CN113754637A

CN113754637A - Pyridine ether compound containing pyrimidinamine

Info

Publication number: CN113754637A
Application number: CN202010490412.3A
Authority: CN
Inventors: 刘卫东; 柳爱平; 刘兴平; 欧晓明; 杨小龙; 李建明; 黄路; 成淑芬; 任叶果; 刘民华
Original assignee: Hunan Research Institute of Chemical Industry
Current assignee: Hunan Research Institute of Chemical Industry
Priority date: 2020-06-02
Filing date: 2020-06-02
Publication date: 2021-12-07
Anticipated expiration: 2040-06-02
Also published as: CN113754637B

Abstract

The invention discloses a pyridine ether compound containing pyrimidinamine shown in formula (I) and a preparation method and application of an isomer or a salt thereof.

Formula (III) R, R¹、R²、R³、R⁴And W has the definitions given in the specification. The compound of formula (I) has insecticidal/acaricidal or fungicidal biological activity, and especially has high activity on pests and germs.

Description

Pyridine ether compound containing pyrimidinamine

Technical Field

The invention belongs to the field of insecticidal/acaricidal and bactericidal agents, and particularly relates to pyridylether compounds containing pyrimidinamine and having insecticidal/acaricidal and bactericidal biological activities, a preparation method thereof, insecticidal/acaricidal and bactericidal agent compositions containing the compounds, and application and a method for controlling pests, acarids and harmful bacteria by using the compounds.

Background

CN109776427A discloses structural formulas of the following pyrimidinamine-containing pyridylether hydrochloride, acetate or maleate salts S1, S2, S3, S4 and S5, and does not disclose structural characteristics and biological activity thereof. Based on the investigation, the non-salt compounds D1, D2, D3, D4 and D5 and other pyridine ether compounds containing pyrimidine amine were not found.

WO2016/184378 discloses that pyrimidine amine-containing pyrazole ether compounds D6 and D7 and the like also have insecticidal/acaricidal activity.

In order to obtain novel active molecules, the inventor carries out intensive research on pyridine ether compounds containing pyrimidinamine and finds that the novel pyridine ether compounds containing pyrimidinamine have broad-spectrum and high-efficiency biological activity.

Disclosure of Invention

The invention provides a pyridine ether compound containing pyrimidinamine and having biological activity of preventing and controlling pests/mites, harmful bacteria and the like as shown in a formula (I), an isomer thereof or a salt of the compound as shown in the formula (I):

wherein:

I.R is selected from C₁-C₁₂Alkyl radical, C₂-C₁₂Alkenyl radical, C₂-C₁₂Alkynyl, C₃-C₁₂Cycloalkyl or C₃-C₁₂A heterocyclic group;

II.R¹is selected from C₁-C₁₂Alkyl radical, C₂-C₁₂Alkenyl radical, C₂-C₁₂Alkynyl, C₃-C₁₂Cycloalkyl or C₃-C₁₂A heterocyclic group;

III.R²、R³、R⁴are identical or different and are selected from the group consisting of hydrogen, nitro, cyano, halogen, C₁-C₁₂Alkyl radical, C₁-C₁₂Alkoxy or C₁-C₁₂An alkylthio group;

w is selected from hydrogen, C₁-C₁₂Alkyl radical, C₂-C₁₂Alkenyl radical, C₂-C₁₂Alkynyl, C₃-C₁₂Cycloalkyl or C₃-C₁₂A heterocyclic group;

v, and R¹The carbon to which is attached is in S configuration, R configuration or R/S configuration in any ratio;

I. in II, III or IV, the hydrogen atoms in the alkyl, alkenyl, alkynyl, cycloalkyl or heterocyclyl groups may be partially or fully substituted by the same or different substituents selected from the group consisting of: halogen, nitro, cyano, amino, hydroxy, C₁-C₆Alkyl radical, C₁-C₆Alkoxy radical, C₁-C₆Alkylthio radical, C₁-C₆An alkylamino group;

in the definitions of the compounds (I) given above, the terms used, whether used alone or in compound words, represent the following substituents:

halogen: fluorine, chlorine, bromine, iodine;

alkyl groups: refers to straight or branched chain alkyl;

an alkenyl group; refers to a straight or branched chain alkyl group, and a double bond may be present at any position;

an alkynyl group; refers to a straight or branched chain alkyl group, and may have a triple bond at any position;

halogenation: refers to a compound in which hydrogen atoms are partially or totally substituted by halogen atoms;

cycloalkyl groups: refers to a saturated or unsaturated cycloalkyl group;

heterocyclic group: saturated or unsaturated heterocycloalkyl, wherein there are at least 1N, O or S;

a salt of a compound of formula (I): refers to salts of compounds of formula (I) with organic or inorganic acids; the organic acid means a carboxylic acid or a sulfonic acid such as acetic acid, trifluoroacetic acid, chloroacetic acid, propionic acid, butyric acid, oxalic acid, adipic acid, lauric acid, citric acid, maleic acid, fumaric acid, benzoic acid, methylbenzoic acid, phthalic acid, methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid or dodecylbenzenesulfonic acid, etc.; inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, carbonic acid, or the like.

Preferred compounds of the invention are compounds of formula (I) and isomers thereof or salts of compounds of formula (I) wherein:

I.R is selected from C₁-C₆Alkyl, halo C₁-C₆Alkyl radical, C₃-C₆Cycloalkyl or halo C₃-C₆A cycloalkyl group;

II.R¹is selected from C₁-C₆Alkyl, halo C₁-C₆Alkyl radical, C₃-C₆Cycloalkyl or halo C₃-C₆A cycloalkyl group;

III.R²、R³、R⁴are identical or different and are selected from the group consisting of hydrogen, nitro, halogen, C₁-C₆Alkyl or halo C₁-C₆An alkyl group;

w is selected from hydrogen, C₁-C₆Alkyl, halo C₁-C₆Alkyl radical, C₃-C₆Cycloalkyl or halo C₃-C₆A cycloalkyl group;

v, and R¹The carbon attached is in the S configuration, R configuration or R/S configuration in any ratio.

III.R²、R³、R⁴are identical or different and are selected from hydrogen, halogen, difluoromethyl, trifluoromethyl, trichloromethyl;

w is selected from hydrogen or methyl; when W is selected from hydrogen, the compound of formula (I) is shown as formula (I-1), and the salt of the compound of formula (I) is shown as formula (I-3); when W is selected from methyl, the compound of formula (I) is shown as formula (I-2), and the salt of the compound of formula (I-2) is shown as formula (I-4); the Acid in the formula (I-3) and the formula (I-4) is an organic Acid or an inorganic Acid as defined above;

Further preferred compounds of the invention are compounds of formula (I) and isomers thereof or salts of compounds of formula (I) wherein:

III.R²、R³、R⁴are identical or different and are selected from the group consisting of hydrogen, halogen, trifluoromethyl；

W is selected from hydrogen or methyl; when W is selected from hydrogen, the compound shown in the formula (I-1) is I-1A, I-1B, I-1C, I-1D, I-1E, I-1F, I-1G, I-1H, I-1I, I-1J, I-1K, I-1L, I-1M, I-1N, I-1O, I-1P, I-1Q, I-1R, I-1S, I-1T, I-1U, I-1V, I-1W or I-1X; when W is selected from methyl, the compound shown in the formula (I-2) is I-2A, I-2B, I-2C, I-2D, I-2E, I-2F, I-2G, I-2H, I-2I, I-2J, I-2K, I-2L, I-2M, I-2N, I-2O, I-2P, I-2Q, I-2R, I-2S, I-2T, I-2U, I-2V, I-2W or I-2X;

the compound salt shown in formula (I-1) is I-3A, I-3B, I-3C, I-3D, I-3E, I-3F, I-3G, I-3H, I-3I, I-3J, I-3K, I-3L, I-3M, I-3N, I-3O, I-3P, I-3Q, I-3R, I-3S, I-3T, I-3U, I-3V, I-3W or I-3X; the compound salt shown in the formula (I-2) is I-4A, I-4B, I-4C, I-4D, I-4E, I-4F, I-4G, I-4H, I-4I, I-4J, I-4K, I-4L, I-4M, I-4N, I-4O, I-4P, I-4Q, I-4R, I-4S, I-4T, I-4U, I-4V, I-4W or I-4X;

RS stands for R¹The carbon to which is attached is of the configuration R/S in any ratio, S representing the bond with R¹The carbon to which is attached being of S configuration, R represents a group with R¹The attached carbon is in the R configuration.

Still further preferred compounds of the invention are of formula I-1A, I-1B, I-1C, I-1D, I-1E, I-1F, I-1G, I-1H, I-1I, I-1J, I-1K, I-1L, I-1M, I-1N, I-1O, I-1P, I-1Q, I-1R, I-1S, I-1T, I-1U, I-1V, I-1W, I-1X, I-2A, I-2B, I-2C, I-2D, I-2E, I-2F, I-2G, I-2H, I-2I, I-2J, I-2K, I-2L, I-2M, I-2N, I-2O, I-2P, I-2Q, I-2R, I-2S, I-2T, I-2U, I-2V, I-2W or I-2X,

wherein: r and R¹Are identical or different and are selected from the group consisting of methyl, ethyl, n-butylPropyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, chloromethyl, fluoromethyl, bromomethyl, iodomethyl, dichloromethyl, difluoromethyl, dibromomethyl, diiodomethyl, trichloromethyl, trifluoromethyl, tribromomethyl, triiodomethyl, 2-trifluoroethyl, 1-fluoroethyl, 1-chloroethyl, 1-bromoethyl, 1-fluoroisopropyl, 1-chloroisopropyl, 1-bromoisopropyl, methoxymethyl, methoxyethyl, ethoxymethyl, cyclopropyl, cyclopentyl, cyclohexyl, 1-oxolanyl, 2-allyl, 2-propargyl, 3-chloro-2-allyl, 3-dichloro-2-allyl, 3-difluoro-2-allyl, heptafluoroisopropyl, or 1-methoxyhexafluoroisopropyl;

or salts of the compounds I-3A, I-3B, I-3C, I-3D, I-3E, I-3F, I-3G, I-3H, I-3I, I-3J, I-3K, I-3L, I-3M, I-3N, I-3O, I-3P, I-3Q, I-3R, I-3S, I-3T, I-3U, I-3V, I-3W, I-3X, I-4A, which are formed by the compounds I-3A, I-3C, I-3-V, I-3-W, I, trifluoroacetic acid, oxalic acid, methanesulfonic acid, p-toluenesulfonic acid, benzoic acid, phthalic acid, maleic acid, fumaric acid, sorbic acid or citric acid, I-4B, I-4C, I-4D, I-4E, I-4F, I-4G, I-4H, I-4I, I-4J, I-4K, I-4L, I-4M, I-4N, I-4O, I-4P, I-4Q, I-4R, I-4S, I-4T, I-4U, I-4V, I-4W or I-4X.

Particularly preferred compounds of the formula (I) according to the invention are the compounds shown in Table 1 or their salts with hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, formic acid, acetic acid, trifluoroacetic acid, oxalic acid, methanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, benzoic acid, phthalic acid, maleic acid, fumaric acid, sorbic acid, malic acid, tartaric acid or citric acid.

TABLE 1 Compounds of formula (I) which are particularly preferred according to the invention

Tables 2,3, 4 and 5 show R and R in the formula (I)¹，R²、R³Or R⁴The moiety of W is a specific substituent, but they are not limited to these substituents. Table 6 lists some specific acids of the Acid in formula (I-3) or formula (I-4), but the Acid is not limited to these acids.

TABLE 2 specific substituents for moieties from which R is selected in the general formula (I)

TABLE 3R in the general formula (I)¹Selected from the group consisting of the moiety-specific substituents

TABLE 4 general formula (I) R²、R³Or R⁴Selected from the group consisting of the moiety-specific substituents

TABLE 5 partial specific substituents of formula (I) wherein W is selected from

TABLE 6 partial acids selected from the group consisting of acids in the general formula (I-3) and the formula (I-4)

No.	Acid	No.	Acid	No.	Acid	No.	Acid
								6-1	Hydrochloric acid	6-2	Sulfuric acid	6-3	Phosphoric acid	6-4	Nitric acid
6-5	Carbonic acid	6-6	Formic acid	6-7	Acetic acid	6-8	Trifluoroacetic acid
								6-9	Propionic acid	6-10	Butyric acid	6-11	Cyclopentanoic acid	6-12	Oxalic acid
6-13	Adipic acid	6-14	Benzoic acid	6-15	Para methyl benzoic acid	6-16	Phthalic acid
								6-17	Methanesulfonic acid	6-18	Trifluoromethanesulfonic acid	6-19	Benzene sulfonic acid	6-20	P-toluenesulfonic acid
6-21	Dodecyl benzene sulfonic acid	6-22	Lauric acid	6-23	Maleic acid	6-24	Fumaric acid
								6-25	Sorbic acid	6-26	Malic acid	6-27	Citric acid	6-28	Tartaric acid

The compound of the invention can be prepared by using the compound numbers I-1A, I-1B, I-1C, I-1D, I-1E, I-1F, I-1G, I-1H, I-1I, I-1J, I-1K, I-1L, I-1M, I-1N, I-1O, I-1P, I-1Q, I-1R, I-1S, I-1T, I-1U, I-1V, I-1W, I-1X, I-2A, I-2B, I-2C, I-2D, I-2E, I-2F, I-2G, I-2H, I-2I, I-2J, I-2K, Specific compounds listed in I-2L, I-2M, I-2N, I-2O, I-2P, I-2Q, I-2R, I-2S, I-2T, I-2U, I-2V, I-2W or I-2X are illustrative, but not limiting, of the invention.

The salt of the compound of the invention can be prepared by using the compound numbers I-3A, I-3B, I-3C, I-3D, I-3E, I-3F, I-3G, I-3H, I-3I, I-3J, I-3K, I-3L, I-3M, I-3N, I-3O, I-3P, I-3Q, I-3R, I-3S, I-3T, I-3U, I-3V, I-3W, I-3X, I-4A, I-4B, I-4C, I-4D, I-4E, I-4F, I-4G, I-4H, I-4I, I-4J, I-4K, Salts of specific compounds listed in I-4L, I-4M, I-4N, I-4O, I-4P, I-4Q, I-4R, I-4S, I-4T, I-4U, I-4V, I-4W or I-4X are illustrative, but not limiting, of the invention.

When R is CH₃，R¹The substituent groups are shown in Table 3, and the I-1A represents the compound numbers of I-1A1-1-I-1A1-40, I-1B1-1-I-1B1-40, I-1C1-1-I-1C1-40, I-1D1-1-I-1D1-40, I-1E1-1-I-1E1-40, I-1F1-1-I-1F1-40, I-1G1-1-I-1G1-40, I-1H1-1-I-1H1-40, I-1I1-1-I-1I1-40, I-1J1-1-I-1J1-40, I-1J 1-1J 1-40, I-1K1-1-I-1K1-40, I-1L1-1-I-1L1-40, I-1M1-1-I-1M1-40, I-1N1-1-I-1N1-40, I-1O1-1-I-1O1-40, I-1P1-1-I-1P1-40, I-1Q1-1-I-1Q1-40, I-1R1-1-I-1R1-40, I-1S1-1-I-1S1-40, I-1T1-1-I-1T1-40, I-1U1-1-I-1U1-40, I-1U 673654-40, I-1V1-1-I-1V1-40, I-1W1-1-I-1W1-40, I-1X1-1-I-1X 1-40; the I-2A represents a compound with the serial number of I-2A1-1-I-2A1-40, I-2B1-1-I-2B1-40, I-2C1-1-I-2C1-40, I-2D1-1-I-2D1-40, I-2E1-1-I-2E1-40 and I-2E1-40 in sequenceF1-1-I-2F1-40、I-2G1-1-I-2G1-40、I-2H1-1-I-2H1-40、I-2I1-1-I-2I1-40、I-2J1-1-I-2J1-40、I-2K1-1-I-2K1-40、I-2L1-1-I-2L1-40、I-2M1-1-I-2M1-40、I-2N1-1-I-2N1-40、I-2O1-1-I-2O1-40、I-2P1-1-I-2P1-40、I-2Q1-1-I-2Q1-40、I-2R1-1-I-2R1-40、I-2S1-1-I-2S1-40、I-2T1-1-I-2T1-40、I-2U1-1-I-2U1-40、I-2V1-1-I-2V1-40、I-2W1-1-I-2W1-40、I-2X1-1-I-2X1-40；

When R is CH₂CH₃，R¹The substituent groups are shown in Table 3, and the I-1A represents the compound numbers of I-1A2-1-I-1A2-40, I-1B2-1-I-1B2-40, I-1C2-1-I-1C2-40, I-1D2-1-I-1D2-40, I-1E2-1-I-1E2-40, I-1F2-1-I-1F2-40, I-1G2-1-I-1G2-40, I-1H2-1-I-1H2-40, I-1I2-1-I-1I2-40, I-1J2-1-I-1J2-40, I-1J 2-1J 2-40, I-1K2-1-I-1K2-40, I-1L2-1-I-1L2-40, I-1M2-1-I-1M2-40, I-1N2-1-I-1N2-40, I-1O2-1-I-1O2-40, I-1P2-1-I-1P2-40, I-1Q2-1-I-1Q2-40, I-1R2-1-I-1R2-40, I-1S2-1-I-1S2-40, I-1T2-1-I-1T2-40, I-1U2-1-I-1U2-40, I-1U 673654-40, I-1V2-1-I-1V2-40, I-1W2-1-I-1W2-40, I-1X2-1-I-1X 2-40; the I-2A represents a compound which is numbered sequentially as I-2A2-1-I-2A2-40, I-2B2-1-I-2B2-40, I-2C2-1-I-2C2-40, I-2D2-1-I-2D2-40, I-2E2-1-I-2E2-40, I-2F2-1-I-2F2-40, I-2G2-1-I-2G2-40, I-2H2-1-I-2H2-40, I-2I2-1-I-2I2-40, I-2J2-1-I-2J2-40, I-2K2-1-I-2K2-40, I-2K 6354-40, I-2L2-1-I-2L2-40, I-2M2-1-I-2M2-40, I-2N2-1-I-2N2-40, I-2O2-1-I-2O2-40, I-2P2-1-I-2P2-40, I-2Q2-1-I-2Q2-40, I-2R2-1-I-2R2-40, I-2S2-1-I-2S2-40, I-2T2-1-I-2T2-40, I-2U2-1-I-2U2-40, I-2V2-1-I-2V2-40, I-2V2-40, I-2W2-1-I-2W2-40, I-2X2-1-I-2X 2-40;

when R is CHF₂，R¹The substituent groups are shown in Table 3, and the I-1A represents the compound numbers of I-1A3-1-I-1A3-40, I-1B3-1-I-1B3-40, I-1C3-1-I-1C3-40, I-1D3-1-I-1D3-40, I-1E3-1-I-1E3-40, I-1F3-1-I-1F3-40, I-1G3-1-I-1G3-40, I-1H3-1-I-1H3-40, I-1I3-1-I-1I3-40, I-1J3-1-I-1J3-40, I-1J 3-1J 3-40, I-1K3-1-I-1K3-40, I-1L3-1-I-1L3-40, I-1M3-1-I-1M3-40, I-1N3-1-I-1N3-40, I-1O3-1-I-1O3-40, I-1P3-1-I-1P3-40, I-1Q3-1-I-1Q3-40, I-1R3-1-I-1R3-40, I-1S3-1-I-1S3-40, I-1T3-1-I-1T3-40, I-1U3-1-I-1U3-40, I-1U 673654-40, I-1V3-1-I-1V3-40, I-1W3-1-I-1W3-40, I-1X3-1-I-1X 3-40; I-2A represents a compoundThe serial numbers are I-2A3-1-I-2A3-40, I-2B3-1-I-2B3-40, I-2C3-1-I-2C3-40, I-2D3-1-I-2D3-40, I-2E3-1-I-2E3-40, I-2F3-1-I-2F3-40, I-2G3-1-I-2G3-40, I-2H3-1-I-2H3-40, I-2I3-1-I-2I3-40, I-2J3-1-I-2J3-40, I-2K3-1-I-2K3-40, I-2K3-40, I-2L3-1-I-2L3-40, I-2M3-1-I-2M3-40, I-2N3-1-I-2N3-40, I-2O3-1-I-2O3-40, I-2P3-1-I-2P3-40, I-2Q3-1-I-2Q3-40, I-2R3-1-I-2R3-40, I-2S3-1-I-2S3-40, I-2T3-1-I-2T3-40, I-2U3-1-I-2U3-40, I-2V3-1-I-2V3-40, I-2V3-40, I-2W3-1-I-2W3-40, I-2X3-1-I-2X 3-40;

when R ═ CF₃，R¹The substituent groups are shown in Table 3, and the I-1A represents the compound numbers of I-1A4-1-I-1A4-40, I-1B4-1-I-1B4-40, I-1C4-1-I-1C4-40, I-1D4-1-I-1D4-40, I-1E4-1-I-1E4-40, I-1F4-1-I-1F4-40, I-1G4-1-I-1G4-40, I-1H4-1-I-1H4-40, I-1I4-1-I-1I4-40, I-1J4-1-I-1J4-40, I-1J 4-1J 4-40, I-1K4-1-I-1K4-40, I-1L4-1-I-1L4-40, I-1M4-1-I-1M4-40, I-1N4-1-I-1N4-40, I-1O4-1-I-1O4-40, I-1P4-1-I-1P4-40, I-1Q4-1-I-1Q4-40, I-1R4-1-I-1R4-40, I-1S4-1-I-1S4-40, I-1T4-1-I-1T4-40, I-1U4-1-I-1U4-40, I-1U 673654-40, I-1V4-1-I-1V4-40, I-1W4-1-I-1W4-40, I-1X4-1-I-1X 4-40; the I-2A represents a compound which is numbered sequentially as I-2A4-1-I-2A4-40, I-2B4-1-I-2B4-40, I-2C4-1-I-2C4-40, I-2D4-1-I-2D4-40, I-2E4-1-I-2E4-40, I-2F4-1-I-2F4-40, I-2G4-1-I-2G4-40, I-2H4-1-I-2H4-40, I-2I4-1-I-2I4-40, I-2J4-1-I-2J4-40, I-2K4-1-I-2K4-40, I-2K 6354-40, I-2L4-1-I-2L4-40, I-2M4-1-I-2M4-40, I-2N4-1-I-2N4-40, I-2O4-1-I-2O4-40, I-2P4-1-I-2P4-40, I-2Q4-1-I-2Q4-40, I-2R4-1-I-2R4-40, I-2S4-1-I-2S4-40, I-2T4-1-I-2T4-40, I-2U4-1-I-2U4-40, I-2V4-1-I-2V4-40, I-2V4-40, I-2W4-1-I-2W4-40, I-2X4-1-I-2X 4-40;

when R is CHClCH₃，R¹The substituent groups are shown in Table 3, and the I-1A represents the compound numbers of I-1A5-1-I-1A5-40, I-1B5-1-I-1B5-40, I-1C5-1-I-1C5-40, I-1D5-1-I-1D5-40, I-1E5-1-I-1E5-40, I-1F5-1-I-1F5-40, I-1G5-1-I-1G5-40, I-1H5-1-I-1H5-40, I-1I5-1-I-1I5-40, I-1J5-1-I-1J5-40, I-1J 5-1J 5-40, I-1K5-1-I-1K5-40, I-1L5-1-I-1L5-40, I-1M5-1-I-1M5-40, I-1N5-1-I-1N5-40, I-1O5-1-I-1O5-40, I-1P5-1-I-1P5-40, I-1Q5-1-I-1Q5-40, I-1R5-1-I-1R5-40, I-1S5-1-I-1S5-40, I-1T5-1-I-1T5-40,I-1U5-1-I-1U5-40, I-1V5-1-I-1V5-40, I-1W5-1-I-1W5-40, I-1X5-1-I-1X 5-40; the I-2A represents a compound which is numbered sequentially as I-2A5-1-I-2A5-40, I-2B5-1-I-2B5-40, I-2C5-1-I-2C5-40, I-2D5-1-I-2D5-40, I-2E5-1-I-2E5-40, I-2F5-1-I-2F5-40, I-2G5-1-I-2G5-40, I-2H5-1-I-2H5-40, I-2I5-1-I-2I5-40, I-2J5-1-I-2J5-40, I-2K5-1-I-2K5-40, I-2K 6354-40, I-2L5-1-I-2L5-40, I-2M5-1-I-2M5-40, I-2N5-1-I-2N5-40, I-2O5-1-I-2O5-40, I-2P5-1-I-2P5-40, I-2Q5-1-I-2Q5-40, I-2R5-1-I-2R5-40, I-2S5-1-I-2S5-40, I-2T5-1-I-2T5-40, I-2U5-1-I-2U5-40, I-2V5-1-I-2V5-40, I-2V5-40, I-2W5-1-I-2W5-40, I-2X5-1-I-2X 5-40;

when R is CHFCH₃，R¹The substituent groups are shown in Table 3, and the I-1A represents the compound numbers of I-1A6-1-I-1A6-40, I-1B6-1-I-1B6-40, I-1C6-1-I-1C6-40, I-1D6-1-I-1D6-40, I-1E6-1-I-1E6-40, I-1F6-1-I-1F6-40, I-1G6-1-I-1G6-40, I-1H6-1-I-1H6-40, I-1I6-1-I-1I6-40, I-1J6-1-I-1J6-40, I-1J 6-1J 6-40, I-1K6-1-I-1K6-40, I-1L6-1-I-1L6-40, I-1M6-1-I-1M6-40, I-1N6-1-I-1N6-40, I-1O6-1-I-1O6-40, I-1P6-1-I-1P6-40, I-1Q6-1-I-1Q6-40, I-1R6-1-I-1R6-40, I-1S6-1-I-1S6-40, I-1T6-1-I-1T6-40, I-1U6-1-I-1U6-40, I-1U 673654-40, I-1V6-1-I-1V6-40, I-1W6-1-I-1W6-40, I-1X6-1-I-1X 6-40; the I-2A represents a compound which is numbered sequentially as I-2A6-1-I-2A6-40, I-2B6-1-I-2B6-40, I-2C6-1-I-2C6-40, I-2D6-1-I-2D6-40, I-2E6-1-I-2E6-40, I-2F6-1-I-2F6-40, I-2G6-1-I-2G6-40, I-2H6-1-I-2H6-40, I-2I6-1-I-2I6-40, I-2J6-1-I-2J6-40, I-2K6-1-I-2K6-40, I-2K 6354-40, I-2L6-1-I-2L6-40, I-2M6-1-I-2M6-40, I-2N6-1-I-2N6-40, I-2O6-1-I-2O6-40, I-2P6-1-I-2P6-40, I-2Q6-1-I-2Q6-40, I-2R6-1-I-2R6-40, I-2S6-1-I-2S6-40, I-2T6-1-I-2T6-40, I-2U6-1-I-2U6-40, I-2V6-1-I-2V6-40, I-2V6-40, I-2W6-1-I-2W6-40, I-2X6-1-I-2X 6-40;

when R is cyclopropyl, R¹The substituent groups are shown in Table 3, and the I-1A represents the compound numbers of I-1A7-1-I-1A7-40, I-1B7-1-I-1B7-40, I-1C7-1-I-1C7-40, I-1D7-1-I-1D7-40, I-1E7-1-I-1E7-40, I-1F7-1-I-1F7-40, I-1G7-1-I-1G7-40, I-1H7-1-I-1H7-40, I-1I7-1-I-1I7-40, I-1J7-1-I-1J7-40, I-1J 7-1J 7-40, I-1K7-1-I-1K7-40, I-1L7-1-I-1L7-40, I-1M7-1-I-1M7-40, I-1N7-1-I-1N7-40, I-1O7-1-I-1O7-40, I-1K 8932-40-1P7-1-I-1P7-40, I-1Q7-1-I-1Q7-40, I-1R7-1-I-1R7-40, I-1S7-1-I-1S7-40, I-1T7-1-I-1T7-40, I-1U7-1-I-1U7-40, I-1V7-1-I-1V7-40, I-1W7-1-I-1W7-40, I-1X7-1-I-1X 7-40; the I-2A represents a compound which is numbered sequentially as I-2A7-1-I-2A7-40, I-2B7-1-I-2B7-40, I-2C7-1-I-2C7-40, I-2D7-1-I-2D7-40, I-2E7-1-I-2E7-40, I-2F7-1-I-2F7-40, I-2G7-1-I-2G7-40, I-2H7-1-I-2H7-40, I-2I7-1-I-2I7-40, I-2J7-1-I-2J7-40, I-2K7-1-I-2K7-40, I-2K 6354-40, I-2L7-1-I-2L7-40, I-2M7-1-I-2M7-40, I-2N7-1-I-2N7-40, I-2O7-1-I-2O7-40, I-2P7-1-I-2P7-40, I-2Q7-1-I-2Q7-40, I-2R7-1-I-2R7-40, I-2S7-1-I-2S7-40, I-2T7-1-I-2T7-40, I-2U7-1-I-2U7-40, I-2V7-1-I-2V7-40, I-2V7-40, I-2W7-1-I-2W7-40, I-2X7-1-I-2X 7-40;

when R is 2-allyl, R¹The substituent groups are shown in Table 3, and the I-1A represents the compound numbers of I-1A8-1-I-1A8-40, I-1B8-1-I-1B8-40, I-1C8-1-I-1C8-40, I-1D8-1-I-1D8-40, I-1E8-1-I-1E8-40, I-1F8-1-I-1F8-40, I-1G8-1-I-1G8-40, I-1H8-1-I-1H8-40, I-1I8-1-I-1I8-40, I-1J8-1-I-1J8-40, I-1J 8-1J 8-40, I-1K8-1-I-1K8-40, I-1L8-1-I-1L8-40, I-1M8-1-I-1M8-40, I-1N8-1-I-1N8-40, I-1O8-1-I-1O8-40, I-1P8-1-I-1P8-40, I-1Q8-1-I-1Q8-40, I-1R8-1-I-1R8-40, I-1S8-1-I-1S8-40, I-1T8-1-I-1T8-40, I-1U8-1-I-1U8-40, I-1U 673654-40, I-1V8-1-I-1V8-40, I-1W8-1-I-1W8-40, I-1X8-1-I-1X 8-40; the I-2A represents a compound which is numbered sequentially as I-2A8-1-I-2A8-40, I-2B8-1-I-2B8-40, I-2C8-1-I-2C8-40, I-2D8-1-I-2D8-40, I-2E8-1-I-2E8-40, I-2F8-1-I-2F8-40, I-2G8-1-I-2G8-40, I-2H8-1-I-2H8-40, I-2I8-1-I-2I8-40, I-2J8-1-I-2J8-40, I-2K8-1-I-2K8-40, I-2K 6354-40, I-2L8-1-I-2L8-40, I-2M8-1-I-2M8-40, I-2N8-1-I-2N8-40, I-2O8-1-I-2O8-40, I-2P8-1-I-2P8-40, I-2Q8-1-I-2Q8-40, I-2R8-1-I-2R8-40, I-2S8-1-I-2S8-40, I-2T8-1-I-2T8-40, I-2U8-1-I-2U8-40, I-2V8-1-I-2V8-40, I-2V8-40, I-2W8-1-I-2W8-40, I-2X8-1-I-2X 8-40;

when R is 2-propargyl, R¹The substituent groups are shown in Table 3, and the I-1A represents the compound numbers of I-1A9-1-I-1A9-40, I-1B9-1-I-1B9-40, I-1C9-1-I-1C9-40, I-1D9-1-I-1D9-40, I-1E9-1-I-1E9-40, I-1F9-1-I-1F9-40, I-1G9-1-I-1G9-40, I-1H9-1-I-1H9-40, I-1I9-1-I-1I9-40, I-1J9-1-I-1J9-40, I-1J 9-1J 9-40, I-1K9-1-I-1K9-40, I-1L9-1-I-1L9-40, I-1M9-1-I-1M9-40, I-1N9-1-I-1N9-40, I-1O9-1-I-1O9-40, I-1P9-1-I-1P9-40, I-1Q9-1-I-1Q9-40, I-1R9-1-I-1R9-40, I-1S9-1-I-1S9-40, I-1T9-1-I-1T9-40, I-1U9-1-I-1U9-40, I-1V9-1-I-1V9-40, I-1V9-40, I-1W9-1-I-1W9-40, I-1X9-1-I-1X 9-40; the I-2A represents a compound which is numbered sequentially as I-2A9-1-I-2A9-40, I-2B9-1-I-2B9-40, I-2C9-1-I-2C9-40, I-2D9-1-I-2D9-40, I-2E9-1-I-2E9-40, I-2F9-1-I-2F9-40, I-2G9-1-I-2G9-40, I-2H9-1-I-2H9-40, I-2I9-1-I-2I9-40, I-2J9-1-I-2J9-40, I-2K9-1-I-2K9-40, I-2K 6354-40, I-2L9-1-I-2L9-40, I-2M9-1-I-2M9-40, I-2N9-1-I-2N9-40, I-2O9-1-I-2O9-40, I-2P9-1-I-2P9-40, I-2Q9-1-I-2Q9-40, I-2R9-1-I-2R9-40, I-2S9-1-I-2S9-40, I-2T9-1-I-2T9-40, I-2U9-1-I-2U9-40, I-2V9-1-I-2V9-40, I-2V9-40, I-2W9-1-I-2W9-40 and I-2X9-1-I-2X 9-40.

When R is CH₃，R¹The substituent group is shown in Table 3, the Acid is shown in Table 6, the I-3A represents the compound number sequentially of I-3A 1-1-I-3A1-40-28, I-3B 1-1-I-3B1-40-28, I-3C 1-1-I-3C1-40-28, I-3D 1-1-I-3D1-40-28, I-3E 1-1-I-3E1-40-28, I-3F1-1-1-I-3F1-40-28, I-3G 1-1-I-3G1-40-28, I-3H 1-1-I-3H1-40-28, I-3I 1-1-I-3I1-40-28, I-3J 1-1-I-3J1-40-28, I-3K 1-1-I-3K1-40-28, I-3L 1-1-I-3L1-40-28, I-3M 1-1-I-3M1-40-28, I-3N 1-1-I-3N1-40-28, I-3O 1-1-I-3O1-40-28, I-3P 1-1-I-3P1-40-28, I-3Q 1-1-I-3Q1-40-28, I-3R 1-1-I-3R1-40-28, I-3S 1-1-I-3S1-40-28, I-3T 1-1-I-3T1-40-28, I-3U 1-1-I-3U1-40-28, I-3V 1-1-I-3V1-40-28, I-3W 1-1-I-3W1-40-28, I-3X 1-1-I-3X 1-40-28; I-4A represents a compound which is numbered sequentially as I-4A1-1-1-I-4A1-40-28, I-4B 1-1-I-4B1-40-28, I-4C 1-1-I-4C1-40-28, I-4D 1-1-I-4D1-40-28, I-4E 1-1-I-4E1-40-28, I-4F1-1-1-I-4F1-40-28, I-4G 1-1-I-4G1-40-28, I-4H 1-1-I-4H1-40-28, I-4I1-1-1-I-4I1-40-28, I-4J 1-1-I-4J1-40-28, I-4K 1-1-I-4K1-40-28, I-4L 1-1-I-4L1-40-28, I-4M 1-1-I-4M1-40-28, I-4N1-1-1-I-4N1-40-28, I-4O1-1-1-I-4O1-40-28, I-4P 1-1-I-4P1-40-28, I-4Q1-1-1-I-4Q1-40-28, I-4R1-1-1-I-4R1-40-28, I-4S 1-1-I-4S1-40-28, I-4T 1-1-I-4T1-40-28, I-4U 1-1-I-4U1-40-28, I-4V 1-1-I-4V1-40-28, I-4W 1-1-I-4W1-40-28、I-4X1-1-1-I-4X1-40-28；

When R is CH₂CH₃，R¹The substituent group is shown in Table 3, the Acid is shown in Table 6, the I-3A represents the compound number sequentially of I-3A 2-1-I-3A 2-40-28, I-3B 2-1-I-3B 2-40-28, I-3C 2-1-I-3C 2-40-28, I-3D 2-1-I-3D 2-40-28, I-3E 2-1-I-3E 2-40-28, I-3F2-1-1-I-3F2-40-28, I-3G 2-1-I-3G 2-40-28, I-3H 2-1-I-3H 2-40-28, I-3I 2-1-I-3I 2-40-28, I-3J 2-1-I-3J 2-40-28, I-3K 2-1-I-3K 2-40-28, I-3L 2-1-I-3L 2-40-28, I-3M 2-1-I-3M 2-40-28, I-3N 2-1-I-3N 2-40-28, I-3O 2-1-I-3O 2-40-28, I-3P 2-1-I-3P 2-40-28, I-3Q 2-1-I-3Q 2-40-28, I-3R 2-1-I-3R 2-40-28, I-3S 2-1-I-3S 2-40-28, I-3T 2-1-I-3T 2-40-28, I-3U 2-1-I-3U 2-40-28, I-3V 2-1-I-3V 2-40-28, I-3W 2-1-I-3W 2-40-28, I-3X 2-1-I-3X 2-40-28; I-4A represents a compound which is numbered sequentially as I-4A2-1-1-I-4A2-40-28, I-4B 2-1-I-4B 2-40-28, I-4C 2-1-I-4C 2-40-28, I-4D 2-1-I-4D 2-40-28, I-4E 2-1-I-4E 2-40-28, I-4F2-1-1-I-4F2-40-28, I-4G 2-1-I-4G 2-40-28, I-4H 2-1-I-4H 2-40-28, I-4I2-1-1-I-4I2-40-28, I-4J 2-1-I-4J 2-40-28, I-4K 2-1-I-4K 2-40-28, I-4L 2-1-I-4L 2-40-28, I-4M 2-1-I-4M 2-40-28, I-4N2-1-1-I-4N2-40-28, I-4O2-1-1-I-4O2-40-28, I-4P 2-1-I-4P 2-40-28, I-4Q2-1-1-I-4Q2-40-28, I-4R2-1-1-I-4R2-40-28, I-4S 2-1-I-4S 2-40-28, I-4T 2-1-I-4T 2-40-28, I-4U 2-1-I-4U 2-40-28, I-4V 2-1-I-4V 2-40-28, I-4W 2-1-I-4W 2-40-28, I-4X 2-1-I-4X 2-40-28;

when R is CHF₂，R¹The substituent group is shown in Table 3, the Acid is shown in Table 6, the I-3A represents the compound number sequentially of I-3A 3-1-I-3A 3-40-28, I-3B 3-1-I-3B 3-40-28, I-3C 3-1-I-3C 3-40-28, I-3D 3-1-I-3D 3-40-28, I-3E 3-1-I-3E 3-40-28, I-3F3-1-1-I-3F3-40-28, I-3G 3-1-I-3G 3-40-28, I-3H 3-1-I-3H 3-40-28, I-3I 3-1-I-3I 3-40-28, I-3J 3-1-I-3J 3-40-28, I-3K 3-1-I-3K 3-40-28, I-3L 3-1-I-3L 3-40-28, I-3M 3-1-I-3M 3-40-28, I-3N 3-1-I-3N 3-40-28, I-3O 3-1-I-3O 3-40-28, I-3P 3-1-I-3P 3-40-28, I-3Q 3-1-I-3Q 3-40-28, I-3R3-1-1-I-3R3-40-28, I-3S3-1-1-I-3S3-40-28, I-3T 3-1-I-3T 3-40-28, I-3U 3-1-I-3U 3-40-28, I-3V 3-1-I-3V 3-40-28, I-3W3-1-1-I-3W3-40-28, I-3X3-1-1-I-3X 3-40-28; I-4A represents a compound which is numbered sequentially as I-4A3-1-1-I-4A3-40-28, I-4B 3-1-I-4B 3-40-28, I-4C 3-1-I-4C 3-40-28, I-4D 3-1-I-4D 3-40-28, I-4E 3-1-I-4E 3-40-28, I-4F3-1-1-I-4F3-40-28, I-4G 3-1-I-4G 3-40-28, I-4H 3-1-I-4H 3-40-28, I-4I3-1-1-I-4I3-40-28, I-4J 3-1-I-4J 3-40-28, I-4K 3-1-I-4K 3-40-28, I-4L 3-1-I-4L 3-40-28, I-4M 3-1-I-4M 3-40-28, I-4N3-1-1-I-4N3-40-28, I-4O3-1-1-I-4O3-40-28, I-4P 3-1-I-4P 3-40-28, I-4Q3-1-1-I-4Q3-40-28, I-4R3-1-1-I-4R3-40-28, I-4S 3-1-I-4S 3-40-28, I-4T 3-1-I-4T 3-40-28, I-4U 3-1-I-4U 3-40-28, I-4V 3-1-I-4V 3-40-28, I-4W 3-1-I-4W 3-40-28, I-4X 3-1-I-4X 3-40-28;

when R ═ CF₃，R¹The substituent group is shown in Table 3, the Acid is shown in Table 6, the I-3A represents the compound number sequentially of I-3A 4-1-I-3A 4-40-28, I-3B 4-1-I-3B 4-40-28, I-3C 4-1-I-3C 4-40-28, I-3D 4-1-I-3D 4-40-28, I-3E 4-1-I-3E 4-40-28, I-3F4-1-1-I-3F4-40-28, I-3G 4-1-I-3G 4-40-28, I-3H 4-1-I-3H 4-40-28, I-3I 4-1-I-3I 4-40-28, I-3J 4-1-I-3J 4-40-28, I-3K 4-1-I-3K 4-40-28, I-3L 4-1-I-3L 4-40-28, I-3M 4-1-I-3M 4-40-28, I-3N 4-1-I-3N 4-40-28, I-3O 4-1-I-3O 4-40-28, I-3P 4-1-I-3P 4-40-28, I-3Q 4-1-I-3Q 4-40-28, I-3R 4-1-I-3R 4-40-28, I-3S 4-1-I-3S 4-40-28, I-3T 4-1-I-3T 4-40-28, I-3U 4-1-I-3U 4-40-28, I-3V 4-1-I-3V 4-40-28, I-3W 4-1-I-3W 4-40-28, I-3X 4-1-I-3X 4-40-28; I-4A represents a compound which is numbered sequentially as I-4A4-1-1-I-4A4-40-28, I-4B 4-1-I-4B 4-40-28, I-4C 4-1-I-4C 4-40-28, I-4D 4-1-I-4D 4-40-28, I-4E 4-1-I-4E 4-40-28, I-4F4-1-1-I-4F4-40-28, I-4G 4-1-I-4G 4-40-28, I-4H 4-1-I-4H 4-40-28, I-4I4-1-1-I-4I4-40-28, I-4J 4-1-I-4J 4-40-28, I-4K 4-1-I-4K 4-40-28, I-4L 4-1-I-4L 4-40-28, I-4M 4-1-I-4M 4-40-28, I-4N4-1-1-I-4N4-40-28, I-4O4-1-1-I-4O4-40-28, I-4P 4-1-I-4P 4-40-28, I-4Q4-1-1-I-4Q4-40-28, I-4R4-1-1-I-4R4-40-28, I-4S 4-1-I-4S 4-40-28, I-4T 4-1-I-4T 4-40-28, I-4U 4-1-I-4U 4-40-28, I-4V 4-1-I-4V 4-40-28, I-4W 4-1-I-4W 4-40-28, I-4X 4-1-I-4X 4-40-28;

when R is CHClCH₃，R¹The substituent group is shown in Table 3, the Acid is shown in Table 6, the I-3A represents the compound number sequentially of I-3A 5-1-I-3A 5-40-28, I-3B 5-1-I-3B 5-40-28, I-3C 5-1-I-3C 5-40-28, I-3D 5-1-I-3D 5-40-28, I-3E 5-1-I-3E 5-40-28, I-3F5-1-1-I-3F5-40-28, I-3G 5-1-I-3G 5-40-28, I-3H 5-1-I-3H 5-40-28, I-3I 5-1-I-3I 5-40-28, I-3J 5-1-I-3J 5-40-28, I-3K 5-1-I-3K 5-40-28, I-3L 5-1-I-3L 5-40-28, I-3M 5-1-I-3M 5-40-28, I-3N 5-1-I-3N 5-40-28, I-3O 5-1-I-3O 5-40-28, I-3P 5-1-I-3P 5-40-28, I-3Q 5-1-I-3Q 5-40-28, I-3R 5-1-I-3R 5-40-28, I-3S 5-1-I-3S 5-40-28, I-3T 5-1-I-3T 5-40-28, I-3U 5-1-I-3U 5-40-28, I-3V 5-1-I-3V 5-40-28, I-3W 5-1-I-3W 5-40-28, I-3X 5-1-I-3X 5-40-28; I-4A represents a compound which is numbered sequentially as I-4A5-1-1-I-4A5-40-28, I-4B 5-1-I-4B 5-40-28, I-4C 5-1-I-4C 5-40-28, I-4D 5-1-I-4D 5-40-28, I-4E 5-1-I-4E 5-40-28, I-4F5-1-1-I-4F5-40-28, I-4G 5-1-I-4G 5-40-28, I-4H 5-1-I-4H 5-40-28, I-4I5-1-1-I-4I5-40-28, I-4J 5-1-I-4J 5-40-28, I-4K 5-1-I-4K 5-40-28, I-4L 5-1-I-4L 5-40-28, I-4M 5-1-I-4M 5-40-28, I-4N5-1-1-I-4N5-40-28, I-4O5-1-1-I-4O5-40-28, I-4P 5-1-I-4P 5-40-28, I-4Q5-1-1-I-4Q5-40-28, I-4R5-1-1-I-4R5-40-28, I-4S 5-1-I-4S 5-40-28, I-4T 5-1-I-4T 5-40-28, I-4U 5-1-I-4U 5-40-28, I-4V 5-1-I-4V 5-40-28, I-4W 5-1-I-4W 5-40-28, I-4X 5-1-I-4X 5-40-28;

when R is CHFCH₃，R¹The substituent group is shown in Table 3, the Acid is shown in Table 6, the I-3A represents the compound number sequentially of I-3A 6-1-I-3A 6-40-28, I-3B 6-1-I-3B 6-40-28, I-3C 6-1-I-3C 6-40-28, I-3D 6-1-I-3D 6-40-28, I-3E 6-1-I-3E 6-40-28, I-3F6-1-1-I-3F6-40-28, I-3G 6-1-I-3G 6-40-28, I-3H 6-1-I-3H 6-40-28, I-3I 6-1-I-3I 6-40-28, I-3J 6-1-I-3J 6-40-28, I-3K 6-1-I-3K 6-40-28, I-3L 6-1-I-3L 6-40-28, I-3M 6-1-I-3M 6-40-28, I-3N 6-1-I-3N 6-40-28, I-3O 6-1-I-3O 6-40-28, I-3P 6-1-I-3P 6-40-28, I-3Q 6-1-I-3Q 6-40-28, I-3R 6-1-I-3R 6-40-28, I-3S 6-1-I-3S 6-40-28, I-3T 6-1-I-3T 6-40-28, I-3U 6-1-I-3U 6-40-28, I-3V 6-1-I-3V 6-40-28, I-3W 6-1-I-3W 6-40-28, I-3X 6-1-I-3X 6-40-28; I-4A represents the compound with the serial numbers of I-4A6-1-1-I-4A6-40-28 and I-4B6-1-1-I-4B6-40-28、I-4C6-1-1-I-4C6-40-28、I-4D6-1-1-I-4D6-40-28、I-4E6-1-1-I-4E6-40-28、I-4F6-1-1-I-4F6-40-28、I-4G6-1-1-I-4G6-40-28、I-4H6-1-1-I-4H6-40-28、I-4I6-1-1-I-4I6-40-28、I-4J6-1-1-I-4J6-40-28、I-4K6-1-1-I-4K6-40-28、I-4L6-1-1-I-4L6-40-28、I-4M6-1-1-I-4M6-40-28、I-4N6-1-1-I-4N6-40-28、I-4O6-1-1-I-4O6-40-28、I-4P6-1-1-I-4P6-40-28、I-4Q6-1-1-I-4Q6-40-28、I-4R6-1-1-I-4R6-40-28、I-4S6-1-1-I-4S6-40-28、I-4T6-1-1-I-4T6-40-28、I-4U6-1-1-I-4U6-40-28、I-4V6-1-1-I-4V6-40-28、I-4W6-1-1-I-4W6-40-28、I-4X6-1-1-I-4X6-40-28；

When R is cyclopropyl, R¹The substituent group is shown in Table 3, the Acid is shown in Table 6, the I-3A represents the compound number sequentially of I-3A 7-1-I-3A 7-40-28, I-3B 7-1-I-3B 7-40-28, I-3C 7-1-I-3C 7-40-28, I-3D 7-1-I-3D 7-40-28, I-3E 7-1-I-3E 7-40-28, I-3F7-1-1-I-3F7-40-28, I-3G 7-1-I-3G 7-40-28, I-3H 7-1-I-3H 7-40-28, I-3I 7-1-I-3I 7-40-28, I-3J 7-1-I-3J 7-40-28, I-3K 7-1-I-3K 7-40-28, I-3L 7-1-I-3L 7-40-28, I-3M 7-1-I-3M 7-40-28, I-3N 7-1-I-3N 7-40-28, I-3O 7-1-I-3O 7-40-28, I-3P 7-1-I-3P 7-40-28, I-3Q 7-1-I-3Q 7-40-28, I-3R 7-1-I-3R 7-40-28, I-3S 7-1-I-3S 7-40-28, I-3T 7-1-I-3T 7-40-28, I-3U 7-1-I-3U 7-40-28, I-3V 7-1-I-3V 7-40-28, I-3W 7-1-I-3W 7-40-28, I-3X 7-1-I-3X 7-40-28; I-4A represents a compound which is numbered sequentially as I-4A7-1-1-I-4A7-40-28, I-4B 7-1-I-4B 7-40-28, I-4C 7-1-I-4C 7-40-28, I-4D 7-1-I-4D 7-40-28, I-4E 7-1-I-4E 7-40-28, I-4F7-1-1-I-4F7-40-28, I-4G 7-1-I-4G 7-40-28, I-4H 7-1-I-4H 7-40-28, I-4I7-1-1-I-4I7-40-28, I-4J 7-1-I-4J 7-40-28, I-4K 7-1-I-4K 7-40-28, I-4L 7-1-I-4L 7-40-28, I-4M 7-1-I-4M 7-40-28, I-4N7-1-1-I-4N7-40-28, I-4O7-1-1-I-4O7-40-28, I-4P 7-1-I-4P 7-40-28, I-4Q7-1-1-I-4Q7-40-28, I-4R7-1-1-I-4R7-40-28, I-4S 7-1-I-4S 7-40-28, I-4T 7-1-I-4T 7-40-28, I-4U 7-1-I-4U 7-40-28, I-4V 7-1-I-4V 7-40-28, I-4W 7-1-I-4W 7-40-28, I-4X 7-1-I-4X 7-40-28;

when R is 2-allyl, R¹The substituent group is shown in Table 3, the Acid is shown in Table 6, the I-3A represents the compound number which is sequentially I-3A8-1-1-I-3A8-40-28, I-3B8-1-1-I-3B8-40-28 and I-3C8-1-1-I-3C8-40-28, I-3D 8-1-I-3D 8-40-28, I-3E 8-1-I-3E 8-40-28, I-3F 8-1-I-3F 8-40-28, I-3G 8-1-I-3G 8-40-28, I-3H8-1-1-I-3H8-40-28, I-3I 8-1-I-3I 8-40-28, I-3J 8-1-I-3J 8-40-28, I-3K 8-1-I-3K 8-40-28, I-3L 8-1-I-3L 8-40-28, I-3M 8-1-I-3M 8-40-28, I-3N 8-1-I-3N 8-40-28, I-3O 8-1-I-3O 8-40-28, I-3P 8-1-I-3P 8-40-28, I-3Q8-1-1-I-3Q8-40-28, I-3R8-1-1-I-3R8-40-28, I-3S 8-1-I-3S 8-40-28, I-3T 8-1-I-3T 8-40-28, I-3T 3542-1-I-3T 8-40-28, I-3U8-1-1-I-3U8-40-28, I-3V8-1-1-I-3V8-40-28, I-3W 8-1-I-3W 8-40-28, I-3X 8-1-I-3X 8-40-28; I-4A represents a compound which is numbered sequentially as I-4A8-1-1-I-4A8-40-28, I-4B 8-1-I-4B 8-40-28, I-4C 8-1-I-4C 8-40-28, I-4D 8-1-I-4D 8-40-28, I-4E 8-1-I-4E 8-40-28, I-4F8-1-1-I-4F8-40-28, I-4G 8-1-I-4G 8-40-28, I-4H 8-1-I-4H 8-40-28, I-4I8-1-1-I-4I8-40-28, I-4J 8-1-I-4J 8-40-28, I-4K 8-1-I-4K 8-40-28, I-4L 8-1-I-4L 8-40-28, I-4M 8-1-I-4M 8-40-28, I-4N8-1-1-I-4N8-40-28, I-4O8-1-1-I-4O8-40-28, I-4P 8-1-I-4P 8-40-28, I-4Q8-1-1-I-4Q8-40-28, I-4R8-1-1-I-4R8-40-28, I-4S 8-1-I-4S 8-40-28, I-4T 8-1-I-4T 8-40-28, I-4U 8-1-I-4U 8-40-28, I-4V 8-1-I-4V 8-40-28, I-4W 8-1-I-4W 8-40-28, I-4X 8-1-I-4X 8-40-28;

when R is 2-propargyl, R¹The substituent group is shown in Table 3, the Acid is shown in Table 6, the I-3A represents the compound number sequentially of I-3A 9-1-I-3A 9-40-28, I-3B 9-1-I-3B 9-40-28, I-3C 9-1-I-3C 9-40-28, I-3D 9-1-I-3D 9-40-28, I-3E 9-1-I-3E 9-40-28, I-3F9-1-1-I-3F9-40-28, I-3G 9-1-I-3G 9-40-28, I-3H 9-1-I-3H 9-40-28, I-3I 9-1-I-3I 9-40-28, I-3J 9-1-I-3J 9-40-28, I-3K 9-1-I-3K 9-40-28, I-3L 9-1-I-3L 9-40-28, I-3M 9-1-I-3M 9-40-28, I-3N 9-1-I-3N 9-40-28, I-3O 9-1-I-3O 9-40-28, I-3P 9-1-I-3P 9-40-28, I-3Q 9-1-I-3Q 9-40-28, I-3R 9-1-I-3R 9-40-28, I-3S 9-1-I-3S 9-40-28, I-3T 9-1-I-3T 9-40-28, I-3U 9-1-I-3U 9-40-28, I-3V 9-1-I-3V 9-40-28, I-3W 9-1-I-3W 9-40-28, I-3X 9-1-I-3X 9-40-28; I-4A represents a compound which is numbered sequentially as I-4A9-1-1-I-4A9-40-28, I-4B 9-1-I-4B 9-40-28, I-4C9-1-1-I-4C9-40-28, I-4D 9-1-I-4D 9-40-28, I-4E 9-1-I-4E 9-40-28, I-4F 9-1-I-4F 9-40-28, I-4G 9-1-I-4G 9-40-28,I-4H9-1-1-I-4H9-40-28、I-4I9-1-1-I-4I9-40-28、I-4J9-1-1-I-4J9-40-28、I-4K9-1-1-I-4K9-40-28、I-4L9-1-1-I-4L9-40-28、I-4M9-1-1-I-4M9-40-28、I-4N9-1-1-I-4N9-40-28、I-4O9-1-1-I-4O9-40-28、I-4P9-1-1-I-4P9-40-28、I-4Q9-1-1-I-4Q9-40-28、I-4R9-1-1-I-4R9-40-28、I-4S9-1-1-I-4S9-40-28、I-4T9-1-1-I-4T9-40-28、I-4U9-1-1-I-4U9-40-28、I-4V9-1-1-I-4V9-40-28、I-4W9-1-1-I-4W9-40-28、I-4X9-1-1-I-4X9-40-28。

The compounds of the present invention may exist in the form of one or more isomers. Isomers include enantiomers, diastereomers, geometric isomers and cis-trans isomers. The compounds of formula (I) according to the invention, in which the carbon-carbon double bonds are linked to different substituents, may form geometrical isomers (different configurations in Z and E, respectively), and the invention includes both the Z and E isomers and mixtures thereof in any proportion. The compound shown in the formula (I) forms stereoisomers (R and S respectively represent different configurations) due to the fact that four different substituents are connected to one carbon atom of the compound, and the compound comprises an R-type isomer, an S-type isomer and a mixture of the R-type isomer and the S-type isomer in any proportion. The invention relates to a compound shown in formula (I), wherein cis-trans isomers (different configurations are respectively represented by cis and trans) are formed by connecting more than 2 substituents on cycloalkyl or heterocycloalkyl, and the invention comprises cis-trans isomers and mixtures of the cis-trans isomers in any proportion.

The stereoisomer of the invention can be prepared by the general formula I-1A, I-1B, I-1C, I-1D, I-1E, I-1F, I-1G, I-1H, I-1I, I-1J, I-1K, I-1L, I-1M, I-1N, I-1O, I-1P, I-1Q, I-1R, I-1S, I-1T, I-1U, I-1V, I-1W, I-1X, I-2A, I-2B, I-2C, I-2D, I-2E, I-2F, I-2G, I-2H, I-2I, I-2J, I-2K, I-2L, I-2M, I-2N, I-2O, I-2P, I-2Q, I-2R, I-2S, I-2T, I-2U, I-2V, I-2W or I-2X, but the invention is not limited thereto. The compound shown by the formula I-1A, I-1D, I-1G, I-1J, I-1M, I-1P, I-1S, I-1V, I-2A, I-2D, I-2G, I-2J, I-2M, I-2P, I-2S or I-2V represents a mixture of R-type isomer and S-type isomer in any proportion; the compound shown in formula I-1B, I-1E, I-1H, I-1K, I-1N, I-1Q, I-1T, I-1W, I-2B, I-2E, I-2H, I-2K, I-2N, I-2Q, I-2T or I-2W represents S-type isomer; the compound shown in formula I-1C, I-1F, I-1I, I-1L, I-1O, I-1R, I-1U, I-1X, I-2C, I-2F, I-2I, I-2L, I-2O, I-2R, I-2U or I-2X represents R-type isomer.

The invention also relates to a composition for controlling pests and harmful bacteria, comprising a biologically effective amount of a compound of formula (I) and at least one further diluent selected from the group consisting of surfactants, solid diluents and liquid diluents.

The invention also relates to a composition for controlling pests and harmful bacteria, comprising a biologically effective amount of a compound of formula (I) and an effective amount of at least one further biologically active compound or agent.

The invention also relates to a method for controlling pests, harmful bacteria, which comprises contacting a biologically effective amount of a compound of formula (I) with the pests, harmful bacteria or their environment. Also disclosed is a method for controlling pests or harmful bacteria by contacting the pests or harmful bacteria or their environment with a biologically effective amount of a compound of formula (I) or a mixture comprising a compound of formula (I) and a biologically effective amount of at least one additional compound or agent.

The compounds of formula (I) according to the invention have a broad spectrum of activity: some compounds can be used for preventing and controlling harmful germs and pests; and some compounds have high biological activity to some target harmful germs, so that good effect can be obtained under low dosage.

Preferred compositions of the invention are those containing the preferred compounds described above. Preferred methods are those using the preferred compounds described above.

The compounds of the present invention are further illustrated by, but not limited to, the compounds of formula (I) listed in Table 7. The melting points given in the present invention are uncorrected. When the compound of formula (I) of the present invention is a viscous solid, some viscous solids will solidify to form a non-viscous solid after standing; when the compound of formula (I) of the present invention is a viscous liquid, some of the viscous liquid will solidify after standing; the compound of the invention can be observed in LC-MS (APCI) to obtain a molecular ion peak; process for preparing compounds¹H NMR internal Standard TMS, CDCl₃As a solvent.

TABLE 7

The salts of the compounds of the present invention are illustrated in Table 8, but are not intended to limit the invention.

Table 8 salts of some of the compounds

The compound of formula (I) of the present invention can be obtained by the reaction formula 1 shown below; the (II) in the reaction formula 1 can be obtained by the reaction formula 2 shown below; (IV) in the reaction formula 2 can be obtained by the reaction formula 3 shown below; (III) in the reaction formula 1, (V) in the reaction formula 2, (VI) and (VIII) in the reaction formula 3 can be synthesized by purchasing or referring to relevant documents; l in the reaction formula 1, the reaction formula 2 and the reaction formula 3 may be the same or different and represents a leaving group of fluorine, chlorine, bromine or iodine, etc., R in the reaction formula 3²A salt of the compound represented by the formula (I) may be obtained by the reaction formula 4 shown below; the Acid in the reaction formula 4 is an organic Acid or an inorganic Acid, and other substituents are as defined above unless otherwise specified.

Reaction formula 1:

reaction formula 2:

reaction formula 3:

reaction formula 4:

the compounds of formula (I) may be prepared by (scheme 1): reacting a compound of formula (II) with a compound of formula (III) in a suitable solvent such as dichloromethane, dichloroethane, toluene, xylene, N-dimethylformamide, N-methylpyrrolidone, dimethylsulfoxide, pyridine, tetrahydrofuran, methanol, ethanol, isopropanol, acetone, butanone, methyl isobutyl ketone, acetonitrile, ethyl acetate, dioxane or the like, at a temperature of-10 ℃ to the reflux temperature of the system, in the absence of a base or in the presence of a suitable base, which may be selected from alkali metal hydrides such as sodium hydride, to obtain a compound of formula (I), and when the reaction is carried out in the presence of a base, the reaction may be accelerated; alkali metal hydroxides such as sodium hydroxide or potassium hydroxide; alkali metal carbonates such as sodium carbonate or potassium carbonate; alkali metal alkoxides such as sodium methoxide or sodium ethoxide; organic amines, such as pyridine, triethylamine or diisopropylethylamine.

The compound of formula (II) may be prepared as follows (scheme 2): reacting a compound of formula (IV) with a compound of formula (V) in a suitable solvent such as dichloromethane, dichloroethane, toluene, xylene, N-dimethylformamide, N-methylpyrrolidone, dimethylsulfoxide, pyridine, tetrahydrofuran, methanol, ethanol, isopropanol, acetone, butanone, methyl isobutyl ketone, acetonitrile, ethyl acetate, dioxane or the like at a temperature of-10 ℃ to the reflux temperature of the system in the absence of a base or a suitable base, which may be selected from alkali metal hydrides such as sodium hydride, to obtain a compound of formula (II), and when the reaction is carried out in the presence of a base, the reaction may be accelerated; alkali metal hydroxides such as sodium hydroxide or potassium hydroxide; alkali metal carbonates such as sodium carbonate or potassium carbonate; alkali metal alkoxides such as sodium methoxide or sodium ethoxide; organic amines, such as pyridine, triethylamine or diisopropylethylamine.

The compound of formula (IV) may be prepared by (reaction formula 3): reacting the compound of the formula (VI) with a chlorinating agent such as chlorine or sulfonyl chloride and the like at 0-50 ℃ in a solvent-free or suitable solvent such as ethyl acetate, dichloromethane, trichloromethane, dichloroethane, acetone, butanone or methyl isobutyl ketone and the like to obtain a compound of the formula (VII); reacting a compound of formula (VII) with a compound of formula (VIII) in a suitable solvent such as methanol, ethanol, propanol, isopropanol, dichloromethane, dichloroethane, toluene, xylene, N-dimethylformamide, N-methylpyrrolidone, dimethylsulfoxide, pyridine, tetrahydrofuran, acetone, methyl ethyl ketone or methyl isobutyl ketone, etc., in the presence of a suitable base such as triethylamine, pyridine, sodium methoxide, sodium ethoxide, sodium hydride, potassium hydroxide, potassium carbonate, sodium hydroxide or sodium carbonate, etc., at 5 ℃ to 50 ℃ to obtain a compound of formula (IX); reacting the compound of formula (IX) with a halogenating agent such as phosphorus oxychloride or phosphorus oxybromide in the presence of a suitable base such as triethylamine, pyridine, sodium methoxide, sodium ethoxide, sodium hydride, potassium hydroxide, potassium carbonate, sodium hydroxide or sodium carbonate to obtain a compound of formula (IV);

salts of compounds of formula (I) may be prepared by (equation 4): reacting the compound of the formula (I) with Acid at the temperature of 0-system reflux temperature in one or two suitable solvents selected from dichloromethane, dichloroethane, trichloromethane, toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, N-dimethylformamide, tetrahydrofuran, ethyl acetate, methanol, ethanol, isopropanol, dioxane and the like to obtain the compound salt of the formula (I).

Specific synthetic methods are set forth in more detail in the examples below.

The compound of formula (I) provided by the invention has broad-spectrum bioactivity at the dosage of 7.5-2250 g of active ingredient per hectare, and can be used for preventing and treating harmful germs and harmful insects or mites. Some compounds have good harmful germ prevention and treatment effects, and can obtain good effects at very low dosage.

The compound of formula (I) provided by the invention has bioactivity, and the compound has good bioactivity, and particularly shows activity in the aspects of preventing and controlling agricultural, horticultural, flower and sanitary pests and harmful bacteria. Pests as used herein include, but are not limited to:

harmful pathogenic bacteria: phytophthora species, erysiphe species, gibberella species, venturia species, sclerotinia species, rhizoctonia species, botrytis species, pyricularia species, fusarium species. Such as rice blast (Pyricularia oryzae); stripe rust (Puccinia striiformis), leaf rust (Puccinia recondita); barley and wheat powdery mildew (Erysiphe graminis), cucumber powdery mildew (Sphaerotheca fuligena), apple powdery mildew (podosphaea leucotricha) and grape powdery mildew (podosphaea leucotricha); sheath and glume blight of wheat (Septoria nodorum). Helminthosporium, Mortierella, Sclerotiella herpotrichoides, Pseudocercospora herpotrichoides, and wheat take-all (Gaeumunnomyces graminis) on cereals. Cercospora arachidicola (Cercospora arachidicola) and Cercospora black spot (Cercospora personata); apple ring rot pathogen (Botryosphaeria berenggiana f.sp. piricola), apple rot pathogen (cytopora sp.); urospora disease on beet, soybean and rice. Tomato, cucumber, grape gray mold (Botrytis cinerea). Diseases of the genus Geobacillus on vegetables such as cucumber. Anthracnose in cucumber, apple scab, cucumber downy mildew, grape downy mildew, blight in potato and tomato, the monad Thanatephorus cupmeris on rice and other rhizoctonia species on other hosts such as wheat and barley, vegetables; sclerotinia sclerotiorum (sclerotiorum); wheat scab (Gibberella zeae); phytophthora capsici (Phytophythora capsicii).

Harmful insects: lepidopteran pests such as oriental armyworm, prodenia litura, diamond back moth, beet armyworm, cabbage looper, orthopteran such as blattaria, thysanoptera such as cotton thrips, rice thrips, melon thrips, homopteran such as leafhopper, plant hopper, aphid, hymenopteran such as leaf bee larva, dipteran such as aedes, culex, fly; acarina pest mites such as Panonychus citri, Tetranychus gossypii, Tetranychus urticae, etc.

The compounds of formula (I) of the present invention are effective for controlling pests, harmful bacteria, alone, and they can also be used together with other biochemical substances such as insecticides, nematocides, acaricides and bactericides.

Agricultural formulations containing the compound of formula (I) as an active ingredient provided by the present invention may be formulated into any desired dosage form, such as dry compressed granules, flowable compositions, granules, wettable powders, water dispersible granules, emulsifiable concentrates, powders, powder concentrates, microemulsions, suspensions, emulsifiable concentrates, aqueous emulsions, soluble liquids, aqueous solutions, dispersible liquids, suitable adjuvants including carrier diluents and other adjuvants such as spreaders, emulsifiers, wetting agents, dispersants, stickers and disintegrants. These formulations comprise the compounds of the present invention in admixture with an inert, pharmacologically acceptable solid or liquid diluent.

Examples of the compositions of the present invention may also be formulated into any desired dosage form such as dry compressed granules, flowable compositions, granules, wettable powders, water dispersible granules, emulsifiable concentrates, dusts, powdered concentrates, microemulsions, suspensions, emulsifiable concentrates, emulsions in water, soluble liquids, mists, dispersible liquids, suitable adjuvants including carrier diluents) and other adjuvants such as spreaders, emulsifiers, wetting agents, dispersants, stickers and disintegrants. These formulations comprise the compounds of the present invention in admixture with an inert, pharmacologically acceptable solid or liquid diluent.

The present invention will be further described with reference to the following examples, but the present invention is not limited thereto.

Synthetic examples

EXAMPLE 1 this example illustrates the preparation of Compound I-1B3-1

Dropwise adding sulfonyl chloride (0.33mol) into a solution of ethyl difluoroacetoacetate (0.30mol) and dichloromethane (50mL) at the temperature of-5 ℃ under the stirring condition, and naturally heating to room temperature to react completely after dropwise adding. The reaction solution was poured into ice water, the organic layer was separated, the aqueous layer was extracted with dichloromethane, the organic phases were combined and dried over anhydrous sodium sulfate, and concentrated under reduced pressure to give the title product as a pale yellow liquid which was used directly in the next reaction.

Dropwise adding 30% methanol solution of sodium methoxide (0.63mol) into a solution of formamidine acetate (0.33mol) and methanol (50mL) at 5-10 ℃ under the stirring condition, continuously stirring for 2-3h after dropwise adding, dropwise adding the obtained ethyl 2-chloro-3-oxo-4, 4-difluorobutyrate, and naturally heating to room temperature for reaction till the reaction is complete. After removing methanol, ethyl acetate was added, insoluble matter was filtered off, and the filtrate was concentrated to give 25.60g of the title product as a yellow solid to be used directly in the next reaction.

Adding 5-chloro-6-difluoromethyl pyrimidine-4-ol (0.15mol) into phosphorus oxychloride (0.35mol) in batches at 0-5 ℃ under the condition of stirring, and dropwise adding triethylamine (0.17mol) after completely dissolving. Naturally heating to room temperature, reacting for 6-10h until the reaction is complete, removing most of phosphorus oxychloride from the reactant, pouring into ice water, and adjusting the pH value to 7-8 by using potassium carbonate. After extraction with dichloromethane and drying of the organic layer over anhydrous sodium sulfate, the solvent was removed under reduced pressure to obtain 17.21g of the title compound.

(S) -1- ((5-chloro-6-difluoromethylpyrimidin-4-yl) amino) -2-propanol to a solution of 4, 5-dichloro-6-difluoromethylpyrimidine (20mmol) and potassium carbonate (30mmol) in tetrahydrofuran (15mL) at room temperature with stirring was added dropwise (S) 1-amino-2-propanol (24mmol) and the mixture was stirred for 15-30min and then warmed to 60-90 ℃ for completion of the reaction. The reaction mixture was cooled and poured into ice water, extracted with dichloromethane, and the organic layer was dried over anhydrous sodium sulfate, and the solvent was removed under reduced pressure to obtain the titled compound (2.36 g).

Adding sodium hydride (6mmol) in batches to a solution of (S) -1- ((5-chloro-6-difluoromethyl pyrimidin-4-yl) amino) -2-propanol (5mmol) in N, N-dimethylformamide (10mL) at 0-5 ℃ under stirring conditions, stirring for 15-30min, adding 2, 3-dichloropyridine (5mmol) in batches, and naturally heating to room temperature to react for 8-16h until the reaction is complete. The reaction mixture was poured into ice water, extracted with dichloromethane, and the organic layer was dried over anhydrous sodium sulfate, and the solvent was removed to give a crude product, which was subjected to column chromatography using petroleum ether and ethyl acetate (V/V ═ 20-30:1) to give the title compound 0.80 g.

EXAMPLE 2 this example illustrates the preparation of Compound I-2D3-1

Dropwise adding sulfonyl chloride (0.33mol) into a solution of ethyl difluoroacetoacetate (0.30mol) and dichloromethane (50mL) at the temperature of-5 ℃ under the stirring condition, and naturally heating to room temperature to react completely after dropwise adding. The reaction solution was poured into ice water, the organic layer was separated, the aqueous layer was extracted with dichloromethane, the organic phases were combined and dried over anhydrous sodium sulfate, and concentrated to give the title compound, which was used in the next reaction.

Dropwise adding a 30% methanol solution of sodium methoxide (0.63mol) into a solution of acetamidine hydrochloride (0.33mol) and methanol (50mL) at 5-10 ℃ under stirring, continuously stirring for 2-3h after dropwise adding, dropwise adding the obtained 2-chloro-3-oxo-4, 4-difluorobutyric acid ethyl ester, and naturally heating to room temperature to react completely. After removing methanol, ethyl acetate was added, insoluble matter was filtered off, and the filtrate was concentrated to give the title compound as a yellow solid (32.90 g) which was used directly in the next reaction.

Adding 5-chloro-2-methyl-6-difluoromethyl pyrimidine-4-ol (0.15mol) into phosphorus oxychloride (0.35mol) in batches at 0-5 ℃ under the condition of stirring, and dropwise adding triethylamine (0.17mol) after completely dissolving. Naturally heating to room temperature, reacting for 6-10h until the reaction is complete, removing most of phosphorus oxychloride from the reactant, pouring into ice water, and adjusting the pH value to 7-8 by using potassium carbonate. After extraction with dichloromethane and drying of the organic layer over anhydrous sodium sulfate, the solvent was removed under reduced pressure to give the title compound (20.66 g).

(RS) -1- ((5-chloro-2-methyl-6-difluoromethyl-pyrimidin-4-yl) amino) -2-propanol to a solution of 4, 5-dichloro-2-methyl-6-difluoromethyl-pyrimidine (20mmol) and potassium carbonate (30mmol) in tetrahydrofuran (15mL) at room temperature with stirring was added dropwise (RS) 1-amino-2-propanol (24mmol), stirred for 15-30min and then warmed to 60-90 ℃ for completion of the reaction. The reaction mixture was cooled and poured into ice water, extracted with dichloromethane, and the organic layer was dried over anhydrous sodium sulfate, and the solvent was removed under reduced pressure to obtain the titled compound (2.52 g).

Adding sodium hydride (6mmol) in batches to a solution of (RS) -1- ((5-chloro-2-methyl-6-difluoromethyl pyrimidine-4-yl) amino) -2-propanol (5mmol) in N, N-dimethylformamide (10mL) at 0-5 ℃ under stirring conditions, stirring for 15-30min, adding 2-chloro-5-trifluoromethylpyridine (5mmol) in batches, and naturally heating to room temperature to react for 8-16h until the reaction is complete. The reaction product was poured into ice water, extracted with dichloromethane, and the organic layer was dried over anhydrous sodium sulfate, and then the solvent was removed to give a crude product, which was subjected to column chromatography using ethyl acetate and petroleum ether to give the titled compound 0.87 g.

EXAMPLE 3 this example illustrates the preparation of hydrochloride salt I-4D3-1-1 of Compound I-2D3-1

Hydrochloride of (RS) -N- (2- ((5-trifluoromethylpyridin-2-yl) oxy) propyl) -5-chloro-2-methyl-6-difluoromethylpyrimidin-4-amine to a solution of (RS) -N- (2- ((5-trifluoromethylpyridin-2-yl) oxy) propyl) -5-chloro-2-methyl-6-difluoromethylpyrimidin-4-amine (2mmol) in ethyl acetate (10mL) at 15-25 ℃ with stirring was added hydrogen chloride (20mmol) and stirring was continued until complete reaction, excess hydrogen chloride and solvent were removed under reduced pressure, and the solvent was washed and further purified to give the title compound.

The yields in the examples are not optimized, and other compounds of the present invention can be synthesized by referring to examples 1 to 3, and if necessary, related references.

Formulation examples

Example 410% preparation of tall oil

Weighing a proper amount (10% by weight) of the compound of formula (I) provided by the invention, such as a compound I-2D3-1 in Table 1, a proper amount of cosolvent (such as ethyl acetate or acetone), a proper amount of pesticide auxiliary agent, a solvent (such as toluene) and the like, putting into a reaction kettle, firstly adding a certain amount of solvent (such as toluene) and defoamer, stirring for 10-30 min, then adding a proper amount of stabilizer, synergist, penetrant and the like, continuing stirring for 10-30 min, adjusting the pH value, then putting an effective amount of solvent into the kettle, uniformly stirring, and discharging to obtain 10% missible oil of the compound I-2D 3-1.

EXAMPLE 520 preparation of wettable powder

Weighing a proper amount (20% by weight) of the compound of the formula (I) provided by the invention, such as the compound I-2D3-1 in the table 1, sodium dodecyl sulfate (2% by weight), sodium lignosulfonate (10% by weight) and kaolin which is complemented to 100%, mixing together, and crushing in a crusher until the particles reach the standard.

Bioassay examples

The compound of the invention is subjected to biological activity screening tests such as sterilization, disinsection/acarid killing and the like, and partial test results are as follows.

Example 6 insecticidal Activity against aphids (Aphis fabae)

The dipping method comprises the following steps: dissolving the compound to be tested in a suitable solvent such as acetone or N, N-dimethylformamide, diluting with clear water containing 0.2% Tween80 emulsifier to desired concentration, setting blank containing no compound to be tested as control, and repeating the treatment for 3 times. The broad bean aphids are inoculated on the just-emerged bean seedlings, each plant is inoculated with more than 20 heads, then the bean seedlings and the test insects are soaked in the compound liquid medicine of the formula (I) of the invention, the bean seedlings are taken out after 5 seconds, the redundant liquid medicine is sucked, the bean seedlings are inserted into absorbent sponge and covered by a glass tube, the number of the living and dead insects is checked after 24 hours, and the average value is taken. Active mortality) is divided into A, B, C, D grades by percentage relative to a blank control, wherein 100% or more of mortality is more than or equal to 90% and is A grade, 90% or more of mortality is more than or equal to 70% and is B grade, 70% or more of mortality is more than or equal to 50% and is C grade, and 50% or more of mortality is more than or equal to 0 and is D grade. Some of the results are listed below:

at a concentration of 500mg/L, compounds I-1B3-1, I-1D2-1, I-1E3-1, I-1F3-1, I-1G2-1, I-1H3-1, I-1J2-1, I-1J3-1, I-1K3-1, I-1M3-1, I-1P3-1, I-1Q3-1, I-2D1-1, I-2D2-1, I-2D3-1, I-2E3-1, I-2F3-1, I-2G2-1, I-2G3-1, I-2H3-1, I-2J1-1, I-2J2-1, I-2J3-1, I-2K3-1, I-2P2-1, I-2P3-1 and the like have A-grade activity on aphids; under the same conditions, the activities of D2 and D4 on aphids are A grade, D6 is B grade, and D7 is C grade;

at the concentration of 200mg/L, the compounds I-1D2-1, I-1E3-1, I-1F3-1, I-1G2-1, I-1J2-1, I-1K3-1, I-2D2-1, I-2D3-1, I-2E3-1, I-2F3-1, I-2G2-1, I-2H3-1, I-2J2-1 and I-2K3-1 have class A activity on aphids;

at the concentration of 50mg/L, the compounds I-1D2-1, I-1G2-1, I-1J2-1, I-2D2-1, I-2D3-1, I-2E3-1, I-2F3-1, I-2G2-1, I-2H3-1, I-2J2-1, I-2K3-1 and the like have A-level activity on aphids;

at a concentration of 12.5mg/L, compounds I-1G2-1, I-1J2-1, I-2D2-1, I-2F3-1, I-2G2-1, I-2G3-1, I-2H3-1, I-2J2-1, I-2K3-1 and the like have class A activity on aphids;

I-1G2-1 and the like are selected for deep screening, and the results show that the compound I-2H3-1 and the like have LC on aphids₅₀The value is below 0.50mg/L, LC of I-2F3-1, I-2J3-1, I-2P3-1 and the like on aphid₅₀LC with value of 0.50-1.00mg/L, I-2D3-1 and I-2G3-1 for aphid₅₀LC with value of 1.00-1.50mg/L, for aphids, such as I-1J2-1, I-2E3-1, I-2G2-1, I-2J2-1 and I-2K3-1₅₀The value is 1.50-6.00 mg/L; LC of D2 against aphids under the same conditions₅₀LC of D4 on aphids with value higher than 2.00mg/L₅₀The value is higher than 8.00 mg/L.

Example 7 evaluation of acaricidal Activity against Tetranychus urticae

The method comprises the following steps: dissolving the compound in a suitable solvent such as N, N-dimethylformamide, diluting with water containing 0.2% Tween80 emulsifier to desired concentration, setting blank containing no compound to be detected as blank control, and repeating the treatment for 3 times; selecting bean seedlings with good growth vigor to inoculate red spiders, after the red spiders colonize, cutting the bean seedlings with mites, soaking the bean seedlings in the prepared liquid medicine of the compound shown in the formula (I) for 10 seconds, taking out the bean seedlings, absorbing the redundant liquid medicine by using filter paper, inserting the bean seedlings into a water-containing beaker, culturing the bean seedlings in an observation room, checking the number of the alive and dead mites after 48 hours, and adding 100 plus 200 mites on each bean seedling. The results were averaged. The activity was graded as in example 6. Some of the results are listed below:

at a concentration of 500mg/L, compounds I-1B3-1, I-1D2-1, I-1D3-1, I-1E3-1, I-1F3-1, I-1H3-1, I-1J2-1, I-1J3-1, I-1K3-1, I-1Q3-1, I-2D1-1, I-2D2-1, I-2D3-1, I-2E3-1, I-2F3-1, I-2G2-1, I-2G3-1, I-2H3-1, I-2J1-1, I-2J2-1, I-2J3-1, I-2K3-1, I-2P2-1, I-2P3-1 and I-2V2-1 have A-grade activity on red spider; under the same conditions, the activities of D2 and D4 on red spiders are A grade, D6 is B grade, and D7 is C grade;

at a concentration of 200mg/L, the compounds I-1J2-1, I-1K3-1, I-2D2-1, I-2D3-1, I-2F3-1, I-2G2-1, I-2H3-1, I-2J2-1, I-2P2-1 and I-2V2-1 have class A activity against red spider, and the compounds I-1D2-1, I-1H3-1 and I-2E3-1 have class B activity; under the same conditions, the activity of D2 on red spiders is A grade;

at the concentration of 50mg/L, the compound I-2J2-1 and the like have A-grade activity on red spider, I-1J2-1, I-2D2-1 and the like have B-grade activity, I-2G2-1, I-2V2-1 and the like have C-grade activity; under the same conditions, the activity of D2 on red spider is B grade;

at a concentration of 12.5mg/L, compound I-2J2-1 has class C activity against red spider; under the same conditions, the activities of D2 and D4 on red spider were of grade D.

Example 8 evaluation of biological Activity of armyworm (Mythimna separata)

A Potter spraying method: dissolving the compound to be detected in a suitable solvent such as N, N-dimethylformamide, diluting with clear water containing 0.2% Tween80 emulsifier to the desired concentration, and setting blank containing no compound to be detected as control. Fresh and tender corn leaves are cut into segments with basically consistent sizes and placed into a culture dish (phi 90mm) in which filter paper is placed in advance. Then 10 heads of mythimna separata larvae of 3 years old are inoculated into the dish, the dish is put under a Potter spray tower for quantitative spraying, the amount of the sprayed liquid medicine is 1ml, and the spraying is repeated for 3 times per concentration. And after the treatment is finished, covering the dish cover, placing the dish cover in a recovery room for culture, regularly observing, checking and recording the death condition of the test insects after 72 hours, calculating the death rate, and averaging the results. The activity was graded as in example 6. Some of the results are as follows:

at the concentration of 500mg/L, the compounds I-1J3-1, I-1K3-1, I-1P3-1, I-2D1-1, I-2F3-1, I-2G3-1, I-2J3-1, I-2K3-1 and I-2P3-1 have class A activity on armyworm, and the compounds I-1D3-1, I-1M3-1, I-1Q3-1 and I-2J1-1 have class B activity; under the same conditions, the activity of D4 on armyworm is grade A, and D2, D6 and D7 show no activity on armyworm.

At the concentration of 200mg/L, the compounds I-1K3-1, I-2F3-1, I-2J3-1, I-2K3-1, I-2P3-1 and the like have A-grade activity on armyworms; under the same conditions, the activity of D4 on armyworm is B grade;

at the concentration of 50mg/L, the compounds I-2J3-1, I-2P3-1 and the like have B-level activity on armyworm, and I-1K3-1, I-2F3-1 and the like have C-level activity; under the same conditions, the activity of D4 on armyworm is grade C;

at the concentration of 50mg/L, the compounds I-2J3-1, I-2P3-1 and the like have C-grade activity on armyworm; under the same conditions, D4 showed no significant activity against armyworm.

Example 9 fungicidal Activity against wheat powdery mildew (Erisiphe grimmins)

Pot culture method: dissolving the compound to be tested in a suitable solvent such as N, N-dimethylformamide, and diluting with sterile water containing 0.2% Tween80 emulsifier to desired concentration; taking pots with straight stems of about 15cm, sowing 20 plump and robust seeds of wheat in each pot, and allowing the wheat to grow into two leaves and one heart for testing; spraying the prepared wheat seedling plant with a medicament with a certain concentration, and inoculating germs after one day. Repeating the treatment for 3 times, and additionally setting a blank without the compound to be detected as a blank contrast and a commercial fungicide flusilazole as a commercial contrast; and (5) after the culture is carried out in a moisture-preserving and temperature-adapting way until blank control is carried out, checking the area of the lesion spots and calculating the control effect of the medicament. The activity is classified into A, B, C, D grades, wherein 100% and 90% of the control effect is grade A, 90% and 70% of the control effect is grade B, 70% and 50% of the control effect are grade C, and 50% and 0% of the control effect are grade D. Some of the results are as follows:

at the concentration of 500mg/L, the compounds I-1B3-1, I-1D2-1, I-1D3-1, I-1E3-1, I-1F3-1, I-1H3-1, I-1J2-1, I-1J3-1, I-1K3-1, I-1M3-1, I-1P3-1, I-1Q3-1, I-2D1-1, I-2D3-1, I-2E3-1, I-2F3-1, I-2G3-1, I-2J1-1, I-2J2-1, I-2J3-1, I-2K3-1, I-2P3-1 and the like have A-grade activity on wheat powdery mildew, I-2P2-1, I-2V2-1 and the like have B-level activity; under the same condition, the activity of D2 on wheat powdery mildew is grade C, D4, D6 and flusilazole are grade A, and the activity of D7 on wheat powdery mildew is less than grade A;

at the concentration of 100mg/L, the compounds I-1B3-1, I-1E3-1, I-1H3-1, I-1K3-1, I-1Q3-1, I-2D3-1, I-2E3-1, I-2F3-1, I-2J2-1, I-2K3-1 and I-2P3-1 have class A activity on wheat powdery mildew, and the compounds I-1D3-1, I-1F3-1, I-1J3-1, I-1P3-1, I-2J3-1, I-1M3-1, I-2P2-1 and the like have class B activity; under the same condition, the activity of D4 on wheat powdery mildew is grade D, and the activities of D6 and flusilazole are grade A;

at the concentration of 50mg/L, the compounds I-1E3-1, I-1H3-1, I-1K3-1, I-2D3-1, I-2E3-1, I-2F3-1, I-2J2-1, I-2K3-1 and the like have class A activity on wheat powdery mildew, and the compounds I-1B3-1, I-1D3-1, I-1Q3-1, I-2P3-1 and the like have class B activity;

I-1E3-1 and the like are selected for deep screening, and the results show that the ED of the compound I-2K3-1 and the like on wheat powdery mildew₅₀The value is less than 0.50mg/L, and ED of I-2E3-1 and the like on wheat powdery mildew₅₀ED of 0.50-1.00mg/L, I-1K3-1, etc. for wheat powdery mildew₅₀ED values of 1.00-2.00mg/L, I-1D3-1, I-1E3-1, I-1H3-1, I-1M3-1, I-2D3-1, I-2F3-1, I-2J2-1, I-2J3-1 and I-2P3-1, etc₅₀The value is 2.00-5.00 mg/L; ED of D6 and flusilazole against wheat powdery mildew under the same conditions₅₀The value was less than 2.00 mg/L.

Example 10 fungicidal Activity against corn rust Puccinia Polysora)

Pot culture method: dissolving the compound in a suitable solvent such as N, N-dimethylformamide, diluting with sterile water containing 0.2% Tween80 emulsifier to desired concentration, and setting blank containing no compound to be tested as blank control and commercial bactericide tebuconazole as commercial control; repeat for 4 times per treatment; cutting the leaf of corn with disease, washing off the spore with 0.05% Tween80 or other appropriate surfactant aqueous solution, filtering with 2-4 layers of gauze to obtain the product with concentration of 1 × 10⁵spore/mL of suspension; when the corn grows to 2 leaves and 1 heartSpraying the liquid medicine of the compound to be tested, spraying and inoculating the spore suspension after 1 day, transferring to a moisturizing cabinet after inoculation, wherein the relative humidity is more than 95%, the temperature is 20-22 ℃, and the illumination intensity is 5000-10000 Lux) under the low-light condition for culturing for 15-24 hours; and when the blank control disease leaf rate reaches more than 50%, investigating the disease condition of each treatment, and calculating the control effect. The activity was graded as in example 9.

The following are partial results:

at a concentration of 500mg/L, compounds I-1B3-1, I-1D2-1, I-1D3-1, I-1E3-1, I-1F3-1, I-1H3-1, I-1J2-1, I-1J3-1, I-1K3-1, I-1M3-1, I-1P3-1, I-1Q3-1, I-2D2-1, I-2D3-1, I-2E3-1, I-2F3-1, I-2G2-1, I-2G3-1, I-2H3-1, I-2J2-1, I-2J3-1, I-2K3-1, I-2P2-1, I-2P 53926-1, I-2P3-1, I-2V2-1 and the like have A-grade activity on corn rust, I-2J1-1 and the like have B-grade activity; under the same conditions, the activity of D2 on the corn rust is grade C, D4 and tebuconazole are grade A, D6 is grade B, and D7 is grade D;

at a concentration of 100mg/L, compounds I-1B3-1, I-1D3-1, I-1E3-1, I-1F3-1, I-1H3-1, I-1K3-1, I-1Q3-1, I-2D3-1, I-2E3-1, I-2F3-1, I-2H3-1, I-2J2-1, I-2J3-1, I-2K3-1, I-2P3-1 and I-2V2-1 have class A activity against corn rust, and I-2G3-1 has class B activity; under the same conditions, the activity of D4 on the corn rust is grade C, and D6 is grade B;

at the concentration of 50mg/L, the compounds I-1F3-1, I-1Q3-1, I-2D3-1, I-2E3-1, I-2F3-1, I-2J2-1, I-2J3-1, I-2K3-1 and I-2P3-1 have class A activity on corn rust, and the compounds I-1B3-1, I-1D3-1, I-1E3-1, I-2G3-1, I-1H3-1 and I-1K3-1 have class B activity; under the same conditions, the activity of D4 on the corn rust is D grade, and D6 is B grade;

I-2J2-1 and the like are selected for deep screening, and the results show that the ED of the compound I-2K3-1 and the like on corn rust disease₅₀The value is less than 0.50mg/L, and ED of I-2D3-1, I-2E3-1, I-2F3-1 and the like on corn rust disease₅₀The ED of the corn rust is 0.50-1.00mg/L, I-2J3-1, I-2K3-1 and I-2P3-1₅₀ED on corn rust with values of 1.00-1.50mg/L, I-1D3-1 and I-1K3-1₅₀The value is 1.50-2.00mg/L, ED of I-1B3-1, I-1E3-1, I-1F3-1, I-2G3-1 and I-1Q3-1 for corn rust₅₀The value is 2.00-3.50 mg/L; ED of D6 and tebuconazole on corn rust under the same conditions₅₀The value is 1.50-2.00 mg/L.

Example 11 fungicidal Activity against Gibberella zeae) of Gibberella tritici

The method comprises the following steps: dissolving the compound to be tested in a suitable solvent such as N, N-dimethylformamide, diluting with sterile water containing 0.2% Tween80 emulsifier to desired concentration, setting blank containing no compound to be tested as control, and repeating for 4 times; 3mL of the liquid medicine is taken by a pipette and added into 27mL of potato agar culture medium PDA) which is cooled to 45 ℃, and the liquid medicine is poured into a culture dish after being fully shaken up; after cooling, taking a hypha block with the diameter of 6mm from the edge of a germ colony cultured for 7 days by using an inoculating needle, and transferring the hypha block to the center of a culture dish, wherein the hypha surface faces downwards; after the treatment, the culture dish is placed in a constant-temperature biochemical incubator at 28 ℃ for culture, the growth diameter of the hyphae is measured after 4 days, analysis is carried out by using EXCEL statistical software, the hypha growth inhibition rate is calculated, the activity is classified into A, B, C, D grades relative to a blank control in percentage, the inhibition rate of 100% is greater than or equal to 90% and is A grade, the inhibition rate of 90% is greater than or equal to 70% and is B grade, the inhibition rate of 70% is greater than or equal to 50% and is C grade, and the inhibition rate of 50% is greater than or equal to 0% and is D grade.

The bactericidal activity of the compound on phytophthora capsici (phytophthora capsaici), Alternaria alternata (Alternaria alternata), Botrytis cinerea (Botrytis cinerea) and sclerotinia sclerotiorum (sclerotiorum) is respectively measured by adopting a method for measuring the bactericidal activity of the fusarium graminearum. The following are partial results:

at a concentration of 25mg/L, the compounds I-2D3-16 and the like have B-level activity on wheat scab germs, I-2F3-1, I-1V2-1 and the like have activity close to B level, I-1D2-1, I-1F3-1, I-1Q3-1, I-2D2-1, I-2F3-1, I-2G2-1, I-2J1-1, I-2J2-1, I-2J3-1, I-2K3-1, I-2P2-1, I-2V2-1 and the like have C level activity; under the same conditions, D2, D4, D6 and D7 have D-class activity against Gibberella zeae.

Under the concentration of 25mg/L, the inhibition rate of compounds I-1J3-1 and the like on phytophthora capsici is more than 65%, the compounds have activity close to B level, and the compounds I-1J2-1, I-2D2-1, I-2H3-1, I-2J3-1 and the like have C level activity; under the same conditions, D2 and D4 have C-level activity on phytophthora capsici and D6 and D7 have D-level activity.

At the concentration of 25mg/L, the compounds I-1H3-1, I-1J2-1, I-2D2-1, I-2G2-1, I-2J1-1, I-2J2-1 and the like have C-grade activity on alternaria alternata; under the same conditions, D2, D4, D6 and D7 have D-grade activity on alternaria alternate.

At the concentration of 25mg/L, the compound I-2J1-1 and the like have B-grade activity on cucumber botrytis cinerea, and the compound I-1J2-1, I-1V2-1, I-2D2-1, I-2G2-1, I-2G3-1 and the like have C-grade activity; under the same conditions, D4 has grade C activity on cucumber botrytis cinerea, and D2, D6 and D7 have grade D activity.

At the concentration of 25mg/L, the compounds I-2J1-1 and the like have B-grade activity on sclerotinia sclerotiorum, and I-1J2-1, I-1V2-1, I-2D2-1, I-2G2-1 and the like have C-grade activity; under the same conditions, the activity of D4 on Sclerotinia sclerotiorum is grade C, and the activities of D2, D6 and D7 are grade D.

Claims

1. Pyridine ether compounds containing pyrimidine amine with biological activity and isomers or salts thereof, which is characterized in that the pyridine ether compounds containing pyrimidine amine and isomers thereof are represented by general formula (I):

wherein:

halogen: fluorine, chlorine, bromine, iodine;

alkyl groups: refers to straight or branched chain alkyl;

cycloalkyl groups: refers to a saturated or unsaturated cycloalkyl group;

a salt of a compound of formula (I): refers to salts of compounds of formula (I) with organic or inorganic acids; the organic acid refers to a carboxylic acid or a sulfonic acid such as acetic acid, trifluoroacetic acid, chloroacetic acid, propionic acid, butyric acid, oxalic acid, adipic acid, lauric acid, citric acid, maleic acid, fumaric acid, benzoic acid, methylbenzoic acid, phthalic acid, methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid or dodecylbenzenesulfonic acid; inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid or carbonic acid.

2. The pyridylether compounds containing pyrimidinamines and the isomers or the salts thereof according to claim 1, characterized in that in the compounds of the general formula (I):

3. Pyridine ether compounds containing pyrimidinamines and isomers or salts thereof according to claim 1 or 2, characterized in that in the compounds of general formula (I):

4. The pyridylether compound containing pyrimidinamine according to claim 1 or 3, wherein:

III.R²、R³、R⁴are identical or different and are selected from hydrogen, halogen, trifluoromethyl;

w is selected from hydrogen or methyl; when W is selected from hydrogen, the compound shown in the formula (I) is I-1A, I-1B, I-1C, I-1D, I-1E, I-1F, I-1G, I-1H, I-1I, I-1J, I-1K, I-1L, I-1M, I-1N, I-1O, I-1P, I-1Q, I-1R, I-1S, I-1T, I-1U, I-1V, I-1W or I-1X; when W is selected from methyl, the compound shown in the formula (I) is I-2A, I-2B, I-2C, I-2D, I-2E, I-2F, I-2G, I-2H, I-2I, I-2J, I-2K, I-2L, I-2M, I-2N, I-2O, I-2P, I-2Q, I-2R, I-2S, I-2T, I-2U, I-2V, I-2W or I-2X;

5. The pyridylether compounds containing pyrimidinamines and isomers or salts thereof according to claim 1 or 4, wherein the compound represented by the general formula (I) is represented by formula I-1A, I-1B, I-1C, I-1D, I-1E, I-1F, I-1G, I-1H, I-1I, I-1J, I-1K, I-1L, I-1M, I-1N, I-1O, I-1P, I-1Q, I-1R, I-1S, I-1T, I-1U, I-1V, I-1W, I-1X, I-2A, I-2B, I-2C, I-2D, I-2E, I-2F, I-2G, I-2H, I-2I, I-2J, I-2K, I-2L, I-2M, I-2N, I-2O, I-2P, I-2Q, I-2R, I-2S, I-2T, I-2U, I-2V, I-2W or I-2X,

wherein: r and R¹Are identical or different and are selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, chloromethyl, fluoromethyl, bromomethyl, iodomethyl, dichloromethyl, difluoromethyl, dibromomethyl, diiodomethyl, trichloromethyl, trifluoromethyl, tribromomethyl, triiodomethyl, 2-trifluoroethyl, 1-fluoroethyl, 1-chloroethyl, 1-bromoethyl, 1-fluoroisopropyl, 1-chloroisopropyl, 1-bromoisopropyl, methoxymethyl, methoxyethyl, ethoxymethyl, cyclopropyl, cyclopentyl, cyclohexyl, 1-oxocyclopentyl, 2-allylic, 2-propargyl, 3-chloro-2-allyl, 3-dichloro-2-allyl, 3, 3-difluoro-2-allyl, heptafluoroisopropyl or 1-methoxyhexafluoroisopropyl;

6. The pyridylether compounds containing pyrimidinamines and the isomers or salts thereof according to claim 1 or 5, wherein the compound represented by the general formula (I) is:

(S) -N- (2- ((3-chloropyridin-2-yl) oxy) propyl) -5-chloro-6-difluoromethylpyrimidin-4-amine;

(RS) -N- (2- ((5-trifluoromethylpyridin-2-yl) oxy) propyl) -5-chloro-6-ethylpyrimidin-4-amine;

(RS) -N- (2- ((5-trifluoromethylpyridin-2-yl) oxy) propyl) -5-chloro-6-difluoromethylpyrimidin-4-amine;

(S) -N- (2- ((5-trifluoromethylpyridin-2-yl) oxy) propyl) -5-chloro-6-difluoromethylpyrimidin-4-amine;

(R) -N- (2- ((5-trifluoromethylpyridin-2-yl) oxy) propyl) -5-chloro-6-difluoromethylpyrimidin-4-amine;

(RS) -N- (2- ((3, 5-dichloropyridin-2-yl) oxy) propyl) -5-chloro-6-ethylpyrimidin-4-amine;

(S) -N- (2- ((3, 5-dichloropyridin-2-yl) oxy) propyl) -5-chloro-6-difluoromethylpyrimidin-4-amine;

(RS) -N- (2- ((3-chloro-5-trifluoromethylpyridin-2-yl) oxy) propyl) -5-chloro-6-ethylpyrimidin-4-amine;

(RS) -N- (2- ((3-chloro-5-trifluoromethylpyridin-2-yl) oxy) propyl) -5-chloro-6-difluoromethylpyrimidin-4-amine;

(S) -N- (2- ((3-chloro-5-trifluoromethylpyridin-2-yl) oxy) propyl) -5-chloro-6-difluoromethylpyrimidin-4-amine;

(RS) -N- (2- ((3,5, 6-trichloropyridin-2-yl) oxy) propyl) -5-chloro-6-difluoromethylpyrimidin-4-amine;

(RS) -N- (2- ((3-fluoro-5-chloropyridin-2-yl) oxy) propyl) -5-chloro-6-difluoromethylpyrimidin-4-amine;

(S) -N- (2- ((3-fluoro-5-chloropyridin-2-yl) oxy) propyl) -5-chloro-6-difluoromethylpyrimidin-4-amine;

(RS) -N- (2- ((5-nitropyridin-2-yl) oxy) propyl) -5-chloro-6-ethylpyrimidin-4-amine;

(RS) -N- (2- ((5-trifluoromethylpyridin-2-yl) oxy) propyl) -5-chloro-2, 6-dimethylpyrimidin-4-amine;

(RS) -N- (2- ((5-trifluoromethylpyridin-2-yl) oxy) propyl) -5-chloro-2-methyl-6-ethylpyrimidin-4-amine;

(RS) -N- (2- ((5-trifluoromethylpyridin-2-yl) oxy) propyl) -5-chloro-2-methyl-6-difluoromethylpyrimidin-4-amine;

(S) -N- (2- ((5-trifluoromethylpyridin-2-yl) oxy) propyl) -5-chloro-2-methyl-6-difluoromethylpyrimidin-4-amine;

(R) -N- (2- ((5-trifluoromethylpyridin-2-yl) oxy) propyl) -5-chloro-2-methyl-6-difluoromethylpyrimidin-4-amine;

(RS) -N- (2- ((3, 5-dichloropyridin-2-yl) oxy) propyl) -5-chloro-2-methyl-6-ethylpyrimidin-4-amine;

(RS) -N- (2- ((3, 5-dichloropyridin-2-yl) oxy) propyl) -5-chloro-2-methyl-6-difluoromethylpyrimidin-4-amine;

(S) -N- (2- ((3, 5-dichloropyridin-2-yl) oxy) propyl) -5-chloro-2-methyl-6-difluoromethylpyrimidin-4-amine;

(RS) -N- (2- ((3, 5-dichloropyridin-2-yl) oxy) propyl) -5-chloro-2, 6-dimethylpyrimidin-4-amine;

(RS) -N- (2- ((3-chloro-5-trifluoromethylpyridin-2-yl) oxy) propyl) -5-chloro-2-methyl-6-ethylpyrimidin-4-amine;

(RS) -N- (2- ((3-chloro-5-trifluoromethylpyridin-2-yl) oxy) propyl) -5-chloro-2-methyl-6-difluoromethylpyrimidin-4-amine;

(S) -N- (2- ((3-chloro-5-trifluoromethylpyridin-2-yl) oxy) propyl) -5-chloro-2-methyl-6-difluoromethylpyrimidin-4-amine;

(RS) -N- (2- ((3-fluoro-5-chloropyridin-2-yl) oxy) propyl) -5-chloro-2-methyl-6-ethylpyrimidin-4-amine;

(RS) -N- (2- ((3-fluoro-5-chloropyridin-2-yl) oxy) propyl) -5-chloro-2-methyl-6-difluoromethylpyrimidin-4-amine;

(RS) -N- (2- ((5-nitropyridin-2-yl) oxy) propyl) -5-chloro-2-methyl-6-ethylpyrimidin-4-amine.

7. The process for producing pyridylether compounds containing pyrimidinamines according to claim 1 or 6, wherein the compound represented by the formula (I) or a salt thereof is produced by the reaction shown below:

reaction formula 1:

reaction formula 2:

reaction formula 3:

reaction formula 4:

reacting a compound of formula (II) with a compound of formula (III) in the solvent dichloromethane, dichloroethane, toluene, xylene, N-dimethylformamide, N-methylpyrrolidone, dimethylsulfoxide, pyridine, tetrahydrofuran, methanol, ethanol, isopropanol, acetone, butanone, methyl isobutyl ketone, acetonitrile, ethyl acetate or dioxane at a temperature of-10 ℃ to the reflux temperature of the system in the absence of a base or in the presence of a suitable base, which may be selected from alkali metal hydrides such as sodium hydride, to obtain a compound of formula (I), wherein the reaction is accelerated when carried out in the presence of a base; alkali metal hydroxides such as sodium hydroxide or potassium hydroxide; alkali metal carbonates such as sodium carbonate or potassium carbonate; alkali metal alkoxides such as sodium methoxide or sodium ethoxide; organic amines such as pyridine, triethylamine or diisopropylethylamine;

reacting a compound of formula (IV) with a compound of formula (V) in the solvent dichloromethane, dichloroethane, toluene, xylene, N-dimethylformamide, N-methylpyrrolidone, dimethylsulfoxide, pyridine, tetrahydrofuran, methanol, ethanol, isopropanol, acetone, butanone, methyl isobutyl ketone, acetonitrile, ethyl acetate or dioxane at a temperature of-10 ℃ to the reflux temperature of the system in the absence of a base or in the presence of a suitable base, which may be selected from alkali metal hydrides such as sodium hydride, to obtain a compound of formula (II), wherein the reaction is accelerated when carried out in the presence of a base; alkali metal hydroxides such as sodium hydroxide or potassium hydroxide; alkali metal carbonates such as sodium carbonate or potassium carbonate; alkali metal alkoxides such as sodium methoxide or sodium ethoxide; organic amines such as pyridine, triethylamine or diisopropylethylamine;

reacting a compound of a formula (VI) with a chlorinating agent chlorine or sulfonyl chloride at 0-50 ℃ in the absence of a solvent or in a solvent of ethyl acetate, dichloromethane, trichloromethane, dichloroethane, acetone, butanone or methyl isobutyl ketone to obtain a compound of a formula (VII); reacting a compound of formula (VII) with a compound of formula (VIII) in the presence of the bases triethylamine, pyridine, sodium methoxide, sodium ethoxide, sodium hydride, potassium hydroxide, potassium carbonate, sodium hydroxide or sodium carbonate at 5-50 ℃ in the solvents methanol, ethanol, propanol, isopropanol, dichloromethane, dichloroethane, toluene, xylene, N-dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide, pyridine, tetrahydrofuran, acetone, butanone or methyl isobutyl ketone to obtain a compound of formula (IX); reacting the compound shown in the formula (IX) with phosphorus oxychloride or phosphorus tribromooxy in the presence of triethylamine, pyridine, sodium methoxide, sodium ethoxide, sodium hydride, potassium hydroxide, potassium carbonate, sodium hydroxide or sodium carbonate serving as an alkali halogenating agent to obtain a compound shown in the formula (IV);

reacting the compound of the formula (I) with Acid at the temperature of 0-system reflux temperature in one or two suitable solvents, wherein the suitable solvents are selected from dichloromethane, dichloroethane, trichloromethane, toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, N-dimethylformamide, tetrahydrofuran, ethyl acetate, methanol, ethanol, isopropanol or dioxane;

formula (III) R, R¹、R²、R³、R⁴W, Acid has the meaning given in claim 1, L is a leaving group fluorine, chlorine, bromine or iodine.

8. The use of the pyridylether compounds containing pyrimidinamines and isomers or salts thereof according to claim 1 or 6, wherein the pyridylether compounds have insecticidal/acaricidal or fungicidal biological activity at an effective ingredient/hectare dose of 7.5 to 2250 g.

9. Use of the pyridylether compounds containing pyrimidinamines and isomers thereof or salts thereof according to claim 1 or 5 for the preparation of medicaments having insecticidal/acaricidal or fungicidal activity.

10. An insecticidal/acaricidal or fungicidal composition, comprising: the pyridine ether compound containing pyrimidinamine and the isomer or the salt thereof as claimed in claim 1 or 5, and an acceptable carrier, wherein the weight percentage of the active component in the composition is 0.5-90%.