spp.), Lutzenliana (Lutzomyia spp.), Culicoides spp.), Tabanus (Chrysophthalmus spp.), Brevus (Leguminosae spp.), Brevus (Odagmia spp.), genus Wilhelmia spp., Strict spp., Strictus (Leguminosae spp.), femora spp., Tamarianus spp., Spanis., Sphagus, Sphagous spp., Pilus (Leguminosae spp.), Strauss spp.), gras spp., Leguminosae spp., Tabyssus spp., Musca, Sphagus (Mucoralis, Sphagus spp.), Sphagus spp., Tabyssus (Legiones spp.), Sphaga (Mus spp.), Sphagus), Strictus spp., Tabyssus (Legiones), Spiricus (Musca), Sphagus spp.), Spiricus (Musca) and Sphaga Sphagus spp. (Legiones (Musca), Sphagus spp.), Musca) of Strictus spp., Tabyssus (Musca), Spirisfiella (Musca) genus, Spirisfiella (Musca) and Spirisfiella) genus, Callyphora (callyphora spp.), Lucilia (Lucilia spp.), chrysomyl (Chrysomyia spp.), dirty muscoid (Wohlfahritia spp.), sarcophagemid (Sarcophaga spp.), lyssodomyl (Oestrus spp.), dermomyl (Hypoderma spp.), gastromyl (Gasterophilus spp.), pedicomyl (Hippoboca spp.), ovis (Lipopepta spp.), tick (Melophas spp.), nasus (Rhinoestus spp.), and rhynchus (Rhinoestus spp.), and mosquito (Tipula spp.); in particular, representative examples are Aedes aegypti (Aedes aegypti), Aedes albopictus (Aedes albopictus), Aedes coracois (Aedes taeniorhihynchus), Anopheles gambiensis (Anopheles gambiae), Anopheles pentamaculans (Anopheles macuripennis), Orthostis erythropolis (Calliphora erythrephala), Takavas magna (Chrysozona pluvialis), Culex quinans (Culex quinquefasciatus), Culex pipiens (Culex pipiens), Culex tarentus (Culex tarsalis), Corydus aestivus (Fannis), Sarcoporia (Sarcina), Sarcoporia (Sarcoporia), Sarcoporia gallica (Stomopsis), Sarcoporia great variety (Tiillus), Lucifera indica (Tacifolia), Lucifera leucopterica (Tacifolia), Lucifera leucopteria (Lucifolia), Lucifera indica), Lucifolia (Lucifera leucotrichia indica), Lucifolia (Lucifolia), Lucifera leucotrichia melanogaster indica), Lucifolia (Lucifolia), Lucifera leucotrichia terreus strain (Lucifolia), Lucifolia (Lucifolia), Luciferries pacifica (Lucifolia), Luciferries terreus strain (Luciferries terreus, Lucifolicus), Luciferries, Lucifolicus), Luciferries terreus, Lucifolius (Luciferries, Luciferries (Lucifolius), Lucifolicus), Luciferries (Lucifolicus), Luciferries, Lucifolicus), Lucifolius (Luciferries), Lucifolius), Luciferries, Lucifolius (Luciferries, Lucifolius), Lucifolicus), Luciferries (Lucifolicus), Lucifolius (Luciferries (Lucifolicus), Lucifolius (Lucifolicus), Luciferries (Lucifolius), Lucifolicus), Luciferries terreus, Lucifolius (Lucifolicus), Luciferries (Luciferries, Lucifolicus), Lucifolius), Lucifolicus), Luciferries (Lucifolius), Lucifolicus), Luciferries (Lucifolicus), Lucifolius (Luciferries (Lucifolius), Lu, Hermetia cubeba (Hybomita), hermetia illucens (Chrysosporium humans), hermetia lutea (Chrysosporium lucidus), Hermatopsis pleius (Haematopota pluvialis), Haematopotalalis, Okayata melanogaster (Musca autumnalis), Musca domestica (Musca domestica), Sarcophaga capitata (Haematobia irdans), Sarcophaga glabra (Haematobia irdans), Sarcophaga ciliata (Haematobia stimulans), Hydrotaea irtans, Sarcophaga leucoderma (Hydrotala alprepucata), Chrysomya Chrysomya, Chrysomya japonica (Chrysomya bezoar), Oyama pallidum (Ovoviridae), Sarcophaga pallidus, and Sarcophaga nivea, skin flies (Hypoderma linearis), Przhevaldiana silenus, human skin flies (Dermatobia hominis), kefir flies (Melophagus ovinus), Lipopetia capreoli, deer sheep lice flies (Lipopetia cervi), Hippoboca variegata, horse lice flies (Hippoboca equina), stomach flies (Gasterophilus intestinalis), stomach flies (Gasterophilus nigroceris), stomach flies (Gasterophilus petatus), and bees (Braziula coeca);
the order Siphonapterida, for example, the genera Siphonapterida (Pulex spp.), Ctenocephalides (Ctenocephalides spp.), Dinophyides (Tunga spp.), Dinophyides (Xenopsylla spp.), and Ceratophyllus spp.); in particular, representative examples are Ctenocephalides canis (Ctenocephacides canis), Ctenocephalides felis (Ctenocephacides felis), human fleas (Pulex irritans), Tetranychus penetrans (Tunga pierrans), Xenopsylla cheopis (Xenopsylla cheopis);
heteroptera (Heteropterida), for example, the genera Clerodera (Cimex spp.), Tolyptera (Triatoma spp.), Triptera triandra (Rhodnius spp.), Triptera (Prussonetia spp.), and Prussonetia (Panstrongylus spp.);
the order of the Blattarida (Blattarida), for example, Blatta orientalis (Blatta orientalis), Periplaneta americana, Blattella germanica, the genus Charcot roach (Supella spp.) (e.g., Supella longipapa);
acarina (Acari) (or Acarina), Metavalvales (Metastigmata) and Mesotimata, for example, Irelaphus (Argas spp.), Iridaceae (Ornithodoros spp.), Ornithodoros (Ornithodoros spp.), Otobius spp, Elyrifos (Ixodes spp.), Ordinium (Amblyomma spp.), Orixomelas (Rhipicephalus Boophilus) spp, Dermacentor spp, Haemophysalis spp, Hymenoptera (Hyomorpha spp.), Dermansussubusspp, Rhipicephalus (Rhipicephalus spp.), Isochrysis (Isochrysophyces spp.), Orthophys (Orthophys spp.), Orthophys spp
Pneumonyssimus spp, Pneumonyssis spp, Ceramix spp, Sternstoma spp, Beauveria spp, and Apis spp; in particular, representative examples are Ipomoea persicae (Argas persicus), Ipomoea batatas (Argas reflexus), Ornithodoros appendiculatus (Ornithodoros moubata), Rhipicephalus auricularis (Otobius megnini), Rhipicephalus cerealis (Rhipicephalus) microplus, Rhipicephalus fasciatus (Rhipicephalus) Anoplopius, Rhipicephalus fasciatus (Rhipicephalus) Anoplopius (Rhipicephalus) Anoplophora, Rhipicephalus appendiculatus (Rhipicephalus) Anoplophora (Rhipicephalus) Anoplus (Rhipicephalus) Anoplophora (Rhipicephalus), Hyalnus (Hyalnicole), Hyalnus nerus (Hyalxophycus), Rhipicephalus sanguinalis (Haemaxophagus), Rhipicephalus sanguinalis (Rhipicephalus), Rhipicephalus indicus (Rhipicephalus), Rhipicephalus (Rhizopus), Rhizopus indicus), Rhizopus (Rhizopus), Rhizopus indicus (Rhizopus), Rhizopus (Rhizopus), Rhizopus indicus (Rhizopus), Rhizopus indicus, Rhizopus (Rhizopus), Rhizopus (Rhizopus), Rhizopus (Rhizopus), Rhizopus), Rhizopus (Rhizopus ), Rhizopus (Rhizopus), Rhizopus (Rhizopus), Rhizopus including Ixos (Rhizopus ), Rhizopus (Rhizopus), Rhizopus including Rhizopus), Rhizopus (Rhizopus), Rhizopus (Rhizopus), Rhizopus), Rhizopus (Rhizopus, Rhizopus (Rhizopus), Rhizopus (Rhizopus including Rhizopus (Rhizopus including Rhizopus), Rhizopus (Rhizopus including Rhizopus), Rhizopus including Rhizopus, Rhizopus including (Rhizopus), Rhizopus including Rhizopus, Rhizopus (Rhizopus including Rhizopus, Rhizopus), Rhizopus (Rhizopus), Rhizopus (Rhi, Black lead ticks (Haemaphysalis leichi), black lead ticks (Haemaphysalis longicornis), Dermacentor marginalis (Dermacentor marginata), Dermacentor reticulare (Dermacentor reticulare), Dermacentor pictus (Dermacentor albitum), Dermacentor albium (Dermacentor albitum), Dermacentor anhyrini (Dermacentor variabilis), Erythrochlia mazeylans (Hyalomma magnum), Rhipicephalus sanguineus (Rhipicephalus sanguineus), Rhipicephalus capsulatus (Rhipicephalus bushua), Rhipicephalus africanus (Rhipicephalus appendiculatus), Rhipicephalus appendiculatus (Ammophila), Ammophila splendens, Ammophila auricula, Ammopsis (Ammophila auricula, Amblyomma Agricus), Ammopsis (Amblyomma Agrimonium), Ammophila auriculatum (Amblyomma Agrimonium), Amblyomma Agrimonium, Ammophila, Amblyomma Agrimonia, Ammopsis (Amblyomma Agrimonia, Acorus niphaea, Acorus niphymatodes, Acorus niphanus);
from the orders of the axyriales (actinodida) (prospectate) and the order of the acarida (acarida) (aspergillia), for example, the genera fagaceae (Acarapis spp.), acanthomonas (cheletella spp.), acanthomonas (avian streptococci spp.), sarcophaga (Myobia spp.), psorales (Psorergates spp.), Demodex spp.), tsutsutsuga (Trombicula spp.), listerorutorus spp.), Acarus (Acarus spp.), tyrosomus (tyroglobus spp.), trichophagous (trichophagous spp.), psorales (trichophys spp.), Psoroptes (trichophys spp.), psorales (trichophys spyptes), psorales (trichophys spp.), psorales (trichophys), psorales (psorales, acarina, psorales (psorales), psorales (trichophytes), psorales (psorales), psorales (trichophytes), psorales (trichophytes sp.); in particular, Geranium elegans (C heylectiella yasguri), Geranium brucei (C heylectiella blakei), Demodex canis (Demodex canis), Demodex bovis (Demodex bovis), Demodex ovis (Demodex ovis), Demodex capris (Demodex caprae), Demodex equi (Demodex equi), Demodex palli, Demodex suis (Demodex suis), Neomycin autumnalis, Neomycin desaleli, Neochlorida heterothermobia, Katsutsumadai (Trombia akamushi), Eremophilus canis (Otodectes cyotis), Cathare acarus (Notoredamisei), scabies canis (Sarcoptis canis), Sarcoptis bovis (Sarcoptis ovis), Sarcoptis ovis (Sarcoptis ovis), Sarcoptis capris (Sarcoptis papicaprae ═ s. caprae), Sarcoptis equi (Sarcoptis equi), Sarcoptis suis (Sarcoptis suis), Sarcoptis suis (Sarcoptis ovis), Sarcoptis ovis (Psoroptes ovis), scrapie (Psoroptes cunicululi), scrapie (Psoroptes equi), Psoroptes bovis (Sarcoptis ovis), psoropts ovis, pneumonyssoididic mange, Sarcoptis canis (Pneumonyssoides), trichoderma woodrupesium (acarus woodii);
nematodes such as Meloidogyne incognita (Meloidogyne incognita), Bursaphelenchus xylophilus (Bursaphelenchus xylophilus), Aphelenchoides besseyi (Aphelenchus besseyi), Heterodera glycines (Heterodera glycines), Heterodera pratyloides spp, and the like;
arthropods, worms and plasmodia that attack animals. Control arthropods, helminths and/or plasmodia, reduce mortality in domestic animals, and improve animal productivity (meat, milk, wool, skin, eggs and honey) and health.
In one possible implementation, the animal parasite control agent is used to control one or more of fleas and American dog ticks.
In one possible implementation, the animal includes one or more of: agricultural animals such as cattle, sheep, goats, horses, pigs, donkeys, camels, buffalo, rabbits, chickens, turkeys, ducks, geese, farmed fish, bees, etc.; also included are pets known as companion animals, e.g., dogs, cats, cage birds, aquarium fish; animals used for experiments such as hamsters, guinea pigs, rats, mice and the like are also included.
The embodiment of the invention also provides an animal parasite control agent, which contains the amide compound as an active component and one or more auxiliary materials.
In one possible implementation, the animal parasite control agent is selected from the following dosage forms: tablets, capsules, drinks, drinkable drugs, granules, ointments and pills, suppositories, injections (intramuscular, subcutaneous, intravenous, intraperitoneal and the like), smears, aerosols, non-pressurized sprays (e.g., pump sprays and aerosol sprays).
In one possible implementation, the above-mentioned active ingredient is contained in the animal parasite control agent in an amount of 1 to 80% by weight.
Embodiments of the present invention also provide an animal parasite control composition comprising a mixture of the above amide compounds and other animal parasite control active compounds (e.g., acaricides, insecticides, parasiticides, plasmodium repellents, etc.). The mixture can be provided in the form of raw material medicine, or can be provided in the form of a commercially available preparation or a use form prepared from the preparation.
Embodiments of the present invention also provide a method of controlling parasites on animals, comprising the steps of: administering to an animal parasite or its growth medium in need of control an effective amount of a material selected from one or more of the group consisting of: the above amide-based compounds; the above-mentioned animal parasite control agent; the animal parasite control composition described above. For example: enterally administering tablets, capsules, potables, drinkable drugs, granules, ointments, pills, and suppositories; parenteral administration based on dermal administration, such as injection (intramuscular, subcutaneous, intravenous, intraperitoneal and the like), implantation, nasal administration, including bathing or soaking, spraying, pouring, dripping, washing and dusting, and by using model articles containing the active compound, such as collars, ear tags, labels, leg bands (leg bands), nets, markers and the like. The active compounds of the invention have low toxicity and can be safely used in warm-blooded animals.
Advantageous effects
The amide-based compound of the present invention has an unexpectedly excellent pesticidal effect, exhibits a suitable controlling effect against toxic pests, and is not phytotoxic to cultivated crop plants. In addition, the compounds of the present invention are useful for controlling a wide variety of pests, such as harmful piercing-sucking insects, chewing insects and other plant parasitic pests, stored grain pests, sanitary pests and the like, and for disinfecting and killing them.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. .
Furthermore, in the following detailed description, numerous specific details are set forth in order to provide a better understanding of the present invention. It will be understood by those skilled in the art that the present invention may be practiced without some of these specific details. In some embodiments, materials, elements, methods, means, and the like that are well known to those skilled in the art are not described in detail in order to not unnecessarily obscure the present invention.
Throughout the specification and claims, unless explicitly stated otherwise, the word "comprise", or variations such as "comprises" or "comprising", will be understood to imply the inclusion of a stated element or component but not the exclusion of any other element or component
The starting materials are commercially available unless otherwise indicated.
In the present invention, the terms used have the following meanings:
halogen: refers to fluorine, chlorine, bromine or iodine.
Halogenated alkyl groups: straight-chain or branched alkyl radicals in which the hydrogen atoms may be partially or wholly replaced by halogen, e.g. difluoromethyl (CHF)2) Trifluoromethyl (CF)3) And the like.
Haloalkoxy groups: the hydrogen atoms of the alkoxy radicals being substituted partly or wholly by halogen, e.g. difluoromethoxy (OCHF)2) Trifluoromethoxy group (OCF)3) And the like.
Cyanoalkyl group: straight-chain or branched alkyl radicals in which the hydrogen atoms may be partially or wholly replaced by cyano radicals, cyano radicals C1-C4In alkyl radical C1-C4Representing the chain length of the alkyl radical, e.g. CH2CN、CH2CH2CN、CH2CH2CH2CN、CH2CH2CH2CH2CN、CH(CH3)CN、CH(CH2CH3)CN、CH(CH2CH2CH3)CN、C(CH3)(CH3) CN or C (CH)3)(CH2CH3)CN。
Insecticide: a substance having an insecticidal effect on pests.
Animal parasite control agents: refers to active compounds that are effective in reducing the incidence of various parasites in animals infected with the parasite. Control means that the active compounds are effective against parasites, inhibiting their growth or reproduction.
Synthetic examples
The compounds of formula I of the present invention can be prepared according to the above-described synthetic routes using different starting compounds, as further detailed below:
example 1: preparation of intermediate II.1
To 30 ml of DMF were added 1.00 g (1.80 mmol) of N- (2, 6-dibromo-4-heptafluoroisopropylphenyl) -2-fluoro-3-aminobenzamide (obtained by the method reported in WO2011093415 or WO2010018714, intermediate III-1), 0.37 g (2.68 mmol) of potassium carbonate, 0.27 g (1.80 mmol) of sodium iodide, and 0.26 g (2.19 mmol) of bromoacetonitrile, and the mixture was heated to 100 ℃. After TLC monitoring reaction, adding water and ethyl acetate for extraction, decompressing and desolventizing the organic phase, and purifying the residue by column chromatography to obtain 0.50 g of white solid, namely the intermediate II.1. Nuclear magnetic and mass spectral data for intermediate ii.1 are as follows:
1H NMR (600 MHz, Chloroform-d) δ 8.11 (d, 1H), 7.88 (s, 2H), 7.64 – 7.58 (m, 1H), 7.29 (t, 1H), 7.05 (td, 1H), 4.52 -4.44(br, 1H), 4.24 (d, 2H). LC-MS(m/z, ESI): 594.01(M+H)+.
example 2: preparation of intermediate II.2
10 g of N- (2-bromo-6-iodo-4-heptafluoroisopropylphenyl) -2-fluoro-3-nitrobenzamide (prepared according to the method reported in CN 109206335A), 15 g of anhydrous stannous chloride, 200 ml of 1, 4-dioxane and 8 ml of concentrated hydrochloric acid are added, and the mixture is heated to 60 ℃ and stirred for reaction. After the completion of the TLC monitoring reaction, the organic solvent was distilled off under reduced pressure. 500 ml of ethyl acetate was added, and an appropriate amount of saturated aqueous sodium hydroxide solution was added to adjust pH =10, after stirring sufficiently, the precipitated insoluble matter was filtered off with celite, the filtrate was extracted with ethyl acetate and water, and the organic layer was dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure to obtain a grayish brown solid, which was purified by column chromatography to obtain 7.91 g of N- (2-bromo-6-iodo-4-heptafluoroisopropylphenyl) -2-fluoro-3-aminobenzamide (intermediate III-2).
To 30 ml of DMF were added 1.00 g (1.66 mmol) of N- (2-bromo-6-iodo-4-heptafluoroisopropylphenyl) -2-fluoro-3-aminobenzamide (intermediate III-2), 0.34 g (2.46 mmol) of potassium carbonate, 0.25 g (1.67 mmol) of sodium iodide and 0.24 g (2.00 mmol) of bromoacetonitrile, and the mixture was heated to 100 ℃. After TLC monitoring reaction, adding water and ethyl acetate for extraction, decompressing and desolventizing the organic phase, and purifying the residue by column chromatography to obtain 0.43 g of white solid, namely the intermediate II.2. Nuclear magnetic and mass spectral data for intermediate ii.2 are as follows:
1H NMR (600 MHz, Chloroform-d) δ 8.12 (d, 1H), 8.08 (d, 1H), 7.90 (d, 1H), 7.61 (t, 1H), 7.29 (t, 1H), 7.05 (td, 1H), 4.54 - 4.47 (br, 1H), 4.24 (d, 2H). LC-MS(m/z, ESI): 642.05(M+H)+.
example 3: preparation of intermediate II.3
To 60 ml of DMF were added 2.00 g (3.67 mmol) of N- (2-bromo-6-trifluoromethyl-4-heptafluoroisopropylphenyl) -2-fluoro-3-aminobenzamide (intermediate III-3, obtained by the method reported in WO2011093415 or WO 2010018714), 0.76 g (5.50 mmol) of potassium carbonate, 0.56 g (3.74 mmol) of sodium iodide, and 0.53 g (4.42 mmol) of bromoacetonitrile, and the mixture was heated to 100 ℃. After TLC monitoring reaction, adding water and ethyl acetate for extraction, decompressing and desolventizing the organic phase, and purifying the residue by column chromatography to obtain 0.78 g of white solid, namely the intermediate II.3. Nuclear magnetic and mass spectral data for intermediate ii.3 are as follows:
1H NMR (600 MHz, Chloroform-d) δ 8.18 (d, 1H), 8.16 – 8.13 (m, 1H), 7.94 – 7.90 (m, 1H), 7.63 – 7.55 (m, 1H), 7.29 (t, 1H), 7.05 (td, 1H), 4.52 – 4.45 (m, 1H),4.24 (d, 2H). LC-MS(m/z, ESI): 584.04(M+H)+.
example 4: preparation of intermediate II.4
To 60 ml of DMF were added 2.00 g (3.67 mmol) of N- (2-bromo-6-trifluoromethyl-4-heptafluoroisopropylphenyl) -2-fluoro-3-aminobenzamide (intermediate III-3), 0.76 g (5.50 mmol) of potassium carbonate, 0.55 g (3.67 mmol) of sodium iodide and 0.59 g (4.40 mmol) of bromopropionitrile, and the mixture was heated to 100 ℃. After TLC monitoring reaction, adding water and ethyl acetate for extraction, decompressing and desolventizing the organic phase, and purifying the residue by column chromatography to obtain 0.22 g of white solid, namely the intermediate II.4. Nuclear magnetic and mass spectral data for intermediate ii.4 are as follows:
1H NMR (600 MHz, Chloroform-d) δ 8.22 (d, 1H),8.16 – 8.13 (m, 1H),7.93 – 7.90 (m, 1H), 7.50 – 7.45 (m, 1H), 7.20 (t, 1H), 6.91 (td, 1H), 4.46 – 4.38 (m, 1H),3.63 (q, 2H), 2.72 (t, 2H). LC-MS(m/z, ESI): 598.05(M+H) +.
example 5: preparation of intermediate II.5
To 40ml of DMF were added 1.30 g (2.39 mmol) of N- (2-bromo-6-trifluoromethyl-4-heptafluoroisopropylphenyl) -2-fluoro-3-aminobenzamide (intermediate III-3), 0.49 g (3.55 mmol) of potassium carbonate, 0.36 g (2.40 mmol) of sodium iodide and 0.46 g (3.13 mmol) of bromobutyronitrile, and the mixture was heated to 100 ℃. After TLC monitoring reaction, adding water and ethyl acetate for extraction, decompressing and desolventizing the organic phase, and purifying the residue by column chromatography to obtain 0.19 g of white solid, namely the intermediate II.5. Nuclear magnetic and mass spectral data for intermediate ii.5 are as follows:
1H NMR (600 MHz, Chloroform-d) δ 8.22 (d, 1H), 8.15 – 8.13 (m, 1H), 7.92 – 7.90 (m, 1H), 7.46 – 7.40 (m, 1H), 7.18 (t, 1H), 6.94 (td, 1H), 4.17 – 4.09 (m, 1H), 3.43 (q, 2H), 2.54 (t, 2H), 2.08 – 2.02 (m, 2H). LC-MS(m/z, ESI): 612.06(M+H) +.
example 6: preparation of intermediate II.6
To 50 ml of DMF were added 1.65 g (3.03 mmol) of N- (2-bromo-6-trifluoromethyl-4-heptafluoroisopropylphenyl) -2-fluoro-3-aminobenzamide (intermediate III-3), 0.62 g (4.50 mmol) of potassium carbonate, 0.46 g (3.07 mmol) of sodium iodide and 0.61 g (3.79 mmol) of bromovaleronitrile, and the mixture was heated to 100 ℃. After TLC monitoring reaction, adding water and ethyl acetate for extraction, decompressing and desolventizing the organic phase, and purifying the residue by column chromatography to obtain 0.21 g of white solid, namely the intermediate II.6. Nuclear magnetic and mass spectral data for intermediate ii.6 are as follows:
1H NMR (600 MHz, Chloroform-d) δ 8.23 (d, 1H), 8.14 (d, 1H), 7.91 (d, 1H), 7.42 – 7.37 (m, 1H), 7.17 (t, 1H), 6.91 (td, 1H), 4.13 – 3.98 (m, 1H), 3.28 (t, 2H), 2.45 (t, 2H), 1.93 – 1.80 (m, 4H). LC-MS(m/z, ESI): 626.05(M+H) +.
example 7: preparation of intermediate II.7
Intermediate ii.7 (white solid) was prepared from intermediate III-4 (prepared according to the methods reported in WO2011093415 or WO 2010018714) and bromoacetonitrile by the method described in example 3. Nuclear magnetic and mass spectral data for intermediate ii.7 are as follows:
1H NMR (600 MHz, Chloroform-d) δ 8.37 – 8.34 (m, 1H), 8.22 (d, 1H), 7.96 – 7.93 (m, 1H), 7.64 – 7.57 (m, 1H), 7.29 (t, 1H), 7.05 (td, 1H), 4.52 – 4.45 (m, 1H), 4.25 (d, 2H).LC-MS(m/z, ESI): 631.99(M+H) +.
example 8: preparation of intermediate II.8
Intermediate II.8 (white solid) was prepared from intermediate III-4 and bromopropionitrile according to the procedure described for example 4. Nuclear magnetic and mass spectral data for intermediate ii.8 are as follows:
1H NMR (600 MHz, Chloroform-d) δ 8.36 (d, 1H), 8.26 (d, 1H), 7.94 (d, 1H), 7.51 – 7.46 (m, 1H), 7.21 (t, 1H), 6.92 (td, 1H), 4.47 – 4.39 (m, 1H), 3.64 (q, 2H), 2.72 (t, 2H). LC-MS(m/z, ESI): 646.02(M+H)+.
example 9: preparation of intermediate II.9
Intermediate II.9 (white solid) was prepared from intermediate III-4 and bromobutyronitrile by the procedure described in example 5. Nuclear magnetic and mass spectral data for intermediate ii.9 are as follows:
1H NMR (600 MHz, Chloroform-d) δ 8.36 – 8.34 (m, 1H), 8.27 (d, 1H), 7.95 – 7.92 (m, 1H), 7.45 – 7.40 (m, 1H), 7.18 (td, 1H), 6.94 (td, 1H), 4.18 – 4.11 (br s, 1H), 3.43 (q, 2H), 2.54 (t, 2H), 2.08 – 2.02 (m, 2H).LC-MS(m/z, ESI): 682.24(M+Na+H)+.
example 10: preparation of intermediate II.10
Intermediate II.10 (white solid) was prepared from intermediate III-4 and bromovaleronitrile according to the procedure described for example 6. Nuclear magnetic and mass spectral data for intermediate ii.10 are as follows:
1H NMR (600 MHz, Chloroform-d) δ 8.35 (d, 1H), 8.28 (d, 1H), 7.93 (d, 1H), 7.43 – 7.38 (m, 1H), 7.17 (t, 1H), 6.91 (td, 1H), 4.22 – 3.90 (br s, 1H), 3.28 (t, 2H), 2.45 (t, 2H), 1.92 – 1.81 (m, 4H).LC-MS(m/z, ESI): 696.26(M+Na+H)+.
example 15: preparation of Compound 1
To 20 ml of toluene were added 0.30 g (0.51 mmol) of intermediate II.1 and 0.12 g (0.72 mmol) of 6-cyanonicotinyl chloride, and the mixture was refluxed. After the completion of the TLC monitoring reaction, the reaction mixture was desolventized under reduced pressure and the residue was purified by column chromatography to obtain 0.23 g of a white solid, i.e., Compound 1. Nuclear magnetic and mass spectral data for compound 1 are as follows:
1H NMR (600 MHz, Chloroform-d) δ 8.71 – 8.66 (m, 1H), 8.19 (t, 1H), 7.93 – 7.86 (m, 4H), 7.64 (d, 1H), 7.58 – 7.54 (m, 1H), 7.42 (t, 1H), 5.00 (d, 1H), 4.65 (d, 1H). LC-MS(m/z, ESI): 724.15(M+H)+.
example 16: preparation of Compound 5
Compound 5 (white solid) was prepared from intermediate II.2 and 6-cyanonicotinyl chloride by the method described in example 15. Nuclear magnetic and mass spectral data for compound 5 are as follows:
1H NMR (600 MHz, Chloroform-d) δ 8.71 – 8.66 (m, 1H), 8.20 (t, 1H), 8.08 (d, 1H), 7.93 – 7.85 (m, 3H), 7.63 (d, 1H), 7.58 (t, 1H), 7.43 (t, 1H), 4.99 (d, 1H), 4.66 (d, 1H). LC-MS(m/z, ESI): 772.20(M+H)+.
example 17: preparation of Compound 9
Compound 9 (yellow solid) was prepared from intermediate II.3 and 6-cyanonicotinyl chloride by the method described for example 15. Nuclear magnetic and mass spectral data for compound 9 are as follows:
1H NMR (600 MHz, Chloroform-d) δ 8.72 – 8.57 (m, 1H), 8.23 – 8.09 (m, 2H), 8.01 (d, 1H), 7.96 – 7.83 (m, 2H), 7.64 (d, 1H), 7.61 – 7.55 (m, 1H), 7.43 (t, 1H), 4.98 (d, 1H), 4.66 (d, 1H). LC-MS(m/z, ESI): 736.29(M+Na+H)+.
example 18: preparation of Compound 10
Compound 10 (yellow solid) was prepared from intermediate II.4 and 6-cyanonicotinyl chloride by the method described for example 15. Nuclear magnetic and mass spectral data for compound 10 are as follows:
1H NMR (600 MHz, Chloroform-d) δ 8.64 (s, 1H), 8.13 (d, 1H), 8.05 (t, 1H), 7.96 (d, 1H), 7.91 – 7.89 (m, 1H), 7.85 (dd, 1H), 7.68 (td, 1H), 7.61 (d, 1H), 7.42 (t, 1H), 4.19 (t, 2H), 3.06 – 2.96 (m, 1H), 2.95 – 2.84 (m, 1H). LC-MS(m/z, ESI): 750.32(M+Na+H)+.
example 19: preparation of Compound 11
Compound 11 (yellow oil) was prepared from intermediate II.5 and 6-cyanonicotinyl chloride by the method described in example 15. Nuclear magnetic and mass spectral data for compound 11 are as follows:
1H NMR (600 MHz, Chloroform-d) δ 8.60 (s, 1H), 8.14 (d, 1H), 8.10 – 8.04 (m, 1H), 7.97 (d, 1H), 7.91 (d, 1H), 7.83 (dd, 1H), 7.62 – 7.53 (m, 2H), 7.38 (t, 1H), 4.16 – 4.04 (m, 2H), 2.56 (t, 2H), 2.18 – 2.02 (m, 2H). LC-MS(m/z, ESI): 764.34(M+Na+H)+.
example 20: preparation of Compound 12
Compound 12 (yellow oil) was prepared from intermediate II.6 and 6-cyanonicotinyl chloride by the method described in example 15. Nuclear magnetic and mass spectral data for compound 12 are as follows:
1H NMR (600 MHz, Chloroform-d) δ 8.60 (s, 1H), 8.20 – 8.11 (m, 2H), 8.02 (t, 1H), 7.90 (d, 1H), 7.83 – 7.76 (m, 1H), 7.58 (d, 1H), 7.55 – 7.49 (m, 1H), 7.39 (t, 1H), 4.25 (br s, 1H), 3.90 – 3.79 (m, 1H), 2.57 – 2.36 (m, 2H), 1.93 – 1.77 (m, 4H). LC-MS(m/z, ESI): 778.37(M+Na+H)+.
example 21: preparation of Compound 13
Compound 13 (yellow solid) was prepared from intermediate II.7 and 6-cyanonicotinyl chloride by the method described for example 15. Nuclear magnetic and mass spectral data for compound 13 are as follows:
1H NMR (600 MHz, Chloroform-d) δ 8.65 (d, 1H), 8.35 (d, 1H), 8.18 – 8.12 (m, 1H), 8.07 (d, 1H), 7.94 (d, 1H), 7.89 (dd, 1H), 7.64 (d, 1H), 7.62 – 7.56 (m, 1H), 7.43 (t, 1H), 4.97 (br s, 1H), 4.67 (br s, 1H). LC-MS(m/z, ESI): 784.32(M+Na+H)+.
example 22: preparation of Compound 14
Compound 14 (yellow solid) was prepared from intermediate II.8 and 6-cyanonicotinyl chloride by the method described for example 15. Nuclear magnetic and mass spectral data for compound 14 are as follows:
1H NMR (600 MHz, Chloroform-d) δ 8.65 (s, 1H), 8.33 (d, 1H), 8.09 – 7.97 (m, 2H), 7.93 (d, 1H), 7.84 (dd, 1H), 7.69 (td, 1H), 7.60 (d, 1H), 7.43 (t, 1H), 4.19 (s, 2H), 3.08 – 2.97 (m, 1H), 2.95 – 2.84 (m, 1H). LC-MS(m/z, ESI): 798.34(M+Na+H)+.
example 23: preparation of Compound 15
Compound 15 (yellow solid) was prepared from intermediate II.9 and 6-cyanonicotinyl chloride by the method described for example 15. Nuclear magnetic and mass spectral data for compound 15 are as follows:
1H NMR (600 MHz, Chloroform-d) δ 8.61 (s, 1H), 8.34 (d, 1H), 8.11 – 7.97 (m, 2H), 7.93 (d, 1H), 7.86 – 7.79 (m, 1H), 7.62 – 7.54 (m, 2H), 7.39 (t, 1H), 4.17 – 4.04 (m, 2H), 2.56 (t, 2H), 2.18 – 2.02 (m, 2H). LC-MS(m/z, ESI): 812.36(M+Na+H)+.
example 24: preparation of Compound 16
Compound 16 (yellow solid) was prepared from intermediate II.10 and 6-cyanonicotinyl chloride by the method described for example 15. Nuclear magnetic and mass spectral data for compound 16 are as follows:
1H NMR (600 MHz, Chloroform-d) δ 8.60 (s, 1H), 8.33 (d, 1H), 8.19 (s, 1H), 8.02 (t, 1H), 7.92 (d, 1H), 7.82 – 7.74 (m, 1H), 7.61 – 7.50 (m, 2H), 7.39 (t, 1H), 4.26 (br s, 1H), 3.83 (br d, 1H), 2.55 – 2.36 (m, 2H), 1.90 – 1.77 (m, 4H). LC-MS(m/z, ESI): 826.41(M+Na+H)+.
other compounds of formula I of the present invention may be prepared by reference to the above examples.
Biological activity assay
Example 25: biological activity assay of armyworm, diamondback moth and chilo suppressalis
Several insects were tested for insecticidal activity using the compounds of the present invention. The measurement method is as follows:
after dissolving a test compound in a mixed solvent of acetone/methanol (1: 1), the test compound was diluted with water containing 0.1% (wt) Tween 80 to a desired concentration.
Takes armyworm, diamondback moth and chilo suppressalis as targets, and adopts an Airbrush spray method to carry out activity determination.
(1) Activity assay for armyworm killing
The determination method comprises the following steps: the corn leaves were cut into 2cm long sections and the pressure of the Airbrush spray treatment was 10psi (approximately 0.7 kg/cm)2) Spraying on the front and back sides of each leaf segment, wherein the liquid spraying amount of the compound to be detected is 0.5 ml. After drying in the shade, 10 larvae of 3 instar larvae were inoculated per treatment, and the treatment was repeated 3 times. After treatment, the treated insects are placed into an observation room with the temperature of 25 ℃ and the relative humidity of 60-70% for culture, the number of the survival insects is investigated 3 days after the treatment, and the death rate is calculated.
The results of the partial test on armyworm are as follows:
at the dose of 0.05mg/L, the lethality of the compounds 1, 5, 9, 10, 11, 12, 13, 14, 15 and 16 to armyworms is more than 90 percent in 3 days after the administration.
(2) Activity assay for killing diamondback moth
The determination method comprises the following steps: the cabbage leaves were punched into a 2 cm-diameter dish by means of a punch, and the pressure of the Airbrush spray treatment was 10psi (approximately 0.7 kg/cm)2) Spraying on the front and back sides of each leaf disc, wherein the spraying amount of the compound to be detected is 0.5 ml. After drying in the shade, 10 larvae of 3 instar larvae were inoculated per treatment, and the treatment was repeated 3 times. After treatment, the treated insects are placed into an observation room with the temperature of 25 ℃ and the relative humidity of 60-70% for culture, the number of the survival insects is investigated 3 days after the treatment, and the death rate is calculated.
Partial test results for plutella xylostella are as follows:
the lethality of the compounds 1, 5, 9, 10, 11, 12, 13, 14, 15 and 16 to plutella xylostella is more than 90% at the dose of 1 mg/L.
At the dose of 0.05mg/L, the lethality of the compounds 9, 10, 11, 12, 13, 14, 15 and 16 to plutella xylostella is more than 90%.
(3) Activity assay for Chilo suppressalis killing
The determination method comprises the following steps: 1) preparing rice seedlings: culturing rice in a constant temperature chamber (temperature is 26-28 ℃, relative humidity is about 60-80%, illumination is 16hL:8 hD) by using a plastic cup with the diameter of 4.5cm and the height of 4cm, and selecting robust rice seedlings with consistent growth vigor for medicament treatment when the rice grows to 4-5 leaf stages, wherein the treatment is repeated for 3 times. 2) Preparing a test insect: chilo suppressalis bred continuously indoors and larvae of 3 years old. 3) Spraying rice stems to inoculate insects. The spraying method is adopted to evenly spray the whole rice seedlings, and 15ml of the pesticide is used for each treatment. The blank control was treated first and the above procedure was repeated in order of the test concentrations from low to high. After the rice seedlings are sprayed, the rice seedlings are placed in a shade place to be dried in the air, and stems about 5cm from the stem base parts are cut to feed the test insects. Preparing glass culture dishes with the diameter of 90mm, filling filter paper at the bottom of the culture dishes, adding water for moisturizing, putting about 5 rice stems into each culture dish, connecting 10 larvae, sealing the culture dishes by using non-woven fabrics, and placing the culture dishes in a constant temperature room for culture. The number of remaining live insects was investigated 3 days after the administration.
The results of the partial test on chilo suppressalis are as follows:
the lethality of the compounds 1, 5, 9, 10, 11, 12, 13, 14, 15 and 16 to Chilo suppressalis is more than 90% at the dose of 1 mg/L.
At the dose of 0.125 mg/L, the lethality of the compounds 9, 10, 11, 12, 13, 14, 15 and 16 to Chilo suppressalis is over 90 percent.
Selecting the compounds 1, 9 and 13 of the invention and a control compound to carry out a parallel comparison test (3 days after drug administration) of the insecticidal activity of the chilo suppressalis, wherein the determination method is the same as that described above; the results are shown in table 2:
table 2 parallel comparison of insecticidal activity of compounds 1, 9, 13 of the invention against Chilo suppressalis as control compounds
Note: in Table 2, "-" indicates no measurement. In the table, 1-1, 1-2, 2-1, 2-2, 3-1, 3-2 are all control compounds provided herein; compounds 1-1, 1-2 are obtainable by the method according to example 15 of the present invention; compounds 2-1, 2-2 are obtainable by the method of example 17 of the present invention; compounds 3-1, 3-2 can be obtained by the method according to example 21 of the present invention; the starting materials are either those which can be prepared according to the methods of the examples of the present invention or are commercially available or can be prepared according to conventional methods.
In the embodiment of the invention, R in the compound of formula I1、R2、R3、R4Groups and combinations thereof were selected to obtain compounds with better insecticidal effect, as shown in table 2, by comparing compound 1 with control compounds 1-1, 1-2, by comparing compound 9 with control compounds 2-1, 2-2, and by comparing compound 13 with control compounds 3-1, 3-2: the cyano group and the adjacent nitrogen atom on the benzene ring are very important, the cyano group and the adjacent nitrogen atom are matched with each other, and none of the cyano group and the adjacent nitrogen atom are matched with each other, so that the activity of the compound on chilo suppressalis is obviously reduced or even lost after the cyano group is reserved and the adjacent nitrogen atom is selected as a carbon atom; when the nitrogen atom is reserved and the adjacent cyano group is selected to be hydrogen, the compound completely loses the activity to chilo suppressalis.
Example 26: insecticidal test against cat fleas
After dissolving 4mg of a test compound in 40ml of acetone to obtain an acetone solution having a concentration of 100ppm, 400. mu.l of a drug solution was applied to the bottom and side surfaces of a petri dish having an inner diameter of 5.3cm, and acetone was evaporated, a thin film of the compound of the present invention was formed on the inner wall of the petri dish. The inner wall of the culture dish used was 40cm2The treatment dose is 1 mu g/cm2(ii) a 10 adult fleas (male and female mixed) were put into the container, covered and stored in a thermostatic chamber at 25 ℃. And (5) checking the number of dead insects after 72h, and calculating the dead insect rate. The test was repeated 3 times. And (3) testing results: compounds 1, 5, 9, 10, 11, 12, 13, 14, 15, 16 showed a mortality rate of 90% or more.
Example 27: insecticidal test on American Canine ticks
After dissolving 4mg of a test compound in 40ml of acetone to obtain an acetone solution with a concentration of 100ppm, 400. mu.l of a drug solution was applied to the bottom and side surfaces of 2 petri dishes with an inner diameter of 5.3cm, and acetone was evaporated, a thin film of the compound of the present invention was formed on the inner wall of the petri dish. The inner wall of the culture dish used was 40cm2The treatment dose is 1 mu g/cm2. To this, 10 american dog tick 1 st nymphs (male-female mix) were placed, 2 dishes were pooled, the junction was sealed with tape to prevent escape, and stored in a thermostatic chamber at 25 ℃. And (5) checking the number of dead insects after 24h, and calculating the dead insect rate. The test was repeated 3 times. And (3) testing results: compounds 1, 5, 9, 10, 11, 12, 13, 14, 15, 16 showed a mortality rate of 90% or more.
Claims (15)
1. An amide compound characterized in that: the structure of the amide compound is shown as a general formula I:
in formula I:
R1selected from halogens;
R2selected from halogen, C1-C4Haloalkyl or C1-C4A haloalkoxy group;
R3selected from CF3Or CF2CF3；
R4Selected from cyano group C1-C4An alkyl group.
2. The compound of claim 1, wherein: in the general formula I
R1Selected from halogens;
R2selected from halogen, C1-C2Haloalkyl or C1-C2A haloalkoxy group;
R3selected from CF3Or CF2CF3；
R4Selected from cyano group C1-C4An alkyl group.
3. The compound of claim 2, wherein: in the general formula I
R1Selected from bromine or iodine;
R2selected from bromo, iodo, trifluoromethyl or difluoromethoxy;
R3selected from CF3Or CF2CF3；
R4Is selected from CH2CN、CH2CH2CN、CH2CH2CH2CN、CH2CH2CH2CH2CN、CH(CH3)CN、CH(CH2CH3)CN、CH(CH2CH2CH3)CN、C(CH3)(CH3) CN or C (CH)3)(CH2CH3)CN。
4. A compound according to claim 3, characterized in that: in the general formula I
R1Selected from bromine or iodine;
R2selected from bromine, iodine or trifluoromethyl;
R3selected from CF3；
R4Is selected from CH2CN、CH2CH2CN、CH2CH2CH2CN or CH2CH2CH2CH2CN。
5. The amide-based compound according to claim 1, wherein the amide-based compound is selected from the group consisting of:
the compounds of Table 1, the compounds of Table 1 have the structure as shown in formula I and R1、R2、R3And R4As shown in table 1;
6. use of the amide-based compound according to any one of claims 1 to 5 for the preparation of a pesticide.
7. Use according to claim 6, characterized in that: the pesticide is used for preventing and controlling one or more of armyworm, diamondback moth and chilo suppressalis.
8. An insecticide formulation characterized by: the pesticide preparation contains the amide compound as claimed in any one of claims 1 to 5 as an active ingredient, and also contains one or more auxiliary materials; alternatively, the amount of the amide-based compound described in any one of claims 1 to 5 in the pesticide preparation is 0.1 to 99% by weight, further alternatively 0.5 to 90% by weight.
9. An insecticide composition characterized by: a mixture comprising the amide-based compound according to any one of claims 1 to 5 and a further active compound selected from one or more of insecticides, baits, disinfectants, acaricides, nematicides, fungicides, growth regulators, herbicides.
10. A method of controlling agricultural or forestry pests, comprising: applying an effective amount of a material to a pest or its growth medium in need of control, the material being selected from one or more of the following:
the amide-based compound according to any one of claims 1 to 5;
the pesticide formulation of claim 8;
the pesticidal composition of claim 9.
11. Use of an amide-based compound according to any one of claims 1 to 5 for the preparation of an animal parasite control agent.
12. Use according to claim 11, characterized in that: the animal parasite control agent is used to control one or more of cat fleas, American dog ticks.
13. An animal parasite control agent characterized by: the animal parasite control agent contains the amide-based compound according to any one of claims 1 to 5 as an active ingredient, and further contains one or more auxiliary materials; alternatively, the amide-based compound described in any one of claims 1 to 5 is contained in the animal parasite control agent in an amount of 1 to 80% by weight.
14. An animal parasite control composition, characterized by: a mixture comprising an amide-based compound according to any one of claims 1 to 5 and a further animal parasite control active compound selected from one or more of an acaricide, an insecticide, a parasiticide, an antimalarial agent.
15. A method of controlling parasites on animals comprising: the method comprises the following steps: administering to an animal parasite or its growth medium in need of control an effective amount of a material selected from one or more of the group consisting of:
amides as claimed in any of claims 1 to 5;
the animal parasite control agent of claim 13;
the animal parasite control composition of claim 14.
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| WO2024109431A1 (en) * | 2022-11-25 | 2024-05-30 | 沈阳中化农药化工研发有限公司 | Insecticidal preparation containing meta-diamide compound and use thereof |
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| WO2019059412A1 (en) * | 2017-09-20 | 2019-03-28 | Mitsui Chemicals Agro, Inc. | Prolonged ectoparasite-controlling agent for animal |
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| CN1926094A (en) * | 2004-01-28 | 2007-03-07 | 三井化学株式会社 | Amide derivatives, process for production of the same, and method for application thereof as insecticide |
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| CN117466813A (en) * | 2023-05-30 | 2024-01-30 | 湖南化工研究院有限公司 | Meta-aminobenzoic acid bisamide compound and intermediate thereof |
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