Pyrimidine-containing propylene ether compound as well as preparation method and application thereof

Abstract

The invention provides a pyrimidine-containing propylene ether compound and a preparation method and application thereof, the structure of the pyrimidine-containing propylene ether compound is as shown in a general formula I: # imgabs0 #, and the pyrimidine-containing propylene ether compound provided by the invention has broad-spectrum bactericidal activity, and has an excellent control effect on wheat powdery mildew, corn rust and the like. The compound disclosed by the invention simultaneously shows good insecticidal and acaricidal activity, and has a relatively high fatality rate on plutella xylostella, armyworm, tetranychus cinnabarinus and the like.

Description

Technical Field

[0001] The invention belongs to the technical field of agricultural sterilization, insecticide and acaricide, and specifically relates to a pyrimidine-containing propene ether compound and a preparation method and application thereof. Background Art

[0002] The prevention and control of pests and diseases has always been the core area of ​​pesticide scientific research, and the widespread use of pesticides has enabled it to be effectively controlled. However, with the continuous expansion of the scale of pesticide application, the problem of resistance of traditional pesticide varieties has become increasingly prominent, and the continuous emergence of new pests and diseases has made the research and development of new pesticides with high efficiency and low toxicity an inevitable choice.

[0003] The following patents report dihalopropene compounds with insecticidal and acaricidal activities: CN1137265, CN1318535, CN1681771, CN1780818, CN1780825, CN1860874, CN101208088, US5872137, US5922880, US6071861, US20060247283, US20050288186, US20040224994, US20070142229, WO2003074498, etc. The representative variety of this type of compound, pyridalyl, is a patented product of Sumitomo Chemical Co., Ltd. of Japan. It has excellent effects on a wide range of lepidopteran pests on vegetables and cotton. The structural formula is as follows:

[0004]

[0005] Pyrimidine compounds are an important class of fungicides developed since the 1950s. They are effective against various diseases caused by Botrytis cinerea. They act as mitochondrial complex I electron transfer inhibitors and are one of the few fungicides for which resistance has not yet been reported. They also have no cross-resistance with common fungicides. These properties indicate that pyrimidines are a class of potential compounds for the discovery of pesticide candidate varieties. For example, diflumetorim, which was approved for registration in Japan in 1997, has excellent control effects on wheat powdery mildew and rust (EP 0370704); and cyprodinil, a fungicide developed by Syngenta, has good control effects on gray mold, powdery mildew and black spot (EP 310550).

[0006]

[0007] Therefore, in order to continue to search for compounds with excellent biological activity from dihalopropene ether derivatives, we plan to adopt the principle of active substructure splicing to rationally combine the substituted pyrimidine group with the dihalopropene ether skeleton, and disclose a class of pyrimidine-containing propene ether compounds with good bactericidal and insecticidal activity. Summary of the invention

[0008] The present invention provides a pyrimidine-containing propene ether compound and a preparation method and use thereof. The pyrimidine-containing propene ether compound of the present invention is used for preparing a drug for preventing and treating pathogens or pests and mites in agriculture or other fields. The compound of the present invention has a broad-spectrum fungicidal activity and has an excellent control effect on wheat powdery mildew, corn rust, etc. At the same time, it exhibits good insecticidal and acaricidal activity and has a high mortality rate against diamondback moth, armyworm, cinnabarinus spider mite, etc.

[0009] The present invention adopts the following technical solutions:

[0010] The pyrimidine-containing propene ether compound is shown in general formula I:

[0011]

[0012] Where:

[0013] R 1 is selected from hydrogen, halogen, cyano, nitro, amino, carboxyl, C 1 -C 4 Alkyl, halogenated C 1 -C 4 Alkyl, C 3 -C 4 Cycloalkyl, C 1 -C 4 Alkoxy, halogenated C 1 -C 4 Alkoxy, C 1 -C 4 Alkylthio, C 1 -C 4 Alkylsulfinyl, C 1 -C 4 Alkylsulfonyl, halo C 1 -C 4 Alkylthio, C 2 -C 4 Alkenyl, halogenated C 2 -C 4 Alkenyl, C 2 -C 4 Alkynyl, halo C 2 -C 4 Alkynyl, C 3 -C 4 Alkenyloxy, halogenated C 3 -C 4Alkenyloxy, C 3 -C 4 Alkynyloxy, halo C 3 -C 4 Alkynyloxy, C 1 -C 4 Alkylamino, di(C 1 -C 4 Alkyl)amino, C 1 -C 4 Alkylaminocarbonyl, halocarbonyl 1 -C 4 Alkylaminocarbonyl, C 1 -C 4 Alkoxycarbonyl, halocarbonyl 1 -C 4 Alkoxycarbonyl, C 1 -C 4 Alkoxy C 1 -C 4 Alkyl or C 1 -C 4 Alkylthio C 1 -C 4 One of the alkyl groups;

[0014] R 2 is selected from hydrogen, halogen, cyano, nitro, aldehyde, amino, carboxyl, formyl, C 1 -C 4 Alkyl, halogenated C 1 -C 4 Alkyl, C 1 -C 4 Alkoxy, halogenated C 1 -C 4 One of alkoxy or halogenated phenyl;

[0015] or R 1 and R 2 Together with the connected pyrimidine ring, it forms a five-membered or six-membered ring containing C, N, O or S;

[0016] W is selected from hydrogen, halogen, amino, carboxyl, C 1 -C 4 Alkyl, halogenated C 1 -C 4 Alkyl, C 3 -C 4 Cycloalkyl, C 1 -C 4 Alkoxy, C 1 -C 4 Alkylthio, C 1 -C 4 Alkylamino, C 1 -C 4 Alkoxycarbonyl or C 1-C 4 One of the alkylsulfonyl groups;

[0017] X is selected from NR 3 , O or S;

[0018] m is selected from an integer from 0 to 3, and when m is selected from 2 or 3, X cannot be O;

[0019] R 3 Selected from hydrogen, hydroxyl, formyl, C 1 -C 4 Alkyl, halogenated C 1 -C 4 Alkyl, C 1 -C 4 Alkoxy, halogenated C 1 -C 4 Alkoxy, C 3 -C 4 Cycloalkyl, C 1 -C 4 Alkylthio, C 2 -C 4 Alkenylthio, C 2 -C 4 Alkenyl, C 2 -C 4 Alkynyl, halo C 2 -C 4 Alkenyl, halogenated C 2 -C 4 Alkynyl, C 1 -C 4 Alkoxy C 1 -C 4 Alkyl, halogenated C 1 -C 4 Alkoxy C 1 -C 4 Alkyl, C 1 -C 4 Alkylthio C 1 -C 4 Alkyl, halogenated C 1 -C 4 Alkylthio C 1 -C 4 Alkyl, C 1 -C 4 Alkylsulfinyl, halo C 1 -C 4 Alkylsulfinyl, C 1 -C 4 Alkylsulfonyl, halo C 1 -C 4 Alkylsulfonyl, C 1 -C 4 Alkylaminosulfonyl, di(C1 -C 4 (alkyl)aminosulfonyl, C 1 -C 4 Alkylsulfonylaminocarbonyl, C 1 -C 4 Alkylcarbonylaminosulfonyl, C 3 -C 4 Cycloalkyloxycarbonyl, C 1 -C 4 Alkylcarbonyl, haloC 1 -C 4 Alkylcarbonyl, C 1 -C 4 Alkoxycarbonyl, halocarbonyl 1 -C 4 Alkoxycarbonyl, C 1 -C 4 Alkylcarbonyl C 1 -C 4 Alkyl, C 1 -C 4 Alkoxycarbonyl C 1 -C 4 Alkyl, C 1 -C 4 Alkylaminocarbonyl, di(C 1 -C 4 alkyl)aminocarbonyl, C 2 -C 4 Alkenyloxycarbonyl, C 2 -C 4 Alkynyloxycarbonyl, C 1 -C 4 Alkoxy C 1 -C 4 Alkoxycarbonyl, C 1 -C 4 Alkylaminothio or di(C 1 -C 4 or unsubstituted or further substituted by 1 to 5 of the following groups (hetero)arylcarbonylC 1 -C 4 Alkyl, (hetero)arylcarbonyl, (hetero)aryloxycarbonyl, (hetero)arylC 1 -C 4 Alkyloxycarbonyl, (hetero)arylC 1 -C 4 Alkyl: halogen, nitro, cyano, C 1 -C 4 Alkyl, halogenated C 1 -C 4 Alkyl, C 1 -C 4 Alkoxy or halogenated C 1 -C4 One of the alkoxy groups;

[0020] Furthermore, the structure of the pyrimidine part in the compound represented by general formula I is T 1 、T 2 、T 3 、T 4 、T 5 or T 6 ,as follows:

[0021]

[0022] R 1 , R 2 and W are the same as above. The structure of the pyrimidine part is T 1 When, it is the structure shown in general formula I.

[0023] X is selected from NR 3 ; R 3 Same as above.

[0024] m is selected from an integer from 0 to 3, and when m is selected from 2 or 3, X cannot be O;

[0025] R 4 Selected from hydrogen, halogen or C 1 -C 4 One of the alkyl groups;

[0026] R 5 Selected from hydrogen, halogen, carboxyl, C 1 -C 4 Alkyl, C 1 -C 4 Alkoxy or C 1 -C 4 Alkoxy C 1 -C 4 One of the alkoxy groups;

[0027] R 6 Selected from hydrogen, halogen, nitro, C 1 -C 4 Alkyl, C 1 -C 4 Alkoxy or C 1 -C 4 Alkoxy C 1 -C 4 One of the alkoxy groups;

[0028] R 7 One selected from hydrogen or halogen;

[0029] R 8 Selected from hydrogen, halogen, carboxyl, C 1 -C 4 Alkyl or C1 -C 4 One of the alkoxycarbonyl groups;

[0030] R 9 Selected from hydrogen, halogen or C 1 -C 4 One of the alkyl groups;

[0031] R 10 One selected from hydrogen or halogen;

[0032] R 11 One selected from hydrogen, halogen or carboxyl;

[0033] R 12 Selected from hydrogen or C 1 -C 4 One of the alkyl groups;

[0034] R 13 Selected from hydrogen, halogen or C 1 -C 4 One of the alkyl groups;

[0035] R 14 Selected from hydrogen, C 1 -C 4 Alkyl, carboxyl C 1 -C 4 Alkyl or 1-pyrrolidinyl C 1 -C 4 One of the alkyl groups;

[0036] R 15 Selected from hydrogen, halogen or C 1 -C 4 One of the alkyl groups.

[0037] Furthermore, in the compound represented by general formula I:

[0038] R 1 is selected from hydrogen, fluorine, chlorine, bromine, iodine, cyano, nitro, amino, carboxyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, monofluoromethyl, monochloromethyl, difluoromethyl, trifluoromethyl, trifluoroethyl, methoxymethyl, ethoxymethyl or trifluoroethoxymethyl;

[0039] R 2 is selected from hydrogen, fluorine, chlorine, bromine, iodine, cyano, nitro, amino, carboxyl, formyl, methyl, ethyl, methoxy, ethoxy, trifluoroethoxy or p-bromophenyl;

[0040] W is selected from hydrogen, fluorine, chlorine, bromine, iodine, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, monofluoromethyl, monochloromethyl, difluoromethyl, trifluoromethyl, trifluoroethyl, methoxy, ethoxy, methylthio, ethylthio, methylsulfonyl or ethylsulfonyl;

[0041] R 3 is selected from hydrogen, hydroxy, formyl, acetyl, propionyl, butyryl, trifluoroacetyl, benzoyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, trifluoromethyl, trifluoroethyl, methoxy, ethoxy, trifluoroethoxy, cyclopropyloxy, methylthio, ethylthio, allyl, propargyl, methylsulfonyl, ethylsulfonyl, trifluoroethylsulfonyl, methylaminosulfonyl, ethylaminosulfonyl, dimethylaminosulfonyl, diethylaminosulfonyl, methylsulfonylaminocarbonyl, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, methylaminocarbonyl, dimethylaminocarbonyl, vinyloxycarbonyl, ethynyloxycarbonyl, methylaminothio, ethylaminothio or dimethylaminothio;

[0042] R 4 is selected from hydrogen, fluorine, chlorine, bromine, iodine, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl or tert-butyl;

[0043] R 5 is selected from hydrogen, fluorine, chlorine, bromine, iodine, carboxyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy, methoxymethoxy, methoxyethoxy, ethoxymethoxy or ethoxyethoxy;

[0044] R 6 is selected from hydrogen, fluorine, chlorine, bromine, iodine, nitro, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy, methoxymethoxy, methoxyethoxy, ethoxymethoxy or ethoxyethoxy;

[0045] R 7 is selected from hydrogen, fluorine, chlorine, bromine or iodine;

[0046] R 8 is selected from hydrogen, fluorine, chlorine, bromine, iodine, carboxyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, methoxycarbonyl, ethoxycarbonyl or propoxycarbonyl;

[0047] R 9 is selected from hydrogen, fluorine, chlorine, bromine, iodine, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl or tert-butyl;

[0048] R 10 is selected from hydrogen, fluorine, chlorine, bromine or iodine;

[0049] R 11 is selected from hydrogen, fluorine, chlorine, bromine, iodine or carboxyl;

[0050] R 12 is selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl or tert-butyl;

[0051] R 13 is selected from hydrogen, fluorine, chlorine, bromine, iodine, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl or tert-butyl;

[0052] R 14 is selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, carboxymethylene, carboxyethyl, 1-pyrrolidinylmethyl or 1-pyrrolidinylethyl;

[0053] R 15 is selected from hydrogen, fluorine, chlorine, bromine, iodine, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl or tert-butyl.

[0054] Furthermore, in the compound represented by general formula I:

[0055] R 1 is selected from chloro, methyl, ethyl or difluoromethyl;

[0056] R 2 is selected from hydrogen, chlorine, bromine, methyl, methoxy or p-bromophenyl;

[0057] W is selected from hydrogen, fluorine, chlorine, methyl or methylsulfonyl;

[0058] m is an integer selected from 1 to 3;

[0059] R 3 is selected from hydrogen or methyl;

[0060] R 4 Selected from hydrogen;

[0061] R 5 is selected from hydrogen or chlorine;

[0062] R 6 is selected from hydrogen or bromine;

[0063] R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R14 , R 15 are selected from hydrogen.

[0064] The present invention also provides a method for preparing a pyrimidine-containing propene ether compound, comprising the following steps:

[0065] Intermediate II and intermediate III react in a solvent under alkaline conditions to obtain a compound of formula I;

[0066]

[0067] The reaction temperature is any temperature from room temperature to the boiling point of the solvent;

[0068] The reaction time is 30 minutes to 20 hours.

[0069] Further, the molar ratio of the intermediate II to the intermediate III is 1:1;

[0070] The base used in the reaction is potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, triethylamine, pyridine, sodium methoxide, sodium ethoxide, sodium hydride, potassium tert-butoxide or sodium tert-butoxide;

[0071] The solvent is tetrahydrofuran, 1,4-dioxane, acetonitrile, toluene, xylene, benzene, N,N-dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide, acetone or butanone;

[0072] The reaction temperature is 20-100°C;

[0073] The reaction time is 1-10 hours.

[0074] The present invention also provides the use of pyrimidine-containing propene ether compounds in the preparation of fungicides or insecticides and acaricides.

[0075] The compounds of the present invention can be applied in the form of preparations. The compounds shown in general formula I are dissolved or dispersed in a carrier as active ingredients or formulated into preparations so as to be more easily dispersed when used as bactericides or insecticides. For example, these chemical preparations can be made into wettable powders, oil suspensions, water suspensions, aqueous emulsions, aqueous solutions or emulsifiable concentrates. In these preparations, at least one liquid or solid carrier is added, and when necessary, a suitable surfactant can be added.

[0076] Furthermore, the bactericide or insecticide acaricide contains pyrimidine-containing propylene ether compounds as active components, and the weight percentage of the active components in the bactericide or insecticide acaricide is 0.1-99%. The bactericide or insecticide acaricide also contains agricultural, forestry and hygienic acceptable carriers.

[0077] Furthermore, the fungicide is a drug for preventing and treating oomycete diseases, deuteromycete diseases, basidiomycete diseases and ascomycete diseases.

[0078] Furthermore, the insecticide and acaricide drug is a drug for preventing and controlling pests of the orders Coleoptera, Dermoptera, Neuroptera, Diptera, Hemiptera, Homoptera and Lepidoptera.

[0079] The method of using the fungicide of the present invention to prevent and control pathogens, insect pests and mites is as follows: the fungicide of the present invention having the functions of killing bacteria, insects and mites is applied to the pathogens or their growth medium. The effective amount is usually 10 to 1000 grams per hectare, and the preferred effective amount is 20 to 500 grams per hectare.

[0080] For certain applications, such as in agriculture, one or more other fungicides, insecticides, acaricides, herbicides, plant growth regulators or fertilizers may be added to the fungicide of the present invention, thereby producing additional advantages and effects.

[0081] The use of the pyrimidine-containing propene ether compound of general formula I of the present invention for preparing fungicides, insecticides and acaricides in agriculture or other fields includes but is not limited to the following:

[0082] It can be used to prevent and control the following diseases: Oomycete diseases, such as downy mildew (cucumber downy mildew, rape downy mildew, soybean downy mildew), white rust (rapeseed white rust, cabbage white rust), late blight (potato late blight, tomato late blight), etc.; Deuteromycete diseases, such as wilt (tomato wilt, bean wilt, cucumber wilt), root rot (pepper root rot, eggplant root rot, bean root rot, cucumber root rot, bitter melon root rot, cotton black root rot, broad bean root rot), damping-off (cotton seedling damping-off, sesame damping-off, pepper damping-off, cucumber damping-off, cabbage damping-off), anthracnose (cucumber anthracnose, bitter melon anthracnose, zucchini anthracnose Anthracnose, wax gourd anthracnose, watermelon anthracnose, melon anthracnose, litchi anthracnose), gray mold (cotton boll gray mold, hemp gray mold, tomato gray mold), etc.; basidiomycete diseases, such as rust (wheat stripe rust, wheat stem rust, wheat leaf rust, flower rust, sunflower rust, sugarcane rust, soybean rust), etc.; ascomycete diseases, such as powdery mildew (wheat powdery mildew, rape powdery mildew, sesame powdery mildew), sclerotinia (soybean sclerotinia, peanut sclerotinia, tobacco sclerotinia, pepper sclerotinia, eggplant sclerotinia, bean sclerotinia, pea sclerotinia, cucumber sclerotinia, bitter melon sclerotinia), scab (apple scab, pear scab), etc.

[0083] The compounds shown in general formula I can be used to control the following pests:

[0084] Coleoptera (Beetles): Acanthoscelides spp. (Weevils), Acanthoscelides obtectus (Common Pea Weevils), Agrilus planipennis (Willow Ash Borer), Agriotes spp. (Wireworms), Anoplophora glabripennis (Asian Longhorn Beetle), Anthonomus spp. (Curculidae), Anthonomus grandis (Cotton Bollworm), Aphidius spp., Apion spp. (Weevils), Apogonia spp. (Grubs), Atacnius sprctulus (Black Velvet Beetle), Atomaria linearis) (pygmy mangold beetle), etc.

[0085] Dermaptcra (earwigs).

[0086] Dictyoptera (cockroaches): Blattella germanica (German cockroach), Blatta orientalis (Oriental cockroach), Parcoblatta pennylvanica)), etc.

[0087] Diptera (flies): Aedes spp. (mosquitoes), Agromyzafrontella (alfalfa blotch leafminer), Agromyza spp. (leaf miner), Anastrepha spp. (fruit flies), Anastrephasuspensa (Caribbean fruit fly), Anopheless spp. (mosquitoes), Batrocera spp. (fruit flies), etc.

[0088] Hemiptera (stink bugs): Acrosternum hilare (green stink bug), Blissus leucopterus (chinch bug), Calocoris norvegicus (potato mirid), Cimex hemipterus (tropical bed bug), Cimex lectularius (bed hug), Hesperus, etc.

[0089] Homoptera (aphids, scale flies, whiteflies, leafhoppers): Acrythosiphonpisum (pea aphid), Adelges spp. (adelgids), Aleurodesproletella (cabbage whitefly), Aleurodicus disperses, Aleurothrixusflccosus (woolly whitefly), Aluacaspis spp., etc.

[0090] Lepidoptera (moths and butterflies): Achoeajanata, Adoxophyes spp., Adoxophyes orana, Agrotis spp. (cutworms), Agrotis ipsilon (black cutworm), Alabama argillacea (cotton leafworm), Amorbiacuneana, Amyelosis transitella (navel orangeworm), Anacamptodes defectaria, Anarsia lineatella (peach twigborer), tobacco coindicate, etc.

[0091] The pyrimidine-containing propene ether compounds can be advantageously used to protect important crops, livestock and breeding stock in agriculture and horticulture, as well as to protect environments frequented by humans from damage by pathogens, insect pests and mites.

[0092] To achieve the desired effect, the amount of pyrimidine-containing propene ether compounds varies depending on various factors, such as the compound used, the crop to be protected, the type of pest, the degree of infection, climatic conditions, the method of application, and the formulation used. The amount of pyrimidine-containing propene ether compounds used is 10 grams to 1 kilogram of compound per hectare, which can provide sufficient control.

[0093] In the above terms, halogen refers to fluorine, chlorine, bromine or iodine. Nitro: -NO 2 . Cyano group: -CN. Sulfonic acid group: -SO 3 H. Trihalomethyl: -CX 3 , X=F, Cl. Formyl: -CHO. . Carboxyl: -COOH. Alkyl: straight chain or branched alkyl, such as methyl, ethyl, propyl, isopropyl, n-butyl or tert-butyl. Cycloalkyl: substituted or unsubstituted cyclic alkyl, such as cyclopropyl, cyclopentyl or cyclohexyl. Haloalkyl: straight chain or branched alkyl, the hydrogen atoms on these alkyl can be partially or completely replaced by halogen atoms, for example, chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, etc. Alkylsulfinyl: straight chain or branched alkyl is connected to the structure through a sulfinyl group (-SO-), such as methylsulfinyl. Haloalkylsulfinyl: straight chain or branched alkylsulfinyl, the hydrogen atoms on its alkyl can be partially or completely replaced by halogen atoms. The aryl moiety in (hetero)aryl, (hetero)arylalkyl, (hetero)arylcarbonyl, (hetero)arylmethylcarbonyl, (hetero)arylcarbonylalkyl, (hetero)aryloxycarbonyl, (hetero)arylalkyloxycarbonyl includes phenyl or naphthyl, etc. Heteroaryl is a five-membered ring or a six-membered ring containing one or more N heteroatoms, such as pyridyl, pyrimidinyl, pyrazinone, pyridazinyl, triazinyl, etc. (hetero)aryl: such as phenyl, etc.

[0094] When X is selected from NR 3 The following table 1 lists some R 3 substituted groups.

[0095] Table 1 The pyrimidine-containing propene ether compound shown in general formula I is as follows:

[0096]

[0097] In the above formula, X is selected from NR 3 , limit m = 1, R 3 =H, the structure of the pyrimidine part in the compound is different. 1 、T 2 、T 3 、T 4 、T 5 and T 6 The substituent R of the pyrimidine moiety is shown 1 , R2 , R 4 -R 15 , W are shown in Table 2, and the representative compound numbers are 2-1 to 2-132.

[0098] Table 2

[0099]

[0100]

[0101]

[0102]

[0103]

[0104]

[0105]

[0106]

[0107] Table 3: In general formula I, when m=1, R 3 =CH 3 When the substituent R 1 , R 2 , R 4 -R 15 , W are consistent with Table 2, corresponding to 2-1 to 2-132 in Table 2, and the representative compound numbers are 3-1 to 3-132.

[0108] Table 4: In general formula I, when m=2, R 3 =H, the substituent R 1 , R 2 , R 4 -R 15 , W are consistent with Table 2, corresponding to 2-1 to 2-132 in Table 2, and the representative compound numbers are 4-1 to 4-132.

[0109] Table 5: In general formula I, when m=2, R 3 =CH 3 When the substituent R 1 , R 2 , R 4 -R 15 , W are consistent with Table 2, corresponding to 2-1 to 2-132 in Table 2, and the representative compound numbers are 5-1 to 5-132.

[0110] Table 6: In general formula I, when m=3, R 3 =H, the substituent R 1, R 2 , R 4 -R 15 , W are consistent with Table 2, corresponding to 2-1 to 2-132 in Table 2, and the representative compound numbers are 6-1 to 6-132.

[0111] Table 7: In general formula I, when m=3, R 3 =CH 3 When the substituent R 1 , R 2 , R 4 -R 15 , W are consistent with Table 2, corresponding to 2-1 to 2-132 in Table 2, and the representative compound numbers are 7-1 to 7-132.

[0112] The pyrimidine-containing propene ether compound of the present invention is prepared according to the following method, and the reaction formula is as follows, wherein the groups in the formula have the same definitions as above unless otherwise specified:

[0113]

[0114] Intermediate II and intermediate III react under basic conditions in a suitable solvent to obtain a compound of formula I.

[0115] Suitable bases can be selected from potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, triethylamine, pyridine, sodium methoxide, sodium ethoxide, sodium hydride, potassium tert-butoxide or sodium tert-butoxide, etc.

[0116] The reaction is carried out in a suitable solvent, which can be selected from tetrahydrofuran, 1,4-dioxane, acetonitrile, toluene, xylene, benzene, N,N-dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide, acetone or butanone.

[0117] The reaction temperature may be between room temperature and the boiling point of the solvent, usually 20-100°C.

[0118] The reaction time is from 30 minutes to 20 hours, usually from 1 to 10 hours.

[0119] Part of the intermediate II is commercially available or can be prepared by known methods, for example, by the methods described in JP2000007662A, US4977264A, US6090815A, US20040092402A1, JP09124613A, US5468751A, US4985426A, US4845097A, Journal of the American Chemical Society (1957), 79, 1455, Journal of Chemical Society (1955), p. 3478-3481.

[0120] The compound represented by intermediate III can be prepared by known methods, for details, see CN1860874A, US20030073847A1 and WO9727173A2.

[0121] Compared with the prior art, the present invention has the following technical effects:

[0122] The compounds of general formula I show excellent activity against a variety of pathogens in agriculture or other fields, and several of them have a higher protective effect against wheat powdery mildew than the commercial pesticide propiconazole. In addition, they also show good activity against pests and mites. DETAILED DESCRIPTION

[0123] The present invention is further described below in conjunction with specific implementation modes.

[0124] The following is the synthesis of the intermediate:

[0125] 1. Synthesis of intermediate 4,5-dichloro-6-methylpyrimidine (one of intermediates II)

[0126] 1) Preparation of 4-hydroxy-5-chloro-6-methylpyrimidine

[0127]

[0128] Under stirring at room temperature, slowly add 8.80g (0.16mol) of sodium methoxide in methanol solution to 11.30g (0.11mol) of formamidine acetate in 50mL of methanol solution, and continue stirring at room temperature for 2h. Then add 11.17g (0.068mol) of the intermediate ethyl 2-chloroacetoacetate to the above solution, and continue stirring at room temperature for 5-7h. After the reaction is completed by TLC monitoring, the solvent is evaporated under reduced pressure, the pH is adjusted to 5-6 with hydrochloric acid, and an orange-yellow solid is obtained by suction filtration. The aqueous phase is extracted with (3×50mL) of ethyl acetate, dried over anhydrous magnesium sulfate, filtered, and desolventized. The residue is dissolved in 50mL of ethyl acetate, left overnight, and filtered to obtain 6.48g of an orange-yellow solid. The yield is 66.00%, and the melting point is 181-184°C.

[0129] 2) Preparation of 4,5-dichloro-6-methylpyrimidine

[0130]

[0131] Dissolve 14.5g (0.1mol) 4-hydroxy-5-chloro-6-methylpyrimidine in 50ml toluene solution, add 50mL phosphorus oxychloride to the reaction bottle under stirring, and heat and reflux for 5-7h. After the reaction is completed, the toluene and excess phosphorus oxychloride are evaporated under reduced pressure, and the reactant is poured into ice water under stirring. The aqueous phase is extracted with (3×50mL) ethyl acetate, and the organic phases are combined, dried over anhydrous magnesium sulfate, filtered, and desolventized. The residue is separated by column chromatography (eluent is ethyl acetate and petroleum ether, volume ratio is 1:5) to obtain 14.43g of yellow liquid, with a yield of 88.50%.

[0132] 2. Synthesis of intermediate 4-chloroquinazoline (one of intermediates II)

[0133] 1) Preparation of quinazolin-4(3H)-one

[0134]

[0135] 13.7 g (0.1 mol) of anthranilic acid and 20 mL of formamide were placed in a 250 mL three-necked flask, heated to 140 °C and reacted for 5-8 h. After the reaction was completed as monitored by TLC, the reaction solution was cooled to 100 °C, 80 mL of water was added dropwise under stirring, and then cooled to room temperature, filtered, and the filter cake was washed with anhydrous ether to obtain 10.96 g of reddish brown, with a yield of 75.10%.

[0136] 2) Preparation of 4-chloroquinazoline

[0137]

[0138] Take 14.6g (0.1mol) of quinazoline-4(3H)-one in a 250mL single-mouth bottle, add 50mL of thionyl chloride as solvent, and heat to reflux for 4-6h. After the reaction is completed, monitor by TLC, cool the reaction solution, pour it into water, stir for 30min, filter and wash with anhydrous ether to obtain 10.96g of red-brown solid, with a yield of 92.70%.

[0139] 3. Synthesis of intermediate 2-(2,6-dichloro-4-((3,3-dichloroallyl)oxy)phenoxy)ethane-1-amine hydrochloride (one of intermediates III)

[0140] 1) Preparation of N-Boc-2-bromoethylamine

[0141]

[0142] 20.5g (0.1mol) of bromoethylamine bromide was placed in 80mL of tetrahydrofuran, and 10.08g (0.12mol) of sodium bicarbonate and 50mL of water were added in sequence. 21.80g (0.1mol) of di-tert-butyl dicarbonate was added dropwise under stirring at room temperature. After the addition was completed, the reaction was continued for 4-10h. After the reaction was completed, the solvent was evaporated under reduced pressure, and (3×50mL) of ethyl acetate was added for extraction. The organic phase was washed with 50mL of saturated brine, and 21.84g of colorless oily liquid was obtained after solvent removal, with a yield of 97.50%.

[0143] 2) Preparation of 2,6-dichloro-4-((3,3-dichloroallyl)oxy)phenol

[0144]

[0145] To a 30 mL toluene solution of 4.10 g (0.019 mol) 4-(3,3-dichloroallyloxy)phenol, 4 drops (0.1 mL) of dibutylamine were added, and a 2-fold (mol) toluene solution of sulfonyl chloride was slowly added dropwise at 65-70°C for about 2 h. The reaction was continued for 1-2 h. After the reaction was completed as monitored by TLC, a saturated sodium bicarbonate solution was added, the toluene layer was separated, the aqueous layer was extracted with toluene, the organic layers were combined, dried, desolventized, and column chromatography was performed to obtain 4.50 g of the intermediate with a yield of 83.80%.

[0146] 3) Preparation of tert-butyl (2-(2,6-dichloro-4-((3,3-dichloroallyl)oxy)phenoxy)ethyl)carbamate

[0147]

[0148] 2.24 g (0.01 mol) of N-Boc-2-bromoethylamine and 2.88 g (0.01 mol) of 2,6-dichloro-4-((3,3-dichloroallyl)oxy)phenol were added to 50 mL of DMF, and 1.66 g (0.012 mol) of potassium carbonate was added. The mixture was heated to 90°C and reacted for 4-10 h. After the reaction was completed as monitored by TLC, the solvent was evaporated under reduced pressure, and (3×50 mL) of ethyl acetate was added for extraction. The organic phase was washed with 50 mL of saturated brine. After desolventization, the residue was subjected to column chromatography (the eluent was ethyl acetate and petroleum ether, in a volume ratio of 1:6) to obtain 3.65 g of a yellow solid with a yield of 84.70%.

[0149] 4) Preparation of 2-(2,6-dichloro-4-((3,3-dichloroallyl)oxy)phenoxy)ethane-1-amine hydrochloride

[0150] 2.16 g (0.005 mol) of tert-butyl (2-(2,6-dichloro-4-((3,3-dichloroallyl)oxy)phenoxy)ethyl)carbamate was added to 50 mL of ethyl acetate, and 6 mL of concentrated hydrochloric acid was added dropwise under stirring at room temperature to dissolve the solid. The mixture was stirred for 4-5 h. After the reaction was completed as monitored by TLC, the solvent was evaporated under reduced pressure, 10 mL of dichloromethane was added, and the mixture was stirred for 0.5 h. The mixture was filtered, and the filter cake was washed with dichloromethane to obtain 1.42 g of a white solid with a yield of 77.20%.

[0151] 4. Synthesis of 3-(2,6-dichloro-4-((3,3-dichloroallyl)oxy)phenoxy)propane-1-amine hydrochloride (one of the intermediates III)

[0152] 1) Preparation of N-Boc-3-bromopropylamine

[0153]

[0154] 21.9g (0.1mol) of bromopropylamine bromide was placed in 80mL of tetrahydrofuran, and 10.08g (0.12mol) of sodium bicarbonate and 50ml of water were added in sequence. 21.80g (0.1mol) of di-tert-butyl dicarbonate was added dropwise under stirring at room temperature. After the addition was completed, the reaction was continued for 4-10h. After the reaction was completed, the solvent was evaporated under reduced pressure, and (3×50mL) of ethyl acetate was added for extraction. The organic phase was washed with 50mL of saturated brine, and 19.60g of colorless oily liquid was obtained after solvent removal, with a yield of 82.40%.

[0155] 2) Preparation of tert-butyl (3-(2,6-dichloro-4-((3,3-dichloroallyl)oxy)phenoxy)propyl)carbamate

[0156]

[0157] 2.38 g (0.01 mol) of N-Boc-3-bromopropylamine and 2.88 g (0.01 mol) of 2,6-dichloro-4-((3,3-dichloroallyl)oxy)phenol were added to 50 mL of DMF, and 1.66 g (0.012 mol) of potassium carbonate was added. The mixture was heated to 90° C. and reacted for 4-10 h. After the reaction was completed as monitored by TLC, the solvent was evaporated under reduced pressure, and (3×50 mL) of ethyl acetate was added for extraction. The organic phase was washed with 50 mL of saturated brine. After solvent removal, the residue was subjected to column chromatography (the eluent was ethyl acetate and petroleum ether, in a volume ratio of 1:6) to obtain 3.82 g of a yellow solid with a yield of 85.80%.

[0158] 3) Preparation of 3-(2,6-dichloro-4-((3,3-dichloroallyl)oxy)phenoxy)propane-1-amine hydrochloride

[0159] 2.23 g (0.005 mol) of tert-butyl (3-(2,6-dichloro-4-((3,3-dichloroallyl)oxy)phenoxy)propyl)carbamate was added to 50 mL of ethyl acetate, and 6 mL of concentrated hydrochloric acid was added dropwise under stirring at room temperature until the solid dissolved. The mixture was stirred for 4-5 h. After the reaction was completed as monitored by TLC, the solvent was evaporated under reduced pressure, 10 mL of dichloromethane was added, and the mixture was stirred for 0.5 h. The mixture was filtered, and the filter cake was washed with dichloromethane to obtain 1.36 g of a yellow solid with a yield of 71.20%.

[0160] 5. Synthesis of 4-(2,6-dichloro-4-((3,3-dichloroallyl)oxy)phenoxy)butane-1-amine hydrochloride (one of the intermediates III)

[0161] 1) Preparation of N-Boc-4-bromobutylamine

[0162]

[0163] 23.3g (0.1mol) of bromobutylamine bromide was placed in 80mL of tetrahydrofuran, and 10.08g (0.12mol) of sodium bicarbonate and 50mL of water were added in sequence. 21.80g (0.1mol) of di-tert-butyl dicarbonate was added dropwise under stirring at room temperature. After the addition was completed, the reaction was continued for 4-10h. After the reaction was completed, the solvent was evaporated under reduced pressure, and (3×50mL) of ethyl acetate was added for extraction. The organic phase was washed with 50mL of saturated brine, and 21.50g of colorless oily liquid was obtained after solvent removal, with a yield of 85.30%.

[0164] 2) Preparation of tert-butyl (4-(2,6-dichloro-4-((3,3-dichloroallyl)oxy)phenoxy)butyl)carbamate

[0165]

[0166] 2.52 g (0.01 mol) of N-Boc-4-bromobutylamine and 2.88 g (0.01 mol) of 2,6-dichloro-4-((3,3-dichloroallyl)oxy)phenol were added to 50 mL of DMF, and 1.66 g (0.012 mol) of potassium carbonate was added. The mixture was heated to 90°C and reacted for 4-10 h. After the reaction was completed as monitored by TLC, the solvent was evaporated under reduced pressure, and (3×50 mL) of ethyl acetate was added for extraction. The organic phase was washed with 50 mL of saturated brine, and the residue after solvent removal was subjected to column chromatography (the eluent was ethyl acetate and petroleum ether, in a volume ratio of 1:6) to obtain 4.01 g of a yellow solid with a yield of 87.40%.

[0167] 3) Preparation of 4-(2,6-dichloro-4-((3,3-dichloroallyl)oxy)phenoxy)butane-1-amine hydrochloride

[0168] 2.30 g (0.005 mol) of tert-butyl (3-(2,6-dichloro-4-((3,3-dichloroallyl)oxy)phenoxy)propyl)carbamate was added to 50 mL of ethyl acetate, and 6 mL of concentrated hydrochloric acid was added dropwise under stirring at room temperature until the solid dissolved. The mixture was stirred for 4-5 h. After the reaction was completed as monitored by TLC, the solvent was evaporated under reduced pressure, 10 mL of dichloromethane was added, and the mixture was stirred for 0.5 h. The mixture was filtered, and the filter cake was washed with dichloromethane to obtain 1.52 g of a light yellow solid with a yield of 76.90%.

[0169] The following is an example of the preparation of the pyrimidine-containing propene ether compound of the present invention:

[0170] Example 1 Preparation of Compound 2-49

[0171]

[0172] 0.37 g (1.0 mmol) of 2-(2,6-dichloro-4-((3,3-dichloroallyl)oxy)phenoxy)ethane-1-amine hydrochloride and 0.17 g (1.2 mmol) of potassium carbonate were added to 20 mL of DMF, and then 0.16 g (1.0 mmol) of 4,5-dichloro-6-methylpyrimidine was added thereto, and the reaction mixture was heated to 90°C for 4 hours. After the reaction was completed by TLC monitoring, the reaction mixture was added to water and extracted with ethyl acetate, the organic phase was washed with water and saturated brine in turn, dried, filtered, and desolventized under reduced pressure, and the residue was purified by column chromatography (eluent was ethyl acetate and petroleum ether (boiling range 60-90°C), volume ratio was 1:5), and 0.37 g of yellow solid was obtained, with a yield of 80.40% and a melting point of 90.5°C.

[0173] The NMR data of the product are as follows: 1 H-NMR (600 MHz, internal standard TMS, solvent CDCl 3 )δ(ppm):8.37(s,1H,pyrimidyl-H),6.85(s,2H,Ph-2H),6.17(s,1H,NH),6.11(t,J=6.3Hz,1H,CHCH 2 ),4.59(d,J=6.3Hz,2H,CHCH 2 ),4.18(t,J=4.9Hz,2H,OCH 2 ),3.93(dd,J=10.0,5.3Hz,2H,CH 2 NH),2.48(s,3H,CH 3 ).

[0174] Example 2: Preparation of Compound 2-62

[0175]

[0176] 0.37 g (1.0 mmol) of 2-(2,6-dichloro-4-((3,3-dichloroallyl)oxy)phenoxy)ethane-1-amine hydrochloride and 0.17 g (1.2 mmol) of potassium carbonate were added to 20 mL of DMF, and then 0.16 g (1.0 mmol) of 4-chloroquinazoline was added thereto, and the reaction mixture was heated to 90°C for 4 h. After the reaction was completed as monitored by TLC, the reaction mixture was added to water and extracted with ethyl acetate. The organic phase was washed with water and saturated brine in turn, dried, filtered, and desolventized under reduced pressure. The residue was purified by column chromatography (eluent was ethyl acetate and petroleum ether (boiling range 60-90°C), volume ratio was 1:4), and 0.34 g of white solid was obtained, with a yield of 74.10% and a melting point of 138.5°C.

[0177] The NMR data of the product are as follows: 1 H-NMR (600 MHz, internal standard TMS, solvent CDCl 3 )δ(ppm):8.67(s,1H,pyrimidyl-H),7.86(d,J=8.3Hz,1H,quinazolinyl-8-H),7.82–7.71(m,2H,quinazolinyl-5,7- 2H),7.51(dd,J=11.2,4.0Hz,1H,quinazolinyl-6-H),6.86(s,2H,Ph-2H),6.54(s,1H,NH),6.11(t,J=6.3Hz,1H,CHCH 2 ),4.59(d,J=6.3Hz,2H,CHCH 2 ),4.28(t,J=4.8Hz,2H,OCH 2 ),4.11(dd,J=9.9,5.2Hz,2H,CH 2 NH).

[0178] Example 3: Preparation of Compound 4-49

[0179]

[0180] 0.38g (1.0mmol) of 3-(2,6-dichloro-4-((3,3-dichloroallyl)oxy)phenoxy)propane-1-amine hydrochloride and 0.17g (1.2mmol) of potassium carbonate were added to 20mL DMF, and then 0.16g (1.0mmol) of 4,5-dichloro-6-methylpyrimidine was added thereto, and the reaction mixture was heated to 90°C for 4h. After the reaction was completed by TLC monitoring, the reaction mixture was added to water and extracted with ethyl acetate, the organic phase was washed with water and saturated brine in turn, dried, filtered, and desolventized under reduced pressure, and the residue was purified by column chromatography (eluent was ethyl acetate and petroleum ether (boiling range 60-90°C), volume ratio was 1:5), and 0.40g of brown solid was obtained, with a yield of 85.10% and a melting point of 84.9°C.

[0181] The NMR data of the product are as follows: 1 H-NMR (600 MHz, internal standard TMS, solvent CDCl 3 )δ(ppm):8.36(s,1H,pyrimidyl-2-H),6.84(s,2H,Ph-2H),6.10(t,J=6.2Hz,1H,CHCH 2 ),5.98(t,J=4.8Hz,1H,NH),4.57(d,J=6.3Hz,2H,CHCH 2 ),4.06(t,J=5.6Hz,2H,OCH 2 ),3.82(dd,J=12.3,6.2Hz,2H,CH 2 NH), 2.43(d, J=1.8Hz, CH 3 ),2.18–2.08(m,2H,OCH 2 CH 2 ).

[0182] Example 4: Preparation of Compound 4-62

[0183]

[0184] 0.38g (1.0mmol) of 3-(2,6-dichloro-4-((3,3-dichloroallyl)oxy)phenoxy)propane-1-amine hydrochloride and 0.17g (1.2mmol) of potassium carbonate were added to 20mL DMF, and then 0.16g (1.0mmol) of 4-chloroquinazoline was added thereto, and the reaction mixture was heated to 90°C for 4h. After the reaction was completed by TLC monitoring, the reaction mixture was added to water and extracted with ethyl acetate, the organic phase was washed with water and saturated brine in turn, dried, filtered, and desolventized under reduced pressure, and the residue was purified by column chromatography (eluent was ethyl acetate and petroleum ether (boiling range 60-90°C), volume ratio was 1:4), and 0.39g of white solid was obtained, with a yield of 82.50% and a melting point of 137.3°C.

[0185] The NMR data of the product are as follows: 1 H-NMR (600 MHz, internal standard TMS, solvent CDCl 3 )δ(ppm):8.66(s,1H,quinazolinyl-2-H),7.81(d,J=8.2Hz,1H,quinazolinyl-8-H),7.72–7.68(m,1H,quinazolinyl-7-H),7.67(d,J=8.2Hz, 1H,quinazolinyl-5-H),7.41(ddd,J=8.1,7.0,1.1Hz,1H,quinazolinyl-6-H),6.87(s,2H,Ph-2H),6.64(s,1H,NH),6.11(t,J=6.3Hz,1H,CHCH 2 ),4.59(d,J=6.3Hz,2H,CHCH 2 ),4.18(dd,J=10.0,4.7Hz,2H,OCH 2 ),4.02–3.95(m,2H,CH 2 NH),2.24(dt,J=11.2,5.7Hz,2H,OCH 2 CH 2 ).

[0186] Example 5: Preparation of Compound 6-49

[0187]

[0188] 0.40g (1.0mmol) of 4-(2,6-dichloro-4-((3,3-dichloroallyl)oxy)phenoxy)butane-1-amine hydrochloride and 0.17g (1.2mmol) of potassium carbonate were added to 20mL DMF, and then 0.16g (1.0mmol) of 4,5-dichloro-6-methylpyrimidine was added thereto, and the reaction mixture was heated to 90°C for 4h. After the reaction was completed by TLC monitoring, the reaction mixture was added to water and extracted with ethyl acetate, the organic phase was washed with water and saturated brine in turn, dried, filtered, and desolventized under reduced pressure, and the residue was purified by column chromatography (eluent was ethyl acetate and petroleum ether (boiling range 60-90°C), volume ratio was 1:7) to obtain 0.42g of yellow solid, yield 85.70%, melting point 89.1°C.

[0189] The NMR data of the product are as follows: 1 H-NMR (600 MHz, internal standard TMS, solvent CDCl 3 )δ(ppm):8.36(s,1H,pyrimidyl-2-H),6.83(s,2H,Ph-2H),6.10(t,J=6.2Hz,1H,CHCH 2 ),5.51(s,1H,NH),4.57(d,J=6.2Hz,2H,CHCH 2 ),3.99(t,J=5.7Hz,2H,OCH 2 ),3.61(q,J=6.5Hz,2H,CH 2 NH),2.44(s,1H,CH 3 ),1.97–1.87(m,4H,CH 2 CH 2 ).

[0190] Example 6: Preparation of Compound 6-62

[0191]

[0192] 0.40g (1.0mmol) of 4-(2,6-dichloro-4-((3,3-dichloroallyl)oxy)phenoxy)butane-1-amine hydrochloride and 0.17g (1.2mmol) of potassium carbonate were added to 20mL DMF, and then 0.16g (1.0mmol) of 4-chloroquinazoline was added thereto, and the reaction mixture was heated to 90°C for 4h. After the reaction was completed by TLC monitoring, the reaction mixture was added to water and extracted with ethyl acetate, the organic phase was washed with water and saturated brine in turn, dried, filtered, and desolventized under reduced pressure, and the residue was purified by column chromatography (eluent was ethyl acetate and petroleum ether (boiling range 60-90°C), volume ratio was 1:3) to obtain 0.41g of white solid, yield 84.20%, melting point 143°C.

[0193] The NMR data of the product are as follows: 1 H-NMR (600 MHz, internal standard TMS, solvent CDCl 3 )δ(ppm):8.66(s,1H,quinazolinyl-2-H),7.82(d,J=8.2Hz,1H,quinazolinyl-8-H),7.73–7.70(m,1H,quinazolinyl-7-H), 7.69(d,J=8.8Hz,1H,quinazolinyl-5-H),7.44–7.38(m,1H,quinazolinyl-6-H),6.84(s,2H,Ph-2H),6.10(t,J=6.2Hz,CHCH 2 ),6.02(s,1H,NH),4.58(d,J=6.2Hz,2H,CHCH 2 ),4.04(t,J=5.8Hz,2H,OCH 2 ),3.78(dd,J=12.4,6.7Hz,2H,CH 2 NH), 2.08–2.01(m,2H,OCH 2 CH 2 ),1.97(ddd,J=9.6,9.2,3.3Hz,CH 2 CH 2 NH).

[0194] Example 7: Preparation of Compound 3-52

[0195]

[0196] 0.49 g (1.0 mmol) of compound 3 and 0.12 g (1.0 mmol) of iodomethane were added to 20 mL of DMF, stirred at room temperature for 5 min, and then 0.03 g (1.2 mmol) of sodium hydride was added to the reaction solution, and the reaction was continued for 4 h. After the reaction was completed by TLC monitoring, the reaction mixture was added to water and extracted with ethyl acetate. The organic phase was washed with water and saturated brine in turn, dried, filtered, and desolventized under reduced pressure. The residue was purified by column chromatography (eluent was ethyl acetate and petroleum ether (boiling range 60-90° C.), and the volume ratio was 1:6) to obtain 0.45 g of a yellow oil with a yield of 88.20%.

[0197] The NMR data of the product are as follows: 1 H-NMR (600 MHz, internal standard TMS, solvent CDCl 3)δ(ppm):8.53(s,1H,pyrimidyl-2-H),6.84(t,J=53.8Hz,1H,CHF 2 ),6.83(s,2H,Ph-2H),6.10(t,J=6.3Hz,1H,CHCH 2 ),4.58(d,J=6.3Hz,2H,CHCH 2 ),4.25(dd,J=10.2,5.1Hz,2H,OCH 2 ),4.13(t,J=5.3Hz,2H,CH 2 NH),3.50(s,3H,NCH 3 ).

[0198] Other compounds of the present invention can be prepared by referring to the above examples. Physical properties and NMR data of some compounds ( 1 HNMR, 600 MHz, internal standard TMS, ppm) is as follows:

[0199] Compound 2-50: melting point 85.3°C. δ(CDCl 3 ):8.42(s,1H,pyrimidyl-H),6.85(s,2H,Ph-2H),6.17(s,1H,NH),6.11(t,J=6.3Hz,1H,CHCH 2 ),4.59(d,J=6.3Hz,2H,CHCH 2 ),4.18(t,J=4.9Hz,2H,OCH 2 ),3.93(dd,J=10.1,5.3Hz,2H,CH 2 NH), 2.81(q, J=7.6Hz,2H,CH 2 CH 3 ),1.27(t,J=7.6Hz,3H,CH 2 CH 3 ).

[0200] Compound 2-52: melting point 82.2°C. δ(CDCl 3 ):8.56(s,1H,pyrimidyl-H)),6.86(s,2H,Ph-2H),6.75(t,J=53.7Hz,1H,CHF 2 ),6.46(s,1H,NH),6.11(t,J=6.2Hz,1H,CHCH 2 ),4.60(d,J=6.3Hz,2H,CHCH 2 ),4.20(t,J=4.9Hz,2H,OCH 2),3.98(dd,J=10.1,5.1Hz,2H,CH 2 NH).

[0201] Compound 2-24: melting point 133.4°C. δ(CDCl 3 ):8.29(s,1H,pyrimidyl-H),6.86(s,2H,Ph-2H),6.11(t,J=6.3Hz,1H,CHCH 2 ),5.56(s,1H,NH),4.60(d,J=6.3Hz,2H,CHCH 2 ),4.19(dd,J=9.7,4.9Hz,2H,OCH 2 ),3.94(dd,J=9.8,5.3Hz,2H,CH 2 NH),2.20(s,3H,CH 3 ).

[0202] Compound 2-23: melting point 114.3°C. δ(CDCl 3 ):8.27(s,1H,pyrimidyl-H),6.84(s,2H,Ph-2H),6.33(s,1H,NH),6.10(t,J=6.2Hz,1H,CHCH 2 ),4.58(d,J=6.2Hz,2H,CHCH 2 ),4.16(t,J=4.6Hz,2H,OCH 2 ),3.94(dd,J=9.6,4.8Hz,2H,CH 2 NH).

[0203] Compound 2-22: melting point 102.1°C. δ(CDCl 3 ):8.29(s,1H,pyrimidyl-H),6.86(s,2H,Ph-2H),6.40(s,1H,NH),6.11(t,J=6.3Hz,1H,CHCH 2 ),4.59(d,J=6.3Hz,2H,CHCH 2 ),4.25–4.11(m,2H,OCH 2 ),3.94(dd,J=9.9,5.3Hz,2H,CH 2 NH).

[0204] Compound 2-26: melting point 131.3°C. δ(CDCl 3):8.14(s,1H,pyrimidyl-H),6.84(s,2H,Ph-2H),6.19(s,1H,NH),6.10(t,J=6.3Hz,1H,CHCH 2 ),4.58(d,J=6.2Hz,2H,CHCH 2 ),4.16(t,J=4.9Hz,2H,OCH 2 ),3.91–3.88(m,2H,CH 2 NH),3.88(s,1H,OCH 3 ).

[0205] Compound 2-29: melting point 154.7°C. δ(CDCl 3 ):8.40(s,1H,pyrimidyl-H),7.66(d,J=8.4Hz,2H,4-Br-Ph-3,5-2H),7.22(d,J=8.4Hz,2H,4-Br-Ph-2,6-2H),6.81(s,2H,Ph-2H),6.10(t,J=6.3Hz,1H,CHCH 2 ),5.44(d,J=4.7Hz,1H,NH),4.57(d,J=6.3Hz,2H,CHCH 2 ),4.07(t,J=4.8Hz,2H,OCH 2 ),3.83(dd,J=9.9,5.1Hz,2H,CH 2 NH).

[0206] Compound 2-15: melting point 137.4°C. δ(CDCl 3 ):8.25(s,1H,pyrimidyl-2-H),7.97(s,1H,pyrimidyl-5-H),7.10(s,2H,Ph-2H),6.57(s,1H,NH),6.44(t,J=6.6Hz,1H,CHCH 2 ),4.64(d,J=6.6Hz,2H,CHCH 2 ),3.99(t,J=5.4Hz,2H,OCH 2 ),3.70(s,2H,CH 2 NH).

[0207] Compound 2-17: melting point 119.8°C. δ(CDCl 3 ):6.84(s,2H,Ph-2H),6.24(s,1H,pyrimidyl-5-H),6.10(t,J=6.2Hz,1H,CHCH 2), 5.57 (s, 1H, NH), 4.57 (d, J = 6.3 Hz, 2H, CHCH 2 ), 4.13 (t, J = 4.9 Hz, 2H, OCH 2 ), 3.77 (s), 2.47 (s, 2H, CH 2 NH).

[0208] Compound 2 - 20: Melting point 115.3 °C. δ(CDCl 3 ): 8.30 (t, J = 5.8 Hz, 1H, NH), 7.13 (s, 2H, Ph - 2H), 6.90 (s, 1H, pyrimidyl - 5 - H), 6.47 (t, J = 6.6 Hz, 1H, CHCH 2 ), 4.68 (d, J = 6.6 Hz, 2H, CHCH 2 ), 4.05 (t, J = 5.8 Hz, 2H, OCH 2 ), 3.66 (q, J = 5.8 Hz, 2H, CH 2 NH), 3.33 (s, 3H, SO 2 CH 3 ).

[0209] Compound 2 - 21: Yellow oil. δ(CDCl 3 ): 6.86 (s, 2H, Ph - 2H), 6.51 (s, 1H, NH), 6.11 (t, J = 6.3 Hz, 1H, CHCH 2 ), 4.60 (d, J = 6.3 Hz, 2H, CHCH 2 ), 4.18 (dd, J = 9.6, 4.8 Hz, 2H, OCH 2 ), 3.95 (dd, J = 9.9, 5.2 Hz, 2H, CH 2 NH).

[0210] Compound 2 - 64: Yellow oil. δ(CDCl 3 ): 7.78 (d, J = 8.2 Hz, 1H, quinazolinyl - 8 - H), 7.75–7.69 (m, 2H, quinazolinyl - 5,7 - 2H), 7.42 (t, J = 7.5 Hz, 1H, quinazolinyl - 6 - H), 6.86 (s, 2H, Ph - 2H), 6.48 (s, 1H, NH), 6.11 (t, J = 6.3 Hz, 1H, CHCH 2 ), 4.59 (d, J = 6.3 Hz, 2H, CHCH 2 ), 4.27 (t, J = 4.9 Hz, 2H, OCH 2), 4.12 (dd, J = 10.0, 5.1 Hz, 2H, CH 2 NH), 2.64 (s, 3H, CH 3 ).

[0211] Compound 2 - 63: Yellow oil. δ(CDCl 3 ): 7.80 (d, J = 8.0 Hz, 1H, quinazolinyl - 8 - H), 7.78–7.71 (m, 2H, quinazolinyl - 5,7 - 2H), 7.52–7.47 (m, 1H, quinazolinyl - 6 - H), 6.86 (s, 2H, Ph - 2H), 6.73 (s, 1H, NH), 6.11 (t, J = 6.3 Hz, 1H, CHCH 2 ), 4.59 (d, J = 6.3 Hz, 2H, CHCH 2 ), 4.27 (t, J = 4.8 Hz, 2H, OCH 2 ), 4.12 (dd, J = 9.9, 5.1 Hz, 2H, CH 2 NH).

[0212] Compound 2 - 82: Melting point 105.5 °C. δ(CDCl 3 ): 8.65 (s, 1H, quinazolinyl - 2 - H), 7.85 (s, 1H, quinazolinyl - 8 - H), 7.72 (d, J = 8.4 Hz, 1H, quinazolinyl - 6 - H), 7.44 (d, J = 8.4 Hz, 1H, quinazolinyl - 5 - H), 6.92 (s, 2H, Ph - 2H), 6.59 (s, 1H, NH), 6.11 (s, 1H, CHCH 2 ), 4.65 (s, 2H, CHCH 2 ), 4.27 (s, 2H, OCH 2 ), 4.10 (s, 2H, CH 2 NH).

[0213] Compound 2 - 84: Melting point 147.9 °C. δ(CDCl 3): 8.67 (s, 1H, quinazolinyl-2-H), 7.93 (s, 1H, quinazolinyl-5-H), 7.82 (d, J = 8.9 Hz, 1H, quinazolinyl-8-H), 7.74 (d, J = 8.8 Hz, 1H, quinazolinyl-7-H), 6.87 (s, 2H, Ph-2H), 6.48 (s, 1H, NH), 6.11 (t, J = 6.0 Hz, 1H, CHCH 2 ), 4.59 (d, J = 5.6 Hz, 2H, CHCH 2 ), 4.35–4.21 (m, 2H, OCH 2 ), 4.10 (d, J = 4.4 Hz, 2H, CH 2 NH).

[0214] Compound 2-113: Melting point 192.5 °C. δ(CDCl 3 ): 10.80 (s, 1H, pyrazolyl-NH), 7.93 (s, 1H, pyrazolyl-H), 6.85 (s, 2H, Ph-2H), 6.34 (s, 1H, NH), 6.10 (s, 1H, CHCH 2 ), 4.58 (d, J = 6.3 Hz, 2H, CHCH 2 ), 4.23 (s, 2H, OCH 2 ), 4.08 (d, J = 3.8 Hz, 2H, CH 2 NH).

[0215] Compound 2-121: Melting point 197.9 °C. δ(CDCl 3 ): 12.15 (s, 1H, imidazolyl-NH), 8.25 (s, 1H, NH), 8.04 (s, 1H, imidazolyl-H), 7.09 (d, J = 3.5 Hz, 2H, Ph-2H), 6.44 (t, J = 6.6 Hz, 1H, CHCH 2 ), 4.63 (d, J = 6.6 Hz, 2H, CHCH 2 ), 4.09 (t, J = 5.8 Hz, 2H, OCH 2 ), 3.78 (d, J = 5.7 Hz, 2H, CH 2 NH).

[0216] Compound 2-95: Yellow oil. δ(CDCl 3): 7.28 (d, J = 5.7 Hz, 1H, thienyl-5-H), 7.14 (d, J = 5.7 Hz, 1H, thienyl-4-H), 6.84 (s, 2H, Ph-2H), 6.18 (t, J = 4.8 Hz, 1H, NH), 6.09 (t, J = 6.4 Hz, 1H, CHCH 2 ), 4.58 (d, J = 6.4 Hz, 2H, CHCH 2 ), 4.22 (t, J = 4.8 Hz, 2H, OCH 2 ), 4.05 (dd, J = 9.9, 5.3 Hz, 2H, CH 2 NH).

[0217] Compound 2-108: Melting point 125.8 °C. δ(CDCl 3 ): 7.74 (d, J = 5.3 Hz, 1H, thienyl-5-H), 7.36 (d, J = 5.4 Hz, 1H, thienyl-4-H), 6.85 (s, 2H, Ph-2H), 6.10 (t, J = 6.3 Hz, 1H, CHCH 2 ), 5.94 (s, 1H, NH), 4.58 (d, J = 6.4 Hz, 2H, CHCH 2 ), 4.28–4.20 (m, 2H, OCH 2 ), 4.08 (dd, J = 9.9, 5.3 Hz, 2H, CH 2 NH).

[0218] Compound 4-50: Melting point 91.9 °C. δ(CDCl 3 ): 8.41 (s, 1H, pyrimidyl-2-H), 6.85 (s, 2H, Ph-2H), 6.10 (t, J = 6.2 Hz, 1H, CHCH 2 ), 6.00 (s, 1H, NH), 4.58 (d, J = 6.2 Hz, 2H, CHCH 2 ), 4.07 (t, J = 5.6 Hz, 2H, OCH 2 ), 3.83 (q, J = 6.2 Hz, 2H, CH 2 NH), 2.77 (q, J = 7.6 Hz, 2H, CH 2 CH 3 ), 2.13 (dt, J = 11.8, 5.9 Hz, 2H, OCH 2 CH 2 ), 1.24 (t, J = 7.5 Hz, 3H, CH 2 CH 3 ).

[0219] Compound 4-52: white oil. δ(CDCl 3 ):8.56(s,1H,pyrimidyl-2-H),6.93(s,2H,Ph-2H),6.73(t,J=53.7Hz,1H,CHF 2 ),6.39(s,1H,NH),6.12(t,J=6.3Hz,1H,CHCH 2 ),4.66(s,2H,CHCH 2 ),4.12(t,J=5.5Hz,2H,OCH 2 ),3.90(dd,J=12.2,6.0Hz,2H,CH 2 NH), 2.29–2.08 (m, 2H, OCH 2 CH 2 ).

[0220] Compound 4-24: melting point 159.7°C. δ(CDCl 3 ):8.27(s,1H,pyrimidyl-2-H),6.85(s,2H,Ph-2H),6.10(t,J=6.2Hz,1H,CHCH 2 ),5.62(s,1H,NH),4.58(d,J=6.4Hz,2H,CHCH 2 ),4.10(t,J=5.3Hz,2H,OCH 2 ),3.82(dd,J=11.8,5.7Hz,2H,CH 2 NH), 2.17–2.11(m,2H,OCH 2 CH 2 ),2.10(s,3H,CH 3 ).

[0221] Compound 4-23: melting point 159.7°C. δ(CDCl 3 ):8.27(s,1H,pyrimidyl-2-H),6.91(s,2H,Ph-2H),6.25(s,1H,NH),6.10(t,J=6.2Hz,1H,CHCH 2 ),4.58(d,J=6.4Hz,2H,CHCH 2 ),4.08(dd,J=10.6,5.2Hz,2H,OCH 2 ),3.86(dd,J=12.2,5.9Hz,2H,CH 2 NH), 2.18–2.09 (m, 2H, OCH 2 CH2 ).

[0222] Compound 4-26: melting point 85.8°C. δ(CDCl 3 ):8.14(s,1H,pyrimidyl-2-H),6.85(s,2H,Ph-2H),6.10(t,J=6.2Hz,1H,CHCH 2 ),6.02(s,1H,NH),4.58(d,J=6.2Hz,2H,CHCH 2 ),4.07(t,J=5.5Hz,2H,OCH 2 ),3.84–3.79(m,2H,CH 2 NH),3.82(s,3H,OCH 3 ),2.18–2.05(m,2H,OCH 2 CH 2 ).

[0223] Compound 4-15: brown oil. δ(CDCl 3 ):8.33(s,1H,pyrimidyl-2-H),6.84(s,2H,Ph-2H),6.37(s,1H,pyrimidyl-5-H),6.10(t,J=6.2Hz,1H,CHCH 2 ),5.66(s,1H,NH),4.58(d,J=6.3Hz,2H,CHCH 2 ),4.07(t,J=5.5Hz,2H,OCH 2 ),3.79–3.53(m,2H,CH 2 NH),2.11(dt,J=11.9,6.0Hz,2H,OCH 2 CH 2 ).

[0224] Compound 4-17: melting point 111.7°C. δ(CDCl 3 ):6.84(s,2H,Ph-2H),6.21(s,1H,pyrimidyl-5-H),6.10(t,J=6.3Hz,1H,CHCH 2 ),5.51(s,1H,NH),4.58(d,J=6.2Hz,2H,CHCH 2 ),4.05(t,J=5.5Hz,2H,OCH 2 ),3.62(s,2H,CH 2 NH),2.46(s,1H,CH 3 ),2.13–2.04(m,2H,OCH2 CH 2 ).

[0225] Compound 4-64: Yellow oil. δ(CDCl 3 ): 7.74 (d, J = 8.2 Hz, 1H, quinazolinyl-8-H), 7.65 (dd, J = 11.6, 4.4 Hz, 1H, quinazolinyl-7-H), 7.62 (d, J = 8.0 Hz, 1H, quinazolinyl-5-H), 7.34 (t, J = 7.6 Hz, 1H, quinazolinyl-6-H), 6.87 (s, 2H, Ph-2H), 6.52 (s, 1H, NH), 6.11 (t, J = 6.2 Hz, 1H, CHCH 2 ), 4.59 (d, J = 6.2 Hz, 2H, CHCH 2 ), 4.17 (t, J = 5.3 Hz, 2H, OCH 2 ), 4.00 (dt, J = 17.1, 5.7 Hz, 2H, CH 2 NH), 2.64 (s, 1H, CH 3 ), 2.23 (dt, J = 11.5, 5.6 Hz, 2H, OCH 2 CH 2 ).

[0226] Compound 4-82: Melting point 175.5 °C. δ(CDCl 3 ): 8.43 (s, 1H, quinazolinyl-2-H), 8.41 (t, J = 5.3 Hz, 1H, NH), 8.23 (d, J = 8.9 Hz, 1H, quinazolinyl-8-H), 7.66 (d, J = 2.0 Hz, 1H, quinazolinyl-7-H), 7.51 (dd, J = 8.7, 2.1 Hz, 1H, quinazolinyl-5-H), 7.08 (s, 2H, Ph-2H), 6.42 (t, J = 6.6 Hz, 1H, CHCH 2 ), 4.63 (d, J = 6.7 Hz, 2H, CHCH 2 ), 3.98 (t, J = 6.1 Hz, 2H, OCH 2 ), 3.73 (dd, J = 13.1, 6.6 Hz, 2H, CH 2 NH), 2.15–2.05 (m, 2H, OCH 2 CH 2 ).

[0227] Compound 6-50: Melting point 91.1 °C. δ(CDCl3 ):8.41(s,1H,pyrimidyl-2-H),6.83(s,2H,Ph-2H),6.10(t,J=6.2Hz,1H,CHCH 2 ),5.52(s,1H,NH),4.57(d,J=6.3Hz,2H,CHCH 2 ),3.99(t,J=5.6Hz,2H,OCH 2 ),3.66–3.57(m,2H,CH 2 NH), 2.77(q, J=7.6Hz,2H,CH 2 CH 3 ),2.01–1.87(m,4H,CH 2 CH 2 ),1.25(t,J=7.6Hz,3H,CH 2 CH 3 ).

[0228] Compound 6-52: melting point 83°C. δ(CDCl 3 ):8.53(s,1H,pyrimidyl-2-H),6.84(s,2H,Ph-2H),6.71(t,J=53.7Hz,1H,CHF 2 ),6.10(t,J=6.3Hz,1H,CHCH 2 ),5.87(s,1H,NH),4.58(d,J=6.2Hz,2H,CHCH 2 ),4.00(t,J=5.7Hz,2H,OCH 2 ),3.68(dd,J=12.5,6.6Hz,2H,CH 2 NH), 2.01–1.85 (m, 4H, CH 2 CH 2 ).

[0229] Biological Activity Assay Example

[0230] The compound of the invention shows good activity against various pathogens, insect pests and mites in the agricultural field.

[0231] Example 8: Bactericidal activity assay

[0232] The samples of the compounds of the present invention were used to test the in vitro antibacterial activity or in vivo protective effect on various fungal diseases of plants. The results of the fungicidal activity test are shown in the following examples.

[0233] In vivo protective activity assay

[0234] The determination method is as follows: adopt the living potted plant determination method, that is, the sample of the compound to be tested is dissolved with a small amount of solvent (the type of solvent is such as acetone, methanol, DMF, etc., and is selected according to its solubility for the sample, and the volume ratio of the amount of solvent to the amount of spraying liquid is equal to or less than 0.05), and diluted with water containing 0.1% Tween 80 to prepare the required concentration of the test solution. On the crop sprayer, the test solution is sprayed on the disease host plant (the host plant is a standard potted seedling cultivated in a greenhouse), and the disease is inoculated 24 hours later. According to the characteristics of the disease, the diseased plants that need to be cultivated with temperature control and moisture retention are inoculated and placed in an artificial climate chamber for cultivation. After the disease infection is completed, they are moved to the greenhouse for cultivation. The diseased plants that do not need moisture retention cultivation are directly inoculated and cultivated in the greenhouse. After the control is fully diseased (usually one week), the disease prevention effect of the compound is evaluated.

[0235] (1) The results of the in vivo protective activity test of some compounds are as follows:

[0236] In vivo protective activity against cucumber downy mildew:

[0237] At a dosage of 400 ppm: Compounds 2-63 and 2-64 had a 100% protective effect against cucumber downy mildew;

[0238] In vivo protective activity against wheat powdery mildew:

[0239] At a dosage of 400 ppm: Compounds 2-63, 2-50, 2-52, 3-52, etc. had a 100% control effect on wheat powdery mildew;

[0240] At a dosage of 100 ppm: Compounds 2-63, 2-50, etc. have a 100% control effect on wheat powdery mildew;

[0241] At a dosage of 25 ppm: Compounds 2-63, 2-50, etc. have a control effect of 80% or more on wheat powdery mildew;

[0242] At a dosage of 6.25 ppm: Compounds 2-63, 2-50, etc. had a control effect of 70% or more on wheat powdery mildew;

[0243] At a dosage of 1.56 ppm: Compound 2-50 had a 30% protective effect against wheat powdery mildew;

[0244] The control pesticide propiconazole has a protective effect of only 30% against wheat powdery mildew at a dosage of 6.25 ppm, which is lower than that of compounds 2-63 and 2-50.

[0245] In vivo protective activity against corn rust:

[0246] At a dosage of 400 ppm: Compounds 2-63, 2-50, etc. had a 100% control effect on corn rust;

[0247] At a dosage of 100 ppm: Compounds 2-63, 2-50, etc. have a control effect of 90% or more on corn rust;

[0248] At a dosage of 25 ppm: Compounds 2-63, 2-50, etc. have an efficacy of 80% or more against corn rust;

[0249] In vivo protective activity against cucumber anthracnose:

[0250] At a dosage of 400 ppm: Compounds 2-50, 2-62, etc. had a 100% protective effect against cucumber anthracnose;

[0251] Example 9: Insecticidal and acaricidal activity assay

[0252] The compounds of the present invention were used to carry out insecticidal activity tests on several insects. The test method is as follows:

[0253] The test compound was dissolved in a mixed solvent of acetone / methanol (1:1) and then diluted with water containing 0.1% (wt) Tween 80 to the desired concentration.

[0254] The insecticidal activity was determined by airbrush spraying with Plutella xylostella, Armyworm and Tetranychus cinnabarinus as targets.

[0255] (1) Determination of activity against Plutella xylostella

[0256] Test method: Use a punch to punch cabbage leaves into leaf discs with a diameter of 2 cm and use an airbrush to spray them at a pressure of 10 psi (about 0.7 kg / cm 2 ), spray each leaf disc on both sides, with a spray volume of 0.5 ml. After drying in the shade, 10 2nd-instar test insects were inoculated in each treatment, and each treatment was repeated 3 times. After treatment, they were placed in an observation room at 25°C and a relative humidity of 60-70%. After 72 hours, the number of surviving insects was investigated and the mortality rate was calculated.

[0257] Some of the test results on Plutella xylostella are as follows:

[0258] At a dosage of 600 ppm, the mortality rates of compounds 2-20, 2-21, 2-22, 2-24, 2-50, 2-52, 2-62, 2-84, 3-52, etc. to Plutella xylostella were all 100%.

[0259] At a dosage of 100 ppm, compounds 2-20, 2-22, 2-52, etc. had a mortality rate of 80% or more against diamondback moth;

[0260] (2) Determination of activity against armyworms;

[0261] Test method: Cut corn leaves into 2 cm long segments and spray with airbrush at a pressure of 10 psi (about 0.7 kg / cm 2 ), spray each leaf segment on both sides, with a spray volume of 0.5 ml. After drying in the shade, 10 2nd-instar test insects were inoculated in each treatment, and each treatment was repeated 3 times. After treatment, they were placed in an observation room at 25°C and a relative humidity of 60-70%. After 72 hours, the number of surviving insects was investigated and the mortality rate was calculated.

[0262] Some of the test results on armyworms are as follows:

[0263] At a dosage of 600 ppm, the lethality of compounds 2-22, 2-29, 2-50, 2-62, etc. to armyworms was 100%.

[0264] At a dosage of 100 ppm, the lethality of compounds 2-22 and the like to armyworms was 100%.

[0265] (3) Determination of activity against green peach aphids

[0266] Determination method: Take a 6cm diameter culture dish, cover the bottom of the dish with a layer of filter paper, and add a proper amount of tap water to keep it moist. Cut a cabbage leaf of appropriate size (about 3cm in diameter) with 15 to 30 aphids from the cabbage plant where peach aphids are cultured, remove the winged aphids and the aphids on the front of the leaf, and place the leaf with the back facing up in the culture dish. The pressure of the airbrush spray treatment is 10psi (about 0.7kg / cm 2 ), the spray volume was 0.5 ml, and each treatment was repeated 3 times. After treatment, the insects were placed in an observation room at 25°C and a relative humidity of 60-70%. After 48 hours, the number of surviving insects was counted and the mortality rate was calculated.

[0267] Some of the test results on green peach aphid are as follows:

[0268] At a dosage of 600 ppm, the lethality of compounds 2-50, 2-63, etc. to peach aphid was 100%.

[0269] (4) Determination of activity against Tetranychus cinnabarinus

[0270] Determination method: Take two true leaf bean seedlings, inoculate them with adult spider mites and investigate the base number, then use an airbrush sprayer to treat the whole plant at a pressure of 10 psi (about 0.7 kg / cm 2 ), the spray volume was 0.5 ml. Each treatment was repeated 3 times, and the mites were placed in a standard observation room after treatment. The number of surviving mites was investigated after 72 hours, and the mortality rate was calculated.

[0271] Some of the test results on Tetranychus cinnabarinus are as follows:

[0272] At a dose of 600 ppm, the lethality of compounds 2-50 and others to Tetranychus cinnabarinus was 100%;

[0273] At a dosage of 100 ppm, the lethality of compounds 2-50 and others to Tetranychus cinnabarinus was 100%;

[0274] The embodiments described above are only preferred embodiments of the present invention and are only used to explain the present invention, not to limit the scope of implementation of the present invention. For those skilled in the art, other implementation methods can certainly be easily made by replacement or modification based on the technical contents disclosed in this specification. Therefore, all changes and improvements made to the principles and process conditions of the present invention should be included in the scope of the patent application of the present invention.

Claims

1. A pyrimidine-containing propene ether compound, characterized in that: The pyrimidine-containing propene ether compound is a compound represented by the general formula I: Where: R1 is selected from hydrogen, halogen, cyano, nitro, amino, carboxyl, C1-C4 alkyl, halogenated C1-C4 alkyl, C3-C4 cycloalkyl, C1-C4 alkoxy, halogenated C1-C4 alkoxy, C1-C4 alkylthio, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, halogenated C1-C4 alkylthio, C2-C4 alkenyl, halogenated C2-C4 alkenyl, C2-C4 alkynyl, halogenated C2-C4 alkynyl, C One of 3-C4 alkenyloxy, halogenated C3-C4 alkenyloxy, C3-C4 alkynyloxy, halogenated C3-C4 alkynyloxy, C1-C4 alkylamino, di(C1-C4 alkyl)amino, C1-C4 alkylaminocarbonyl, halogenated C1-C4 alkylaminocarbonyl, C1-C4 alkoxycarbonyl, halogenated C1-C4 alkoxycarbonyl, C1-C4 alkoxyC1-C4 alkyl or C1-C4 alkylthioC1-C4 alkyl; R2 is selected from one of hydrogen, halogen, cyano, nitro, aldehyde, amino, carboxyl, formyl, C1-C4 alkyl, halogenated C1-C4 alkyl, C1-C4 alkoxy, halogenated C1-C4 alkoxy or halogenated phenyl; Or R1 and R2 together with the connected pyrimidine ring form a five-membered or six-membered ring containing C, N, O or S; W is selected from one of hydrogen, halogen, amino, carboxyl, C1-C4 alkyl, halogenated C1-C4 alkyl, C3-C4 cycloalkyl, C1-C4 alkoxy, C1-C4 alkylthio, C1-C4 alkylamino, C1-C4 alkoxycarbonyl or C1-C4 alkylsulfonyl; X is selected from one of NR3, O or S; m is selected from an integer of 1 to 3, and when m is selected from 2 or 3, X cannot be O; R3 is selected from hydrogen, hydroxy, formyl, C1-C4 alkyl, halogenated C1-C4 alkyl, C1-C4 alkoxy, halogenated C1-C4 alkoxy, C3-C4 cycloalkyl, C1-C4 alkylthio, C2-C4 alkenylthio, C2-C4 alkenyl, C2-C4 alkynyl, halogenated C2-C4 alkenyl, halogenated C2-C4 alkynyl, C1-C4 alkoxy C1-C4 alkyl, halogenated C1-C4 alkoxy C1-C4 alkyl, C1-C4 cycloalkyl, C1-C4 alkylthio, C2-C4 alkenylthio, C2-C4 alkenyl, C2-C4 alkynyl, halogenated C2-C4 alkenyl, halogenated C2-C4 alkynyl, C1-C4 alkylthio, halogenated C1-C4 alkylthio, C1-C4 alkylsulfinyl, halogenated C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, halogenated C1-C4 alkylsulfonyl, C1-C4 alkylaminosulfonyl, di(C1-C4 alkyl)aminosulfonyl, C1-C4 alkylsulfonylaminocarbonyl, C1-C4 alkylcarbonylaminosulfonyl, C3-C4 cycloalkyloxycarbonyl, C1-C4 alkylthio, C1-C4 alkylsulfinyl, halogenated C1-C4 alkylsulfonyl, C1-C4 alkylsulfonyl, halogenated C1-C4 alkylsulfonyl, C1-C4 alkylaminosulfonyl, di(C1-C4 alkyl)aminosulfonyl, C1-C4 alkylsulfonylaminocarbonyl, C1-C4 alkylcarbonylaminosulfonyl, C3-C4 cycloalkyloxycarbonyl, C1-C4 alkylsulfon ... -C4 alkylcarbonyl, halogenated C1-C4 alkylcarbonyl, C1-C4 alkoxycarbonyl, halogenated C1-C4 alkoxycarbonyl, C1-C4 alkylcarbonyl C1-C4 alkyl, C1-C4 alkoxycarbonyl C1-C4 alkyl, C1-C4 alkylaminocarbonyl, di(C1-C4 alkyl)aminocarbonyl, C2-C4 alkenyloxycarbonyl, C2-C4 alkynyloxycarbonyl, C1-C4 alkoxy C1-C4 alkoxycarbonyl, C1-C4 alkyl Aminothio or di(C1-C4 alkyl)aminothio; or (hetero)arylcarbonyl C1-C4 alkyl, (hetero)arylcarbonyl, (hetero)aryloxycarbonyl, (hetero)aryl C1-C4 alkyloxycarbonyl, (hetero)aryl C1-C4 alkyl which are unsubstituted or further substituted by 1 to 5 of the following groups: one of halogen, nitro, cyano, C1-C4 alkyl, halo-substituted C1-C4 alkyl, C1-C4 alkoxy or halo-substituted C1-C4 alkoxy.

2. The pyrimidine-containing propene ether compound according to claim 1, characterized in that: The structure of the pyrimidine part in the compound represented by general formula I is T1, T2, T3, T4, T5 or T6, as follows: X is selected from NR3; R4 is selected from one of hydrogen, halogen or C1-C4 alkyl; R5 is selected from one of hydrogen, halogen, carboxyl, C1-C4 alkyl, C1-C4 alkoxy or C1-C4 alkoxy C1-C4 alkoxy; R6 is selected from one of hydrogen, halogen, nitro, C1-C4 alkyl, C1-C4 alkoxy or C1-C4 alkoxy C1-C4 alkoxy; R7 is selected from one of hydrogen and halogen; R8 is selected from one of hydrogen, halogen, carboxyl, C1-C4 alkyl or C1-C4 alkoxycarbonyl; R9 is selected from one of hydrogen, halogen or C1-C4 alkyl; R 10 One selected from hydrogen or halogen; R 11 One selected from hydrogen, halogen or carboxyl; R 12 One selected from hydrogen or C1-C4 alkyl; R 13 One selected from hydrogen, halogen or C1-C4 alkyl; R 14 One selected from hydrogen, C1-C4 alkyl, carboxyl C1-C4 alkyl or 1-pyrrolidinyl C1-C4 alkyl; R 15 One selected from hydrogen, halogen or C1-C4 alkyl.

3. The pyrimidine-containing propene ether compound according to claim 2, characterized in that: R1 is selected from one of hydrogen, fluorine, chlorine, bromine, iodine, cyano, nitro, amino, carboxyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, monofluoromethyl, monochloromethyl, difluoromethyl, trifluoromethyl, trifluoroethyl, methoxymethyl, ethoxymethyl or trifluoroethoxymethyl; R2 is selected from one of hydrogen, fluorine, chlorine, bromine, iodine, cyano, nitro, amino, carboxyl, formyl, methyl, ethyl, methoxy, ethoxy, trifluoroethoxy or p-bromophenyl; W is selected from one of hydrogen, fluorine, chlorine, bromine, iodine, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, monofluoromethyl, monochloromethyl, difluoromethyl, trifluoromethyl, trifluoroethyl, methoxy, ethoxy, methylthio, ethylthio, methylsulfonyl or ethylsulfonyl; R3 is selected from one of hydrogen, hydroxyl, formyl, acetyl, propionyl, butyryl, trifluoroacetyl, benzoyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, trifluoromethyl, trifluoroethyl, methoxy, ethoxy, trifluoroethoxy, cyclopropyloxy, methylthio, ethylthio, allyl, propargyl, methylsulfonyl, ethylsulfonyl, trifluoroethylsulfonyl, methylaminosulfonyl, ethylaminosulfonyl, dimethylaminosulfonyl, diethylaminosulfonyl, methylsulfonylaminocarbonyl, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, methylaminocarbonyl, dimethylaminocarbonyl, vinyloxycarbonyl, ethynyloxycarbonyl, methylaminothio, ethylaminothio or dimethylaminothio; R4 is selected from one of hydrogen, fluorine, chlorine, bromine, iodine, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl or tert-butyl; R5 is selected from one of hydrogen, fluorine, chlorine, bromine, iodine, carboxyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy, methoxymethoxy, methoxyethoxy, ethoxymethoxy or ethoxyethoxy; R6 is selected from one of hydrogen, fluorine, chlorine, bromine, iodine, nitro, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy, methoxymethoxy, methoxyethoxy, ethoxymethoxy or ethoxyethoxy; R7 is selected from one of hydrogen, fluorine, chlorine, bromine or iodine; R8 is selected from one of hydrogen, fluorine, chlorine, bromine, iodine, carboxyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, methoxycarbonyl, ethoxycarbonyl or propoxycarbonyl; R9 is selected from one of hydrogen, fluorine, chlorine, bromine, iodine, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl or tert-butyl; R 10 One selected from hydrogen, fluorine, chlorine, bromine or iodine; R 11 One selected from hydrogen, fluorine, chlorine, bromine, iodine or carboxyl; R 12 One selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl or tert-butyl; R 13 One selected from hydrogen, fluorine, chlorine, bromine, iodine, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl or tert-butyl; R 14 One selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, carboxymethylene, carboxyethyl, 1-pyrrolidinylmethyl or 1-pyrrolidinylethyl; R 15 One selected from hydrogen, fluorine, chlorine, bromine, iodine, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl or tert-butyl.

4. The pyrimidine-containing propene ether compound according to claim 3, characterized in that: R1 is selected from one of chlorine, methyl, ethyl or difluoromethyl; R2 is selected from one of hydrogen, chlorine, bromine, methyl, methoxy or p-bromophenyl; W is selected from one of hydrogen, fluorine, chlorine, methyl or methylsulfonyl; m is an integer selected from 1 to 3; R3 is selected from hydrogen or methyl; R4 is selected from hydrogen; R5 is selected from hydrogen or chlorine; R6 is selected from hydrogen or bromine; R7, R8, R9, R 10 , R 11 , R 12 , R 13 , R 14 , R 15 are selected from hydrogen.

5. The method for preparing a pyrimidine-containing propene ether compound according to any one of claims 1 to 4, characterized in that: The following steps are involved: Intermediate II and intermediate III react in a solvent under alkaline conditions to obtain a compound of formula I; The reaction temperature is any temperature from room temperature to the boiling point of the solvent; The reaction time is 30 minutes to 20 hours.

6. The method for preparing a pyrimidine-containing propene ether compound according to claim 5, characterized in that: The molar ratio of the intermediate II to the intermediate III is 1:1; The base used in the reaction is potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, triethylamine, pyridine, sodium methoxide, sodium ethoxide, sodium hydride, potassium tert-butoxide or sodium tert-butoxide; The solvent is tetrahydrofuran, 1,4-dioxane, acetonitrile, toluene, xylene, benzene, N,N-dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide, acetone or butanone; The reaction temperature is 20-100°C; The reaction time is 1-10 hours.

7. Use of the pyrimidine-containing propenyl ether compound according to any one of claims 1 to 4 in the preparation of fungicides or insecticides and acaricides.

8. The use according to claim 7, characterized in that: The pyrimidine-containing propenyl ether compound in the bactericide or insecticide acaricide is used as an active component, and the weight percentage of the active component in the bactericide or insecticide acaricide is 0.1-99%.

9. The use according to claim 7, characterized in that: The fungicide is a drug for preventing and treating oomycete diseases, deuteromycete diseases, basidiomycete diseases and ascomycete diseases.

10. The use according to claim 7, characterized in that: The insecticide and acaricide medicine is a medicine for preventing and controlling pests of the orders Coleoptera, Dermoptera, Neuroptera, Diptera, Hemiptera, Homoptera and Lepidoptera.

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