CN108059629B - Pyrimidine-containing substituted pyrazole compound and preparation method and application thereof - Google Patents

Pyrimidine-containing substituted pyrazole compound and preparation method and application thereof Download PDF

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CN108059629B
CN108059629B CN201610978801.4A CN201610978801A CN108059629B CN 108059629 B CN108059629 B CN 108059629B CN 201610978801 A CN201610978801 A CN 201610978801A CN 108059629 B CN108059629 B CN 108059629B
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关爱莹
杨金龙
李志念
许磊川
王军锋
孙旭峰
刘长令
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Shenyang Sinochem Agrochemicals R&D Co Ltd
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    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
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    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
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    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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Abstract

The invention discloses a pyrimidine-containing substituted pyrazole compound, which has a structure shown in a general formula I:

Description

Pyrimidine-containing substituted pyrazole compound and preparation method and application thereof
Technical Field
The invention belongs to the field of chemistry, and particularly relates to a pyrimidine-containing substituted pyrazole compound, and a preparation method and application thereof.
Background
Patent WO9507278 discloses substituted pyrazole compounds containing pyrimidine represented by the following general formula and specific compounds CK1 and CK2, and their application as agricultural bactericide, insecticide, acaricide, etc.
Figure BDA0001147669920000011
The following compounds CK3, CK4 and CK5 were retrieved online by Scfinider, but no specific reference is made.
Figure BDA0001147669920000012
However, the pyrimidine-containing substituted pyrazole compounds with the structure shown in the general formula I are not reported.
Disclosure of Invention
The invention aims to provide a pyrimidine-containing substituted pyrazole compound capable of controlling various pathogenic bacteria, a preparation method thereof and application of the pyrimidine-containing substituted pyrazole compound in preparation of medicines for preventing and treating pathogenic bacteria in agriculture or other fields.
In order to achieve the purpose, the technical scheme of the invention is as follows:
the invention provides a pyrimidine-containing substituted pyrazole compound, which is a compound shown as a general formula I,
Figure BDA0001147669920000013
in the formula:
R1selected from hydrogen, halogen, cyano, nitro, amino, carboxyl, C1-C12Alkyl, halo C1-C12Alkyl radical, C3-C12Cycloalkyl radical, C1-C12Alkoxy, halo C1-C12Alkoxy radical, C1-C12Alkylthio, halo C1-C12Alkylthio radical, C1-C12Alkylsulfinyl radical, C1-C12Alkylsulfonyl radical, C2-C12Alkenyl, halo C2-C12Alkenyl radical, C2-C12Alkynyl, halo C2-C12Alkynyl, C3-C12Alkenyloxy, halogeno C3-C12Alkenyloxy radical, C3-C12Alkynyloxy, halo C3-C12Alkynyloxy, C1-C12Alkylamino radical, di (C)1-C12Alkyl) amino, C1-C12Alkylaminocarbonyl, halogenGeneration C1-C12Alkylaminocarbonyl radical, C1-C12Alkoxycarbonyl, halo C1-C12Alkoxycarbonyl group, C1-C12Alkoxy radical C1-C12Alkyl or C1-C2Alkylthio group C1-C12An alkyl group;
R2selected from hydrogen, halogen, cyano, nitro, amino, carboxyl, formyl, C1-C12Alkyl, halo C1-C12Alkyl radical, C1-C12Alkoxy or halo C1-C12An alkoxy group;
R1and R2Can also form a five-membered, six-membered, seven-membered or eight-membered ring containing C, N, O or S together with the connected pyrimidine ring;
x is selected from NR3O or S;
R3selected from hydrogen, hydroxy, formyl, C1-C12Alkyl, halo C1-C12Alkyl radical, C1-C12Alkoxy, halo C1-C12Alkoxy radical, C3-C12Cycloalkyl radical, C1-C12Alkylthio radical, C2-C12Alkenylthio radical, C2-C12Alkenyl radical, C2-C12Alkynyl, halo C2-C12Alkenyl, halo C2-C12Alkynyl, C1-C12Alkoxy radical C1-C12Alkyl, halo C1-C12Alkoxy radical C1-C12Alkyl radical, C1-C12Alkylthio group C1-C12Alkyl, halo C1-C12Alkylthio group C1-C12Alkyl radical, C1-C12Alkylsulfinyl, halogeno C1-C12Alkylsulfinyl radical, C1-C12Alkylsulfonyl, halo C1-C12Alkylsulfonyl radical, C1-C12Alkylaminosulfonyl, di (C)1-C12Alkyl) aminosulfonyl, C1-C12Alkylsulfonylaminocarbonyl group, C1-C12Alkyl carbo groupAminosulfonyl radical, C3-C12Cycloalkyloxycarbonyl radical, C1-C12Alkylcarbonyl, halo C1-C12Alkylcarbonyl group, C1-C12Alkoxycarbonyl, halo C1-C12Alkoxycarbonyl group, C1-C12Alkyl carbonyl radical C1-C12Alkyl radical, C1-C12Alkoxycarbonyl radical C1-C12Alkyl radical, C1-C12Alkylaminocarbonyl, di (C)1-C12Alkyl) aminocarbonyl, C2-C12Alkenyloxycarbonyl radical, C2-C12Alkynyloxycarbonyl group, C1-C12Alkoxy radical C1-C12Alkoxycarbonyl group, C1-C12Alkylaminosulfenyl, di (C)1-C12Alkyl) aminothio, arylcarbonyl C unsubstituted or substituted by 1 to 51-C6Alkyl, arylcarbonyl, aryloxycarbonyl, aryl C1-C6Alkyloxycarbonyl, aryl C1-C6Alkyl, heteroaryl carbonyl C1-C6Alkyl, heteroarylcarbonyl, heteroaryloxycarbonyl, heteroaryl C1-C6Alkyloxycarbonyl, heteroaryl C1-C6Alkyl, the following groups are halogen, nitro, cyano, C1-C6Alkyl, halo C1-C6Alkyl radical, C1-C6Alkoxy or halo C1-C6An alkoxy group;
R4、R5same or different are respectively selected from hydrogen, halogen and C1-C12Alkyl, halo C1-C12Alkyl radical, C1-C12Alkoxy or halo C1-C12An alkoxy group;
wherein R is4、R5C attached thereto may also form C3-C8A ring of (a);
R6、R7same or different are respectively selected from hydrogen, halogen and C1-C12Alkyl, halo C1-C12Alkyl radical, C1-C12Alkoxy or halo C1-C12An alkoxy group;
wherein R is6、R7C attached thereto may also form C3-C8A ring of (a);
m is an integer from 0 to 5;
R8selected from hydrogen, cyano, halogen, C1-C12Alkyl, halo C1-C12Alkyl radical, C1-C12Alkoxycarbonyl, halo C1-C12Alkoxycarbonyl, unsubstituted or substituted by 1 to 5R10Substituted aryl, arylmethyl, arylcarbonyl, arylmethylcarbonyl, aryloxycarbonyl, heteroaryl, heteroarylmethyl, heteroarylcarbonyl, heteroarylmethylcarbonyl, or heteroaryloxycarbonyl;
R9selected from hydrogen, C1-C12Alkyl radical, C3-C8Cycloalkyl, halo C1-C12Alkyl radical, C1-C12Alkylcarbonyl, halo C1-C12Alkylcarbonyl group, C1-C12Alkylsulfonyl, halo C1-C12Alkylsulfonyl radical, C1-C12Alkoxycarbonyl group, C1-C12Alkoxy radical C1-C12Alkyl radical, C1-C12Alkoxycarbonyl radical C1-C12Alkyl, unsubstituted or substituted by 1-5R10Substituted aryl, arylmethyl, arylcarbonyl, arylmethylcarbonyl, aryloxycarbonyl, heteroaryl, heteroarylmethyl, heteroarylcarbonyl, heteroarylmethylcarbonyl, or heteroaryloxycarbonyl;
R10selected from halogen, hydroxy, amino, cyano, nitro, C1-C12Alkyl, halo C1-C12Alkyl radical, C1-C12Alkoxy, halo C1-C12Alkoxy radical, C3-C12Cycloalkyl radical, C1-C12Alkylamino, halogeno C1-C12Alkylamino radical, di (C)1-C12Alkyl) amino, halo-di (C)1-C12Alkyl) amino, C (═ O) NR11R12、C1-C12Alkylthio, halo C1-C12Alkylthio radical, C2-C12Alkenyl radical, C2-C12Alkynyl, C2-C12Alkenyloxy, halogeno C2-C12Alkenyloxy radical, C2-C12Alkynyloxy, halo C2-C12Alkynyloxy, C1-C12Alkylsulfonyl, halo C1-C12Alkylsulfonyl radical, C1-C12Alkylcarbonyl, halo C1-C12Alkylcarbonyl group, C1-C12Alkoxycarbonyl, halo C1-C12Alkoxycarbonyl group, C1-C12Alkoxy radical C1-C12Alkyl, halo C1-C12Alkoxy radical C1-C12Alkyl radical, C1-C12Alkylthio group C1-C12Alkyl, halo C1-C12Alkylthio group C1-C12Alkyl radical, C1-C12Alkoxycarbonyl radical C1-C12Alkyl, halo C1-C12Alkoxycarbonyl radical C1-C12Alkyl radical, C1-C12Alkylthio carbonyl group C1-C12Alkyl, halo C1-C12Alkylthio carbonyl group C1-C12Alkyl radical, C1-C12Alkylcarbonyloxy, halo C1-C12Alkylcarbonyloxy, C1-C12Alkoxycarbonyloxy, halo C1-C12Alkoxycarbonyloxy, C1-C12Alkylsulfonyloxy, halo C1-C12Alkylsulfonyloxy, C1-C12Alkoxy radical C1-C12Alkoxy or halo C1-C12Alkoxy radical C1-C12An alkoxy group;
R11、R12same or different are respectively selected from hydrogen and C1-C12Alkyl or halo C1-C12An alkyl group;
w is selected from hydrogen, halogen, C1-C12Alkyl, halo C1-C12Alkyl radical, C3-C8Cycloalkyl radical, C1-C12Alkoxy radical, C1-C12Alkylthio or C1-C12An alkylsulfonyl group;
q is selected from unsubstituted or substituted by 1-5R10Substituted aryl, arylmethyl, arylcarbonyl, arylmethylcarbonyl, aryloxycarbonyl, heteroaryl, heteroarylmethyl, heteroarylcarbonyl, heteroarylmethylcarbonyl, or heteroaryloxycarbonyl;
or a salt of a compound of formula I.
Above, R9And in Q with respect to R10The substituents are independently selected.
In the pyrimidine-containing substituted pyrazole compounds of the invention, optional compounds include: in the general formula I:
R1selected from hydrogen, halogen, cyano, nitro, amino, carboxyl, C1-C6Alkyl, halo C1-C6Alkyl radical, C3-C6Cycloalkyl radical, C1-C6Alkoxy, halo C1-C6Alkoxy radical, C1-C6Alkylthio radical, C1-C6Alkylsulfinyl radical, C1-C6Alkylsulfonyl, halo C1-C6Alkylthio radical, C2-C6Alkenyl, halo C2-C6Alkenyl radical, C2-C6Alkynyl, halo C2-C6Alkynyl, C3-C6Alkenyloxy, halogeno C3-C6Alkenyloxy radical, C3-C6Alkynyloxy, halo C3-C6Alkynyloxy, C1-C6Alkylamino radical, di (C)1-C6Alkyl) amino, C1-C6Alkylaminocarbonyl, halogeno C1-C6Alkylaminocarbonyl radical, C1-C6Alkoxycarbonyl, halo C1-C6Alkoxycarbonyl group, C1-C6Alkoxy radical C1-C6Alkyl or C1-C6Alkylthio group C1-C6An alkyl group;
R2selected from hydrogen,Halogen, cyano, nitro, amino, carboxyl, formyl, C1-C6Alkyl, halo C1-C6Alkyl radical, C1-C6Alkoxy or halo C1-C6An alkoxy group;
R1and R2Can also form a five-membered ring or a six-membered ring containing C, N, O or S together with the connected pyrimidine ring;
x is selected from NR3O or S;
R3selected from hydrogen, hydroxy, formyl, C1-C6Alkyl, halo C1-C6Alkyl radical, C1-C6Alkoxy, halo C1-C6Alkoxy radical, C3-C6Cycloalkyl radical, C1-C6Alkylthio radical, C2-C6Alkenylthio radical, C2-C6Alkenyl radical, C2-C6Alkynyl, halo C2-C6Alkenyl, halo C2-C6Alkynyl, C1-C6Alkoxy radical C1-C6Alkyl, halo C1-C6Alkoxy radical C1-C6Alkyl radical, C1-C6Alkylthio group C1-C6Alkyl, halo C1-C6Alkylthio group C1-C6Alkyl radical, C1-C6Alkylsulfinyl, halogeno C1-C6Alkylsulfinyl radical, C1-C6Alkylsulfonyl, halo C1-C6Alkylsulfonyl radical, C1-C6Alkylaminosulfonyl, di (C)1-C6Alkyl) aminosulfonyl, C1-C6Alkylsulfonylaminocarbonyl group, C1-C6Alkylcarbonylaminosulfonyl radical, C3-C6Cycloalkyloxycarbonyl radical, C1-C6Alkylcarbonyl, halo C1-C6Alkylcarbonyl group, C1-C6Alkoxycarbonyl, halo C1-C6Alkoxycarbonyl group, C1-C6Alkyl carbonyl radical C1-C6Alkyl radical, C1-C6Alkoxycarbonyl radical C1-C6Alkyl radical, C1-C6Alkylaminocarbonyl, di (C)1-C6Alkyl) aminocarbonyl, C2-C6Alkenyloxycarbonyl radical, C2-C6Alkynyloxycarbonyl group, C1-C6Alkoxy radical C1-C6Alkoxycarbonyl group, C1-C6Alkylaminosulfenyl, di (C)1-C6Alkyl) aminosulfanyl, arylcarbonyl C which is unsubstituted or further substituted by 1 to 51-C6Alkyl, arylcarbonyl, aryloxycarbonyl, aryl C1-C6Alkyloxycarbonyl, aryl C1-C6Alkyl, heteroaryl carbonyl C1-C6Alkyl, heteroarylcarbonyl, heteroaryloxycarbonyl, heteroaryl C1-C6Alkyloxycarbonyl, heteroaryl C1-C6Alkyl, the following groups are halogen, nitro, cyano, C1-C6Alkyl, halo C1-C6Alkyl radical, C1-C6Alkoxy or halo C1-C6An alkoxy group;
R4、R5same or different are respectively selected from hydrogen, halogen and C1-C6Alkyl, halo C1-C6Alkyl radical, C1-C6Alkoxy or halo C1-C6An alkoxy group;
wherein R is4、R5C attached thereto may also form C3-C6A ring of (a);
R6、R7same or different are respectively selected from hydrogen, halogen and C1-C6Alkyl, halo C1-C6Alkyl radical, C1-C6Alkoxy or halo C1-C6An alkoxy group;
wherein R is6、R7C attached thereto may also form C3-C6A ring of (a);
m is an integer from 0 to 4;
R8selected from hydrogen, cyano, halogen, C1-C6Alkyl, halo C1-C6Alkyl, aryl, heteroaryl, and heteroaryl,C1-C6Alkoxycarbonyl, halo C1-C6Alkoxycarbonyl, unsubstituted or substituted by 1 to 5R10Substituted aryl, arylmethyl, arylcarbonyl, arylmethylcarbonyl, aryloxycarbonyl, heteroaryl, heteroarylmethyl, heteroarylcarbonyl, heteroarylmethylcarbonyl, or heteroaryloxycarbonyl;
R9selected from hydrogen, C1-C6Alkyl radical, C3-C6Cycloalkyl, halo C1-C6Alkyl radical, C1-C6Alkylcarbonyl, halo C1-C6Alkylcarbonyl group, C1-C6Alkylsulfonyl, halo C1-C6Alkylsulfonyl radical, C1-C6Alkoxycarbonyl group, C1-C6Alkoxy radical C1-C6Alkyl radical, C1-C6Alkoxycarbonyl radical C1-C6Alkyl, unsubstituted or substituted by 1-5R10Substituted aryl, arylmethyl, arylcarbonyl, arylmethylcarbonyl, aryloxycarbonyl, heteroaryl, heteroarylmethyl, heteroarylcarbonyl, heteroarylmethylcarbonyl, or heteroaryloxycarbonyl;
R10selected from halogen, hydroxy, amino, cyano, nitro, C1-C6Alkyl, halo C1-C6Alkyl radical, C1-C6Alkoxy, halo C1-C6Alkoxy radical, C3-C6Cycloalkyl radical, C1-C6Alkylamino, halogeno C1-C6Alkylamino radical, di (C)1-C6Alkyl) amino, halo-di (C)1-C6Alkyl) amino, C (═ O) NR11R12、C1-C6Alkylthio, halo C1-C6Alkylthio radical, C2-C6Alkenyl radical, C2-C6Alkynyl, C2-C6Alkenyloxy, halogeno C2-C6Alkenyloxy radical, C2-C6Alkynyloxy, halo C2-C6Alkynyloxy, C1-C6Alkylsulfonyl, halo C1-C6Alkylsulfonyl radical, C1-C6Alkylcarbonyl, halo C1-C6Alkylcarbonyl group, C1-C6Alkoxycarbonyl, halo C1-C6Alkoxycarbonyl group, C1-C6Alkoxy radical C1-C6Alkyl, halo C1-C6Alkoxy radical C1-C6Alkyl radical, C1-C6Alkylthio group C1-C6Alkyl, halo C1-C6Alkylthio group C1-C6Alkyl radical, C1-C6Alkoxycarbonyl radical C1-C6Alkyl, halo C1-C6Alkoxycarbonyl radical C1-C6Alkyl radical, C1-C6Alkylthio carbonyl group C1-C6Alkyl, halo C1-C6Alkylthio carbonyl group C1-C6Alkyl radical, C1-C6Alkylcarbonyloxy, halo C1-C6Alkylcarbonyloxy, C1-C6Alkoxycarbonyloxy, halo C1-C6Alkoxycarbonyloxy, C1-C6Alkylsulfonyloxy, halo C1-C6Alkylsulfonyloxy, C1-C6Alkoxy radical C1-C6Alkoxy or halo C1-C6Alkoxy radical C1-C6An alkoxy group;
R11、R12same or different are respectively selected from hydrogen and C1-C12Alkyl or halo C1-C12An alkyl group;
w is selected from hydrogen, halogen, C1-C6Alkyl, halo C1-C6Alkyl radical, C3-C6Cycloalkyl radical, C1-C6Alkoxy radical, C1-C6Alkylthio or C1-C6An alkylsulfonyl group;
q is selected from unsubstituted or substituted by 1-5R10Substituted aryl, arylmethyl, arylcarbonyl, arylmethylcarbonyl, aryloxycarbonyl, heteroaryl, heteroarylmethyl, heteroarylcarbonyl, heteroarylmethylcarbonyl, or heteroaryloxycarbonyl.
The invention relates to substituted pyridine containing pyrimidineAmong the azole compounds, more optional compounds include those in which Q is selected from unsubstituted or substituted by 1-5R10Substituted aryl, the compound of formula I is further represented by formula I-1;
Figure BDA0001147669920000041
in the formula (I), the compound is shown in the specification,
R1selected from hydrogen, halogen, cyano, nitro, amino, carboxyl, C1-C4Alkyl, halo C1-C4Alkyl radical, C3-C4Cycloalkyl radical, C1-C4Alkoxy, halo C1-C4Alkoxy radical, C1-C4Alkylthio radical, C1-C4Alkylsulfinyl radical, C1-C4Alkylsulfonyl, halo C1-C4Alkylthio radical, C2-C4Alkenyl, halo C2-C4Alkenyl radical, C2-C4Alkynyl, halo C2-C4Alkynyl, C3-C4Alkenyloxy, halogeno C3-C4Alkenyloxy radical, C3-C4Alkynyloxy, halo C3-C4Alkynyloxy, C1-C4Alkylamino radical, di (C)1-C4Alkyl) amino, C1-C4Alkylaminocarbonyl, halogeno C1-C4Alkylaminocarbonyl radical, C1-C4Alkoxycarbonyl, halo C1-C4Alkoxycarbonyl group, C1-C4Alkoxy radical C1-C4Alkyl or C1-C4Alkylthio group C1-C4An alkyl group;
R2selected from hydrogen, halogen, cyano, nitro, amino, carboxyl, formyl, C1-C4Alkyl, halo C1-C4Alkyl radical, C1-C4Alkoxy or halo C1-C4An alkoxy group;
R1and R2Can also be combined with an attached pyrimidine ring to form a ring containing C, NA five or six membered ring of O or S;
x is selected from NR3O or S;
R3selected from hydrogen, hydroxy, formyl, C1-C4Alkyl, halo C1-C4Alkyl radical, C1-C4Alkoxy, halo C1-C4Alkoxy radical, C3-C4Cycloalkyl radical, C1-C4Alkylthio radical, C2-C4Alkenylthio radical, C2-C4Alkenyl radical, C2-C4Alkynyl, halo C2-C4Alkenyl, halo C2-C4Alkynyl, C1-C4Alkoxy radical C1-C4Alkyl, halo C1-C4Alkoxy radical C1-C4Alkyl radical, C1-C4Alkylthio group C1-C4Alkyl, halo C1-C4Alkylthio group C1-C4Alkyl radical, C1-C4Alkylsulfinyl, halogeno C1-C4Alkylsulfinyl radical, C1-C4Alkylsulfonyl, halo C1-C4Alkylsulfonyl radical, C1-C4Alkylaminosulfonyl, di (C)1-C4Alkyl) aminosulfonyl, C1-C4Alkylsulfonylaminocarbonyl group, C1-C4Alkylcarbonylaminosulfonyl radical, C3-C4Cycloalkyloxycarbonyl radical, C1-C4Alkylcarbonyl, halo C1-C4Alkylcarbonyl group, C1-C4Alkoxycarbonyl, halo C1-C4Alkoxycarbonyl group, C1-C4Alkyl carbonyl radical C1-C4Alkyl radical, C1-C4Alkoxycarbonyl radical C1-C4Alkyl radical, C1-C4Alkylaminocarbonyl, di (C)1-C4Alkyl) aminocarbonyl, C2-C4Alkenyloxycarbonyl radical, C2-C4Alkynyloxycarbonyl group, C1-C4Alkoxy radical C1-C4Alkoxycarbonyl group, C1-C4An alkylaminosulfur group,Two (C)1-C4Alkyl) aminosulfanyl, arylcarbonyl C which is unsubstituted or further substituted by 1 to 51-C4Alkyl, arylcarbonyl, aryloxycarbonyl, aryl C1-C4Alkyloxycarbonyl, aryl C1-C4Alkyl, heteroaryl carbonyl C1-C4Alkyl, heteroarylcarbonyl, heteroaryloxycarbonyl, heteroaryl C1-C4Alkyloxycarbonyl, heteroaryl C1-C4Alkyl, the following groups are halogen, nitro, cyano, C1-C4Alkyl, halo C1-C4Alkyl radical, C1-C4Alkoxy or halo C1-C6An alkoxy group;
R4、R5same or different are respectively selected from hydrogen, halogen and C1-C4Alkyl, halo C1-C4Alkyl radical, C1-C4Alkoxy or halo C1-C4An alkoxy group;
wherein R is4、R5C attached thereto may also form C3-C4A ring of (a);
R6、R7same or different are respectively selected from hydrogen, halogen and C1-C4Alkyl, halo C1-C4Alkyl radical, C1-C4Alkoxy or halo C1-C4An alkoxy group;
wherein R is6、R7C attached thereto may also form C3-C4A ring of (a);
m is an integer from 0 to 3;
R8selected from hydrogen, cyano, halogen, C1-C4Alkyl, halo C1-C4Alkyl radical, C1-C4Alkoxycarbonyl, halo C1-C4Alkoxycarbonyl, unsubstituted or substituted by 1 to 5R10Substituted aryl, arylmethyl, arylcarbonyl, arylmethylcarbonyl, aryloxycarbonyl, heteroaryl, heteroarylmethyl, heteroarylcarbonyl, heteroarylmethylcarbonyl, or heteroaryloxycarbonyl;
R9selected from hydrogen, C1-C4Alkyl radical, C3-C4Cycloalkyl, halo C1-C4Alkyl radical, C1-C4Alkylcarbonyl, halo C1-C4Alkylcarbonyl group, C1-C4Alkylsulfonyl, halo C1-C4Alkylsulfonyl radical, C1-C4Alkoxycarbonyl group, C1-C4Alkoxy radical C1-C4Alkyl radical, C1-C4Alkoxycarbonyl radical C1-C4Alkyl, unsubstituted or substituted by 1-5R10Substituted aryl, arylmethyl, arylcarbonyl, arylmethylcarbonyl, aryloxycarbonyl, heteroaryl, heteroarylmethyl, heteroarylcarbonyl, heteroarylmethylcarbonyl, or heteroaryloxycarbonyl;
R10selected from halogen, hydroxy, amino, cyano, nitro, C1-C4Alkyl, halo C1-C4Alkyl radical, C1-C4Alkoxy, halo C1-C4Alkoxy radical, C3-C4Cycloalkyl radical, C1-C4Alkylamino, halogeno C1-C4Alkylamino radical, di (C)1-C4Alkyl) amino, halo-di (C)1-C4Alkyl) amino, C (═ O) NR12R13、C1-C4Alkylthio, halo C1-C4Alkylthio radical, C2-C4Alkenyl radical, C2-C4Alkynyl, C2-C4Alkenyloxy, halogeno C2-C4Alkenyloxy radical, C2-C4Alkynyloxy, halo C2-C4Alkynyloxy, C1-C4Alkylsulfonyl, halo C1-C4Alkylsulfonyl radical, C1-C4Alkylcarbonyl, halo C1-C4Alkylcarbonyl group, C1-C4Alkoxycarbonyl, halo C1-C4Alkoxycarbonyl group, C1-C4Alkoxy radical C1-C4Alkyl, halo C1-C4Alkoxy radical C1-C4Alkyl radical, C1-C4Alkylthio group C1-C4Alkyl, halo C1-C4Alkylthio group C1-C4Alkyl radical, C1-C4Alkoxycarbonyl radical C1-C4Alkyl, halo C1-C4Alkoxycarbonyl radical C1-C4Alkyl radical, C1-C4Alkylthio carbonyl group C1-C4Alkyl, halo C1-C4Alkylthio carbonyl group C1-C4Alkyl radical, C1-C4Alkylcarbonyloxy, halo C1-C4Alkylcarbonyloxy, C1-C4Alkoxycarbonyloxy, halo C1-C4Alkoxycarbonyloxy, C1-C4Alkylsulfonyloxy, halo C1-C4Alkylsulfonyloxy, C1-C4Alkoxy radical C1-C4Alkoxy or halo C1-C4Alkoxy radical C1-C4An alkoxy group;
R11、R12same or different are respectively selected from hydrogen and C1-C12Alkyl or halo C1-C12An alkyl group;
w is selected from hydrogen, halogen, C1-C4Alkyl, halo C1-C4Alkyl radical, C3-C4Cycloalkyl radical, C1-C4Alkoxy radical, C1-C4Alkylthio or C1-C4An alkylsulfonyl group.
In the pyrimidine-containing substituted pyrazole compounds, further optional compounds include compounds represented by the general formula I-1, wherein the structure of the compounds is as follows: I-1A, I-1B, I-1C, I-1D;
Figure BDA0001147669920000061
in the formula:
R4、R5same or different are respectively selected from hydrogen, halogen and C1-C4Alkyl, halo C1-C4Alkyl radical, C1-C4Alkoxy or halo C1-C4An alkoxy group;
wherein R is4、R5C attached thereto may also form C3-C4A ring of (a);
R6、R7same or different are respectively selected from hydrogen, halogen and C1-C4Alkyl, halo C1-C4Alkyl radical, C1-C4Alkoxy or halo C1-C4An alkoxy group;
wherein R is6、R7C attached thereto may also form C3-C4A ring of (a);
m is an integer from 0 to 3;
R8、R9same or different are respectively selected from hydrogen, cyano, halogen, C1-C4Alkyl, halo C1-C4Alkyl radical, C1-C4Alkoxycarbonyl, halo C1-C4Alkoxycarbonyl, unsubstituted or substituted by 1 to 5R10Substituted aryl, arylmethyl, arylcarbonyl, arylmethylcarbonyl, aryloxycarbonyl, heteroaryl, heteroarylmethyl, heteroarylcarbonyl, heteroarylmethylcarbonyl, or heteroaryloxycarbonyl;
R10selected from halogen, hydroxy, amino, cyano, nitro, C1-C4Alkyl, halo C1-C4Alkyl radical, C1-C4Alkoxy, halo C1-C4Alkoxy radical, C3-C4Cycloalkyl radical, C1-C4Alkylamino, halogeno C1-C4Alkylamino radical, di (C)1-C4Alkyl) amino, halo-di (C)1-C4Alkyl) amino, C (═ O) NR11R12、C1-C4Alkylthio, halo C1-C4Alkylthio radical, C2-C4Alkenyl radical, C2-C4Alkynyl, C2-C4Alkenyloxy, halogeno C2-C4Alkenyloxy radical, C2-C4Alkynyloxy, halo C2-C4Alkynyloxy, C1-C4Alkylsulfonyl, halo C1-C4Alkylsulfonyl radical, C1-C4Alkylcarbonyl, halo C1-C4Alkylcarbonyl group, C1-C4Alkoxycarbonyl, halo C1-C4Alkoxycarbonyl group, C1-C4Alkoxy radical C1-C4Alkyl, halo C1-C4Alkoxy radical C1-C4Alkyl radical, C1-C4Alkylthio group C1-C4Alkyl, halo C1-C4Alkylthio group C1-C4Alkyl radical, C1-C4Alkoxycarbonyl radical C1-C4Alkyl, halo C1-C4Alkoxycarbonyl radical C1-C4Alkyl radical, C1-C4Alkylthio carbonyl group C1-C4Alkyl, halo C1-C4Alkylthio carbonyl group C1-C4Alkyl radical, C1-C4Alkylcarbonyloxy, halo C1-C4Alkylcarbonyloxy, C1-C4Alkoxycarbonyloxy, halo C1-C4Alkoxycarbonyloxy, C1-C4Alkylsulfonyloxy, halo C1-C4Alkylsulfonyloxy, C1-C4Alkoxy radical C1-C4Alkoxy or halo C1-C4Alkoxy radical C1-C4An alkoxy group;
n is an integer of 0 to 5, and when n is 0, no substituent is arranged on a benzene ring; when n is greater than 1, R10The same or different;
R11、R12same or different are respectively selected from hydrogen and C1-C4Alkyl or halo C1-C4An alkyl group;
w is selected from hydrogen, halogen, C1-C4Alkyl, halo C1-C4Alkyl radical, C3-C4Cycloalkyl radical, C1-C4Alkoxy radical, C1-C4Alkylthio or C1-C4An alkylsulfonyl group;
and, when the compound is of formula I-1D, X is O or S;
when the compounds are of the general formulae I-1A and I-1D,
R1selected from hydrogen, halogen, cyano, nitro, amino, carboxyl, C1-C4Alkyl, halo C1-C4Alkyl radical, C3-C4Cycloalkyl radical, C1-C4Alkoxy, halo C1-C4Alkoxy radical, C1-C4Alkylthio, halo C1-C4Alkylthio radical, C1-C4Alkylsulfinyl radical, C1-C4Alkylsulfonyl radical, C2-C4Alkenyl, halo C2-C4Alkenyl radical, C2-C4Alkynyl, halo C2-C4Alkynyl, C3-C4Alkenyloxy, halogeno C3-C4Alkenyloxy radical, C3-C4Alkynyloxy, halo C3-C4Alkynyloxy, C1-C4Alkylamino radical, di (C)1-C4Alkyl) amino, C1-C4Alkylaminocarbonyl, halogeno C1-C4Alkylaminocarbonyl radical, C1-C4Alkoxycarbonyl, halo C1-C4Alkoxycarbonyl group, C1-C4Alkoxy radical C1-C4Alkyl or C1-C4Alkylthio group C1-C4An alkyl group;
R2selected from hydrogen, halogen, cyano, nitro, amino, carboxyl, formyl, C1-C4Alkyl, halo C1-C4Alkyl radical, C1-C4Alkoxy or halo C1-C4An alkoxy group;
when the compounds are of the general formulae I-1A, I-1B and I-1C,
R3selected from hydrogen, hydroxy, formyl, C1-C4Alkyl, halo C1-C4Alkyl radical, C1-C4Alkoxy, halo C1-C4Alkoxy radical, C3-C4Cycloalkyl radical, C1-C4Alkyl sulfideBase, C2-C4Alkenylthio radical, C2-C4Alkenyl radical, C2-C4Alkynyl, halo C2-C4Alkenyl, halo C2-C4Alkynyl, C1-C4Alkoxy radical C1-C4Alkyl, halo C1-C4Alkoxy radical C1-C4Alkyl radical, C1-C4Alkylthio group C1-C4Alkyl, halo C1-C4Alkylthio group C1-C4Alkyl radical, C1-C4Alkylsulfinyl, halogeno C1-C4Alkylsulfinyl radical, C1-C4Alkylsulfonyl, halo C1-C4Alkylsulfonyl radical, C1-C4Alkylaminosulfonyl, di (C)1-C4Alkyl) aminosulfonyl, C1-C4Alkylsulfonylaminocarbonyl group, C1-C4Alkylcarbonylaminosulfonyl radical, C3-C4Cycloalkyloxycarbonyl radical, C1-C4Alkylcarbonyl, halo C1-C4Alkylcarbonyl group, C1-C4Alkoxycarbonyl, halo C1-C4Alkoxycarbonyl group, C1-C4Alkyl carbonyl radical C1-C4Alkyl radical, C1-C4Alkoxycarbonyl radical C1-C4Alkyl radical, C1-C4Alkylaminocarbonyl, di (C)1-C4Alkyl) aminocarbonyl, C2-C4Alkenyloxycarbonyl radical, C2-C4Alkynyloxycarbonyl group, C1-C4Alkoxy radical C1-C4Alkoxycarbonyl group, C1-C4Alkylaminosulfenyl, di (C)1-C4Alkyl) aminosulfanyl, arylcarbonyl C which is unsubstituted or further substituted by 1 to 51-C4Alkyl, arylcarbonyl, aryloxycarbonyl, aryl C1-C4Alkyloxycarbonyl, aryl C1-C4Alkyl, heteroaryl carbonyl C1-C4Alkyl, heteroarylcarbonyl, heteroaryloxycarbonyl, heteroaryl C1-C4Alkyl radicalOxycarbonyl, heteroaryl C1-C4Alkyl, the following groups are halogen, nitro, cyano, C1-C4Alkyl, halo C1-C4Alkyl radical, C1-C4Alkoxy or halo C1-C4An alkoxy group;
when the compound is of the general formula I-1B,
R13、R14、R15or R16The same or different is respectively selected from hydrogen, halogen, hydroxyl, amino, cyano, nitro and C1-C4Alkyl, halo C1-C4Alkyl radical, C1-C4Alkoxy, halo C1-C4Alkoxy or C3-C4A cycloalkyl group;
when the compound is of the formula I-1C,
R17、R18same or different are respectively selected from hydrogen, halogen and C1-C4Alkyl, halo C1-C4Alkyl radical, C1-C4Alkoxy, halo C1-C4Alkoxy radical, C1-C4Alkylthio, halo C1-C4Alkylthio radical, C3-C4Cycloalkyl, unsubstituted or substituted by 1-5R10Substituted aryl, arylmethyl, arylcarbonyl, arylmethylcarbonyl, aryloxycarbonyl, heteroaryl, heteroarylmethyl, heteroarylcarbonyl, heteroarylmethylcarbonyl, or heteroaryloxycarbonyl;
in the pyrimidine-containing substituted pyrazole compounds, further optional compounds comprise compounds shown in general formulas I-1A, I-1B, I-1C, I-1D:
R4、R5identical or different from hydrogen, fluorine, chlorine, bromine, iodine, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy or tert-butoxy;
R6、R7the same or different are respectively selected from hydrogen, fluorine, chlorine, bromine, iodine, methyl, ethyl and n-propylA group selected from the group consisting of alkyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy and tert-butoxy;
R8、R9the same or different is selected from hydrogen, cyano, fluorine, chlorine, bromine, iodine, methyl, ethyl or trifluoromethyl;
R10selected from the group consisting of fluoro, chloro, bromo, iodo, cyano, amino, nitro, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, trifluoromethyl, trichloromethyl, difluorochloromethyl, dichlorofluoromethyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy, methylthio, ethylthio, trifluoromethoxy, trifluoroethoxy, methoxycarbonyl, ethoxycarbonyl, aminocarbonyl, methylaminocarbonyl, ethylaminocarbonyl, or dimethylaminocarbonyl;
n is an integer of 0 to 5, and when n is 0, no substituent is arranged on a benzene ring; when n is greater than 1, R10May be the same or different;
w is selected from hydrogen, fluoro, chloro, bromo, iodo, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, monofluoromethyl, monochloromethyl, difluoromethyl, trifluoromethyl, trifluoroethyl, methoxy, ethoxy, methylthio, ethylthio, methylsulfonyl or ethylsulfonyl;
and, when the compounds are of the general formulae I-1A and I-1D,
R1selected from hydrogen, fluoro, chloro, bromo, iodo, cyano, nitro, amino, carboxy, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, monofluoromethyl, chloromethyl, difluoromethyl, trifluoromethyl, trifluoroethyl, methoxymethyl, ethoxymethyl or trifluoroethoxymethyl;
R2selected from hydrogen, fluoro, chloro, bromo, iodo, cyano, nitro, amino, carboxy, formyl, methyl, ethyl, methoxy, ethoxy or trifluoroethoxy;
when the compounds are of the general formulae I-1A, I-1B and I-1C,
R3selected from the group consisting of 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, acetylenyloxycarbonyl, methylaminothio, ethylaminothio or dimethylaminosulfanyl;
when the compound is of the general formula I-1B,
R13、R14、R15or R16Identical or different radicals are each selected from the group consisting of hydrogen, fluorine, chlorine, bromine, iodine, amino, cyano, nitro, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, trifluoromethyl, trichloromethyl, difluorochloromethyl, dichlorofluoromethyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy, trifluoromethoxy and trifluoroethoxy;
when the compound is of the formula I-1C,
R17、R18identical or different from hydrogen, fluorine, chlorine, bromine, iodine, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, trifluoromethyl, trichloromethyl, difluorochloromethyl, dichlorofluoromethyl, trifluoroethyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy, trifluoromethoxy, trifluoroethoxy, unsubstituted or substituted by 1 to 5R10Substituted aryl, arylmethyl, arylcarbonyl, arylmethylcarbonyl, aryloxycarbonyl, heteroaryl, heteroarylmethyl, heteroarylalkylAlkylcarbonyl, heteroarylmethylcarbonyl or heteroaryloxycarbonyl;
in the pyrimidine-containing substituted pyrazole compounds, further optional compounds comprise compounds shown in a general formula I-1A, I-1B, I-1C, I-1D:
R4、R5the same or different is selected from hydrogen, fluorine, chlorine, bromine or methyl;
R6、R7are all selected from hydrogen;
R8is hydrogen or methyl;
R9selected from hydrogen or methyl;
R10selected from fluoro, chloro, bromo, iodo, cyano, nitro, methyl, ethyl, trifluoromethyl, methoxy, methylthio or trifluoromethoxy;
n is an integer of 0 to 5, and when n is 0, no substituent is arranged on a benzene ring; when n is greater than 1, R10May be the same or different;
w is selected from hydrogen, fluorine, chlorine, bromine, iodine or methyl;
and, when the compounds are of the general formulae I-1A and I-1D,
R1selected from hydrogen, fluoro, chloro, bromo, iodo, methyl, ethyl or difluoromethyl;
R2selected from hydrogen, fluoro, chloro, bromo, iodo, nitro, amino, formyl, methyl, ethyl, methoxy or ethoxy;
when the compounds are of the general formulae I-1A, I-1B and I-1C,
R3selected from hydrogen, methyl, acetyl, trifluoroacetyl, methoxy, methylthio, allyl, methylsulfonyl, methylaminosulfonyl, dimethylaminosulfonyl, methoxycarbonyl, methylaminocarbonyl, dimethylaminocarbonyl, methylaminothio or dimethylaminosulfanyl;
when the compound is of the general formula I-1B,
R13、R14、R15or R16The same or different is selected from hydrogen, fluorine, chlorine, bromine, iodine or methyl;
when the compound is of the formula I-1C,
R17、R18the same or different is selected from hydrogen, fluorine, chlorine, bromine or iodine;
among the pyrimidine-containing substituted pyrazoles of the present invention, further optional compounds include: in the compounds of formula I-1A, I-1B, I-1C, I-1D:
R4、R5may be the same or different and is independently selected from hydrogen or methyl;
R6、R7are all selected from hydrogen;
R8is hydrogen or methyl;
R9is selected from methyl;
R10selected from fluoro, chloro, bromo, iodo, cyano, nitro, methyl, ethyl, trifluoromethyl, methoxy, methylthio or trifluoromethoxy;
n is an integer of 1 to 5, and when n is greater than 1, R10May be the same or different;
w is selected from hydrogen, fluorine, chlorine, bromine or iodine;
and, when the compounds are of the general formulae I-1A and I-1D,
R1selected from fluoro, chloro, bromo, iodo, methyl, ethyl or difluoromethyl;
R2selected from fluorine, chlorine, bromine, iodine, nitro, amino, formyl, methyl or methoxy;
when the compounds are of the general formulae I-1A, I-1B and I-1C,
R3selected from hydrogen, methyl, acetyl, methoxy, allyl, methylsulfonyl, methoxycarbonyl, methylaminocarbonyl, dimethylaminocarbonyl or dimethylaminosulfanyl;
when the compound is of the general formula I-1B,
R13、R14、R15、R16are all selected from hydrogen;
when the compound is of the formula I-1C,
R17selected from hydrogen;
R18selected from chlorine;
a preparation method of a pyrimidine-containing substituted pyrazole compound is as follows:
Figure BDA0001147669920000101
the application of the pyrimidine-containing substituted pyrazole compound shown in the general formula I in preparation of bactericide medicaments in agriculture or other fields.
A sterilization composition takes a pyrimidine-containing substituted pyrazole compound shown in the general formula I as an active component; wherein, the weight percentage of the active components in the composition is 0.1 to 99 percent.
In the definitions of the compounds of the general formula I given above, the terms used are generally defined as follows:
halogen: refers to fluorine, chlorine, bromine or iodine. Alkyl groups: straight-chain or branched alkyl groups, such as methyl, ethyl, propyl, isopropyl, n-butyl or tert-butyl. Cycloalkyl groups: substituted or unsubstituted cyclic alkyl groups, such as cyclopropyl, cyclopentyl or cyclohexyl. Substituents such as methyl, halogen, and the like. Halogenated alkyl groups: straight-chain or branched alkyl groups in which the hydrogen atoms may be partially or completely substituted with halogen atoms, for example, chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl and the like. Alkylsulfinyl group: straight or branched chain alkyl groups are attached to the structure via a sulfinyl (-SO-) group, such as methylsulfinyl. Haloalkylsulfinyl group: straight-chain or branched alkylsulfinyl groups in which the hydrogen atoms of the alkyl group may be partially or fully substituted by halogen atoms. Haloalkylsulfonyl group: straight-chain or branched alkylsulfonyl wherein the hydrogen atoms of the alkyl group may be partially or wholly substituted by halogen atoms. Alkylaminosulfenyl: such as CH3NHS-、C2H5NHS-. Dialkylaminosulfenyl: such as (CH)3)2NS-、(C2H5)2NS-. Alkylaminosulfonyl: alkyl-NH-SO2-. Dialkylaminosulfonyl: (alkyl group)2-N-SO2-. Alkylsulfonylaminocarbonyl group: alkyl-SO2-NH-CO-. Alkylcarbonylaminosulfonyl: alkyl-CO-NH-SO2-. Alkane (I) and its preparation methodAlkylcarbonylalkyl group: alkyl-CO-alkyl-. Alkylsulfonyloxy group: alkyl-S (O)2-O-. Haloalkylsulfonyloxy: the hydrogen atoms of the alkyl group of the alkylsulfonyloxy group may be partially or wholly substituted by halogen atoms, e.g. CF3-SO2-O. Cycloalkyloxycarbonyl group: such as cyclopropyloxycarbonyl, cyclohexyloxycarbonyl, and the like. Alkoxy groups: straight or branched chain alkyl groups attached to the structure via oxygen atom linkages. Haloalkoxy groups: straight-chain or branched alkoxy groups in which the hydrogen atoms may be partially or completely replaced by halogen atoms. For example, chloromethoxy, dichloromethoxy, trichloromethoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorofluoromethoxy, trifluoroethoxy and the like. Halogenated alkoxycarbonyl group: the hydrogen atoms of the alkyl group of the alkoxycarbonyl group may be partially or wholly replaced by halogen atoms, e.g. ClCH2CH2OCO-、CF3CH2OCO-, etc. Alkoxyalkyl groups: alkyl-O-alkyl-, e.g. CH3OCH2-. Haloalkoxyalkyl groups: the hydrogen atoms of the alkyl groups of alkoxyalkyl groups may be partially or fully substituted by halogen atoms, e.g. ClCH2CH2OCH2-、CF3CH2OCH2-and the like. Alkoxycarbonylalkyl groups: alkoxycarbonyl-alkyl-, e.g. CH3OCOCH2-. Haloalkoxycarbonylalkyl: the hydrogen atoms of the alkyl group of the alkoxycarbonylalkyl group may be partially or fully substituted by halogen atoms, e.g. CF3CH2OCOCH2-. Alkylcarbonyloxy group: such as CH3COO-, etc. Haloalkylcarbonyloxy: the hydrogen atoms of the alkylcarbonyloxy group may be partially or fully substituted by halogen atoms, e.g. CF3COO-, etc. Alkoxycarbonyloxy: alkoxycarbonyl-oxy-, e.g. CH3OCOO-. Haloalkoxycarbonyl group: the hydrogen atoms of the alkyl group of the alkoxycarbonyloxy group may be partially or wholly substituted by halogen atoms, e.g. CF3OCOO-. Alkylthio-carbonylalkyl: alkylthiocarbonyl-alkyl-, e.g. CH3SCOCH2-. Haloalkylthiocarbonylalkyl: the hydrogen atoms of the alkyl group of the alkylthiocarbonylalkyl group may be partially or wholly substituted by halogen atoms, e.g. CF3CH2SCOCH2-. Alkoxyalkoxy group: such as CH3OCH2O-, etc. Haloalkoxyalkyl: the hydrogen atoms of the alkoxy groups being partially or wholly replaced by halogen atoms, e.g. CF3OCH2O-is formed. Alkoxy alkoxycarbonyl group: such as CH3OCH2CH2OCO-, etc. Alkylthio group: straight or branched chain alkyl groups attached to the structure via a sulfur atom. Haloalkylthio: straight-chain or branched alkylthio groups in which the hydrogen atoms may be partially or wholly replaced by halogen atoms. For example, chloromethylthio, dichloromethylthio, trichloromethylthio, fluoromethylthio, difluoromethylthio, trifluoromethylthio, chlorofluoromethylthio and the like. Alkylthioalkyl: alkyl-S-alkyl-, e.g. CH3SCH2-. Haloalkylthioalkyl: the hydrogen atoms of the alkyl group of an alkylthioalkyl group may be partially or fully substituted by halogen atoms, e.g. ClCH2CH2SCH2-、CF3CH2SCH2-and the like. Alkylamino group: straight or branched chain alkyl, linked to the structure via a nitrogen atom. Haloalkylamino group: straight-chain or branched alkylamino groups in which the hydrogen atoms may be partially or fully substituted by halogen atoms. Dialkylamino group: such as (CH)3)2N-，(CH3CH2)2N-is provided. Halogenated dialkylamino group: the hydrogen atoms of the alkyl groups being partially or wholly replaced by halogen atoms, e.g. (CF)3)2N-，(CF3CH2)2N-is provided. Alkenyl: straight-chain or branched alkenes, for example ethenyl, 1-propenyl, 2-propenyl and the different butenyl, pentenyl and hexenyl isomers. Alkenyl also includes polyenes such as 1, 2-allenyl and 2, 4-hexadienyl. Halogenated alkenyl groups: straight-chain or branched alkenes in which the hydrogen atoms may be partially or completely replaced by halogen atoms. Alkenyloxy: linear or branched alkenes linked to the structure via oxygen atoms. Haloalkenyloxy: straight-chain or branched alkenyloxy groups in which the hydrogen atoms may be partially or completely replaced by halogen atoms. Alkenylthio group: linear or branched alkenes linked to the structure via a sulfur atom bond. Such as CH2＝CHCH2S-. Alkenyloxycarbonyl radical: such as CH2＝CHCH2OCO-, etc. Alkynyl: straight barChain or branched alkynes, such as ethynyl, 1-propynyl, 2-propynyl and the different butynyl, pentynyl and hexynyl isomers. Alkynyl also includes groups consisting of multiple triple bonds, such as 2, 5-hexadiynyl. Halogenated alkynyl group: straight-chain or branched alkynes, in which the hydrogen atoms may be partially or completely replaced by halogen atoms. Alkynyloxy: straight or branched alkynes, linked to the structure via oxygen atom bonds. Haloalkynyloxy: straight-chain or branched alkynyloxy, in which the hydrogen atoms may be partially or completely substituted by halogen atoms. Alkynyloxycarbonyl group: such as CH ≡ CCH2OCO-, etc. An alkylsulfonyl group: straight or branched chain alkyl via sulfonyl (-SO)2-) is attached to a structure, such as a methylsulfonyl group. Haloalkylsulfonyl group: straight-chain or branched alkylsulfonyl wherein the hydrogen atoms of the alkyl group may be partially or wholly substituted by halogen atoms. An alkylcarbonyl group: the alkyl radical being bound to the structure via a carbonyl group, e.g. CH3CO-，CH3CH2CO-. Halogenated alkylcarbonyl group: the hydrogen atoms of the alkyl group of the alkylcarbonyl group may be partially or fully substituted by halogen atoms, e.g. CF3CO-. Alkoxycarbonyl group: the alkoxy group is attached to the structure via a carbonyl group. Such as CH3OCO-，CH3CH2OCO-. Aminocarbonyl group: such as NH2CO-. Alkyl amino carbonyl: alkyl-NH-CO-, e.g. CH3NHCO-，CH3CH2NHCO-. Dialkylaminocarbonyl group: such as (CH)3)2NCO-，(CH3CH2)2NCO-. The aryl moiety in (hetero) aryl, (hetero) arylalkyl, (hetero) arylcarbonyl, (hetero) arylmethylcarbonyl, (hetero) arylcarbonylalkyl, (hetero) aryloxycarbonyl, (hetero) arylalkyloxycarbonyl, and the like includes phenyl or naphthyl. Heteroaryl is a five or six membered ring containing 1 or more heteroatoms N, O, S. Such as furyl, pyrazolyl, thiazolyl, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazinyl, quinolinyl, and the like. (hetero) aryl group: such as phenyl, and the like. (hetero) arylalkyl: such as benzyl, phenethyl, p-chlorobenzyl, 2-chloropyridin-5-yl, 2-chloro-thiazol-5-yl, and the like. (hetero) arylcarbonyl group: such as benzoyl, 4-chlorobenzoyl and the like. (hetero) arylmethylcarbonyl: such as PhCH2CO-. (hetero) arylcarbonylalkyl: such as PhCOCH2-. (hetero) aryloxycarbonyl group: such as phenoxycarbonyl, 4-chlorophenoxycarbonyl, 4-nitrophenoxycarbonyl, naphthyloxycarbonyl, etc. Arylalkyloxycarbonyl group: such as benzyloxycarbonyl, 4-chlorobenzyloxycarbonyl, 4-trifluoromethylbenzyloxycarbonyl and the like. (hetero) arylalkyloxycarbonyl: such as PhCH2OCO-、4-Cl-PhCH2OCO-, etc.
Tables 1,2, 3, 4,5, 6, 7 and 8 show the R in the general formula I1、R2、R3(X＝NR3)、R4And R5、R6And R7、R8、R9And W are not limited to these substituents.
Figure BDA0001147669920000111
TABLE 1R1Substituent group
Figure BDA0001147669920000121
TABLE 2R2Substituent group
R2 R2 R2 R2
H F Cl Br
I CN NO2 NH2
CHO CH3 C2H5 n-C3H7
i-C3H7 n-C4H9 s-C4H9 i-C4H9
t-C4H9 OCH3 OC2H5 OC3H7-n
OC3H7-i OC4H9-n OC4H9-i OC4H9-t
OCH2F OCHF2 OCF3 OCH2CF3
TABLE 3R3Substituent group
Figure BDA0001147669920000122
Figure BDA0001147669920000131
Figure BDA0001147669920000141
TABLE 4R4(R5) Substituent group
Figure BDA0001147669920000142
TABLE 5R6(R7) Substituent group
Figure BDA0001147669920000143
TABLE 6R8Substituent group
Figure BDA0001147669920000151
TABLE 7R9Substituent group
Figure BDA0001147669920000152
Figure BDA0001147669920000161
TABLE 8W substituents
Figure BDA0001147669920000162
Some of the compounds of the present invention are illustrated by specific compounds listed in tables 9 to 32, but are not intended to limit the present invention. In compounds of the general formula I-1A, I-1B, I-1C, W ═ R6＝R7＝R13＝R14＝R15＝R16＝R17＝H，R9＝CH3。
In the general formula I-1A,
Figure BDA0001147669920000163
when R is1＝Cl、R2＝Cl、R3＝R4＝R5＝H，R8When m is 1, (R)10)nThe substituents are shown in Table 9, and represent the compound numbers of 9-1-9-279 in sequence.
TABLE 9
Figure BDA0001147669920000164
Figure BDA0001147669920000171
Figure BDA0001147669920000181
Figure BDA0001147669920000191
Table 9-1: in the general formula I-1A, when R is1＝Cl、R2＝CH3、R3＝R4＝R5＝H，R8When m is 1, a substituent (R)10)nIn accordance with the substituents shown in Table 9, the substituents correspond in turn to 9-1-9-279 of Table 9, and represent the compound numbers in turn 9-1-9-1-279.
Table 9-2: in the general formula I-1A, when R is1＝Cl、R2＝OCH3、R3＝R4＝R5＝H，R8When m is 1, a substituent (R)10)nIn accordance with the substituents shown in Table 9, the substituents correspond in turn to 9-1-9-279 of Table 9, and represent the compound numbers in turn 9-2-1-9-2-279.
Tables 9 to 3: in the general formula I-1A, when R is1＝Cl、R2＝CHO、R3＝R4＝R5＝H，R8When m is 1, a substituent (R)10)nIn accordance with substituent 9 shown in the table, the substituents correspond in turn to 9-1-9-279 of Table 9, and represent the compound numbers in turn 9-3-1-9-3-279.
Tables 9 to 4: in the general formula I-1A, when R is1＝Cl、R2＝Br、R3＝R4＝R5＝H，R8When m is 1, a substituent (R)10)nIn accordance with the substituents shown in Table 9, the substituents correspond in turn to 9-1-9-279 of Table 9, and represent the compound numbers in turn 9-4-1-9-4-279.
Table 10: in the general formula I-1A, when R is1＝CH3、R2＝Cl、R3＝R4＝R5＝H，R8When m is 1, a substituent (R)10)nIn accordance with the substituents shown in Table 9, the substituents correspond in turn to 9-1-9-279 of Table 9, and represent compound numbers in turn 10-1-10-279.
TABLE 10-1: in the general formula I-1A, when R is1＝CH3、R2＝Cl、R3＝R4＝R5＝H，R8＝CH3When m is 1, a substituent (R)10)nAs shown in Table 9The substituents are consistent, the substituents sequentially correspond to 9-1-9-279 of Table 9, and the representative compound numbers are sequentially 10-1-10-1-279.
Table 10-2: in the general formula I-1A, when R is1＝CH3、R2＝Cl、R3＝R4＝R5＝H，R8When m is 2, the substituent (R)10)nIn accordance with the substituents shown in Table 9, the substituents correspond in turn to 9-1-9-279 of Table 9, and represent the compound numbers in turn 10-2-1-10-2-279.
Tables 10 to 3: in the general formula I-1A, when R is1＝CH3、R2＝Cl、R3＝R4＝R5＝H，R8＝CH3When m is 2, a substituent (R)10)nIn accordance with the substituents shown in Table 9, the substituents correspond in turn to 9-1-9-279 of Table 9, and represent the compound numbers in turn 10-3-1-10-3-279.
Table 11: in the general formula I-1A, when R is1＝C2H5、R2＝Cl、R3＝R4＝R5＝H，R8When m is 1, a substituent (R)10)nIn accordance with the substituents shown in Table 9, the substituents correspond in turn to 9-1-9-279 of Table 9, and represent compound numbers in turn 11-1-11-279.
Table 11-1: in the general formula I-1A, when R is1＝C2H5、R2＝Cl、R3＝R4＝R5＝H，R8＝CH3When m is 1, a substituent (R)10)nIn accordance with the substituents shown in Table 9, the substituents correspond in turn to 9-1-9-279 of Table 9, and represent the compound numbers in turn 11-1-1-11-1-279.
Table 11-2: in the general formula I-1A, when R is1＝C2H5、R2＝Cl、R3＝R4＝R5＝H，R8When m is 2, the substituent (R)10)nIn accordance with the substituents shown in Table 9, the substituents correspond in turn to 9-1-9-279 of Table 9, and represent the compound numbers in turn 11-2-1-11-2-279.
Tables 11 to 3: in the general formula I-1A, when R is1＝C2H5、R2＝Cl、R3＝R4＝R5＝H，R8＝CH3When m is 2, a substituent (R)10)nIn accordance with the substituents shown in Table 9, the substituents correspond in turn to 9-1-9-279 of Table 9, and represent the compound numbers in turn 11-3-1-11-3-279.
Table 12: in the general formula I-1A, when R is1＝CHF2、R2＝Cl、R3＝R4＝R5＝H，R8When m is 1, a substituent (R)10)nIn accordance with the substituents shown in Table 9, the substituents correspond in turn to 9-1-9-279 of Table 9, and represent compound numbers in turn 12-1-12-279.
Table 12-1: in the general formula I-1A, when R is1＝CHF2、R2＝Cl、R3＝R4＝R5＝H，R8＝CH3When m is 1, a substituent (R)10)nIn accordance with the substituents shown in Table 9, the substituents correspond in turn to 9-1-9-279 of Table 9, and represent the compound numbers in turn 12-1-12-1-279.
Table 12-2: in the general formula I-1A, when R is1＝CHF2、R2＝Cl、R3＝R4＝R5＝H，R8When m is 2, the substituent (R)10)nIn accordance with the substituents shown in Table 9, the substituents correspond in turn to 9-1-9-279 of Table 9, and represent the compound numbers in turn 12-2-1-12-2-279.
Tables 12 to 3: in the general formula I-1A, when R is1＝CHF2、R2＝Cl、R3＝R4＝R5＝H，R8＝CH3When m is 2, a substituent (R)10)nIn accordance with the substituents shown in Table 9, the substituents correspond in turn to 9-1-9-279 of Table 9, and represent the compound numbers in turn 12-3-1-12-3-279.
Table 13: in the general formula I-1A, when R is1＝CF3、R2＝Cl、R3＝R4＝R5＝H，R8When m is 1, a substituent (R)10)nAnd a substituent group-A shown in Table 9Thus, the substituents correspond in turn to 9-1-9-279 of Table 9, and the representative compound numbers are in turn 13-1-13-279.
Table 14: in the general formula I-1A, when R is1＝Cl、R2＝Cl、R3＝R4＝H、R5＝CH3，R8When m is 1, a substituent (R)10)nIn accordance with the substituents shown in Table 9, the substituents correspond in turn to 9-1-9-279 of Table 9, and represent compound numbers in turn 14-1-14-279.
Table 15: in the general formula I-1A, when R is1＝CH3、R2＝Cl、R3＝R4＝H、R5＝CH3，R8When m is 1, a substituent (R)10)nIn accordance with the substituents shown in Table 9, the substituents correspond in turn to 9-1-9-279 of Table 9, and represent compound numbers in turn 15-1-15-279.
Table 16: in the general formula I-1A, when R is1＝C2H5、R2＝Cl、R3＝R4＝H、R5＝CH3，R8When m is 1, a substituent (R)10)nIn accordance with the substituents shown in Table 9, the substituents correspond in turn to 9-1-9-279 of Table 9, and represent compound numbers in turn 16-1-16-279.
Table 17: in the general formula I-1A, when R is1＝CHF2、R2＝Cl、R3＝R4＝H、R5＝CH3，R8When m is 1, a substituent (R)10)nIn accordance with the substituents shown in Table 9, the substituents correspond in turn to 9-1-9-279 of Table 9, and represent compound numbers in turn 17-1-17-279.
Table 18: in the general formula I-1A, when R is1＝CF3、R2＝Cl、R3＝R4＝H、R5＝CH3，R8When m is 1, a substituent (R)10)nIn accordance with the substituents shown in Table 9, the substituents correspond in turn to 9-1-9-279 of Table 9, and represent compound numbers in turn 18-1-18-279.
In the general formula I-1B
Figure BDA0001147669920000201
Table 19: in the general formula I-1B, when R is3＝R4＝R5＝H，R8When m is 1, a substituent (R)10)nIn accordance with the substituents shown in Table 9, the substituents correspond in turn to 9-1-9-279 of Table 9, and represent compound numbers in turn 19-1-19-279.
Table 19-1: in the general formula I-1B, when R is3＝R4＝R5＝H，R8＝CH3When m is 1, a substituent (R)10)nIn accordance with the substituents shown in Table 9, the substituents correspond in turn to 9-1-9-279 of Table 9, and represent the compound numbers in turn 19-1-19-1-279.
Table 19-2: in the general formula I-1B, when R is3＝R4＝R5＝H，R8When m is 2, the substituent (R)10)nIn accordance with the substituents shown in Table 9, the substituents correspond in turn to 9-1-9-279 of Table 9, and represent the compound numbers in turn 19-2-1-19-2-279.
Tables 19 to 3: in the general formula I-1B, when R is3＝R4＝R5＝H，R8＝CH3When m is 2, a substituent (R)10)nIn accordance with the substituents shown in Table 9, the substituents correspond in turn to 9-1-9-279 of Table 9, and represent the compound numbers in turn 19-3-1-19-3-279.
Table 20: in the general formula I-1B, when R is3＝R4＝H、R5＝CH3，R8When m is 1, a substituent (R)10)nIn accordance with the substituents shown in Table 9, the substituents correspond in turn to 9-1-9-279 of Table 9, and represent compound numbers in turn 20-1-20-279.
In the general formula I-1C
Figure BDA0001147669920000211
Table 21: in the general formula I-1C, when R is3＝R4＝R5＝H，R18＝Cl，R8When m is 1, a substituent (R)10)nIn accordance with the substituents shown in Table 9, the substituents correspond in turn to 9-1-9-279 of Table 9, and represent the compound numbers in turn 21-1-21-279.
Table 21-1: in the general formula I-1C, when R is3＝R4＝R5＝H，R18＝Cl，R8＝CH3When m is 1, a substituent (R)10)nIn accordance with the substituents shown in Table 9, the substituents correspond in turn to 9-1-9-279 of Table 9, and represent the compound numbers in turn 21-1-1-21-1-279.
Table 21-2: in the general formula I-1C, when R is3＝R4＝R5＝H，R18＝Cl，R8When m is 2, the substituent (R)10)nIn accordance with the substituents shown in Table 9, the substituents correspond in turn to 9-1-9-279 of Table 9, and represent the compound numbers in turn 21-2-1-21-2-279.
Tables 21 to 3: in the general formula I-1C, when R is3＝R4＝R5＝H，R18＝Cl，R8＝CH3When m is 2, a substituent (R)10)nIn accordance with the substituents shown in Table 9, the substituents correspond in turn to 9-1-9-279 of Table 9, and represent the compound numbers in turn 21-3-1-21-3-279.
Table 22: in the general formula I-1C, when R is3＝R4＝R5＝H，R18＝CH3，R8When m is 1, a substituent (R)10)nIn accordance with the substituents shown in Table 9, the substituents correspond in turn to 9-1-9-279 of Table 9, and represent the compound numbers in turn 22-1-22-279.
Table 23: in the general formula I-1C, when R is3＝R4＝H、R5＝CH3，R18＝Cl，R8When m is 1, a substituent (R)10)nIn accordance with the substituents shown in Table 9, the substituents correspond in turn to 9-1-9-279 of Table 9, and represent the compound numbers in turn 23-1-23-279.
Table 24: in the general formula I-1C, when R is3＝R4＝H、R5＝CH3，R18＝CH3，R8When m is 1, a substituent (R)10)nIn accordance with the substituents shown in Table 9, the substituents correspond in turn to 9-1-9-279 of Table 9, and represent the compound numbers in turn 24-1-24-279.
In the general formula I-1D
Figure BDA0001147669920000221
Table 25: in the general formula I-1D, when R is1＝CH3、R2＝Cl、R3＝R4＝R5＝H、X＝O，R8When m is 1, a substituent (R)10)nIn accordance with the substituents shown in Table 9, the substituents correspond in turn to 9-1-9-279 of Table 9, and represent compound numbers in turn 25-1-25-279.
Table 26: in the general formula I-1D, when R is1＝C2H5、R2＝Cl、R3＝R4＝R5＝H、X＝O，R8When m is 1, a substituent (R)10)nIn accordance with the substituents shown in Table 9, the substituents correspond in turn to 9-1-9-279 of Table 9 and represent the compound numbers in turn 26-1-26-279.
Table 27: in the general formula I-1D, when R is1＝CHF2、R2＝Cl、R3＝R4＝R5＝H、X＝O，R8When m is 1, a substituent (R)10)nIn accordance with the substituents shown in Table 9, the substituents correspond in turn to 9-1-9-279 of Table 9 and represent the compound numbers 27-1-27-279 in turn.
Table 28: in the general formula I-1D, when R is1＝CH3、R2＝Cl、R3＝R4＝R5＝H、X＝S，R8When m is 1, a substituent (R)10)nIn accordance with the substituents shown in Table 9, the substituents correspond in turn to 9-1-9-279 of Table 9, and represent compound numbers in turn 28-1-28-279.
Table 29: in the general formula I-1D, when R is1＝C2H5、R2＝Cl、R3＝R4＝R5＝H、X＝S，R8When m is 1, a substituent (R)10)nIn accordance with the substituents shown in Table 9, the substituents correspond in turn to 9-1-9-279 of Table 9 and represent the compound numbers in turn 29-1-29-279.
Table 30: in the general formula I-1D, when R is1＝CHF2、R2＝Cl、R3＝R4＝R5＝H、X＝S，R8When m is 1, a substituent (R)10)nIn accordance with the substituents shown in Table 9, the substituents correspond in turn to 9-1-9-279 of Table 9, and represent compound numbers in turn 30-1-30-279.
In the general formula I-1A, when R is1＝CH3、R2＝Cl、R4＝R5＝H、(R10)n＝4-CH3，R8When m is 1, the substituent R3(not hydrogen) are different substituents as shown in Table 31, representing compound numbers 31-1-31-140 in sequence.
Watch 31
Figure BDA0001147669920000222
Figure BDA0001147669920000231
Figure BDA0001147669920000241
The salts of some of the compounds of the present invention are illustrated by the salts of the specific compounds listed in Table 32, but are not intended to limit the present invention.
Table 32 partial compound salts
Figure BDA0001147669920000242
Figure BDA0001147669920000251
The compounds of the invention are prepared according to the following process, the reaction scheme being as follows, wherein the groups are as defined above unless otherwise stated:
the compounds of formula I are prepared by the following method:
Figure BDA0001147669920000252
and reacting the intermediates II and III in a proper solvent under the alkaline condition to obtain the compound shown in the general formula I.
Suitable bases may be selected from, for example, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, triethylamine, pyridine, sodium methoxide, sodium ethoxide, sodium hydride, potassium tert-butoxide, sodium tert-butoxide, etc.
The reaction is carried out in a suitable solvent, which may be selected from, for example, tetrahydrofuran, 1, 4-dioxane, acetonitrile, toluene, xylene, benzene, N-dimethylformamide, N-methylpyrrolidone, dimethylsulfoxide, acetone, or butanone.
The reaction temperature may be between room temperature and the boiling temperature of the solvent, and is generally from 20 to 100 ℃.
The reaction time is from 30 minutes to 20 hours, usually from 1 to 10 hours.
Intermediates II are commercially available in part and can also be prepared by known methods, for example, by methods described in references JP2000007662, US4977264, US6090815, US20040092402, JP09124613, US5468751, US4985426, US4845097, Journal of the American Chemical Society (1957),79,1455, Journal of Chemical Society (1955), p.3478-3481.
Intermediate III is a key intermediate for preparing the compound of the general formula I, and is prepared by the following method:
Figure BDA0001147669920000253
intermediate M1 was reacted with dimethyl carbonate at a suitable temperature in a suitable solvent for 30 minutes to 20 hours, typically 1-10 hours, to give intermediate M2, which was carried out according to Tetrahedron: Asymmetry,24(15-16), 925-936; 2013 and Angewandte Chemie, International Edition,53(45), 12210-; 2014; m2 was subjected to electrophilic substitution to obtain M3, which was performed in the manner described in Pest Management science,66(1),2010, 107-112; m3 and X1 react to obtain M4, which is described in Pest Management science,66(1),2010, 107-112; finally, M4 was reacted with the corresponding halide to give III, which was carried out in accordance with U.S. Pat. Nos. 20100158860, WO2011133444 and Bioorganic & Medicinal Chemistry,20(20), 6109-.
Further, the compound of formula I-1 can be prepared by the following method: the reaction conditions of each step refer to the corresponding steps for preparing the compound of the general formula I and relevant references.
Figure BDA0001147669920000261
The intermediates II and III are reacted in a suitable solvent under basic conditions to give the compounds of formula I-1.
Suitable bases may be selected from, for example, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, triethylamine, pyridine, sodium methoxide, sodium ethoxide, sodium hydride, potassium tert-butoxide, sodium tert-butoxide, etc.
The reaction is carried out in a suitable solvent, which may be selected from, for example, tetrahydrofuran, 1, 4-dioxane, acetonitrile, toluene, xylene, benzene, N-dimethylformamide, N-methylpyrrolidone, dimethylsulfoxide, acetone, or butanone.
The reaction temperature may be between room temperature and the boiling temperature of the solvent, and is generally from 20 to 100 ℃.
The reaction time is from 30 minutes to 20 hours, usually from 1 to 10 hours.
Intermediates II are commercially available in part and can also be prepared by known methods, for example, by methods described in references JP2000007662, US4977264, US6090815, US20040092402, JP09124613, US5468751, US4985426, US4845097, Journal of the American Chemical Society (1957),79,1455, Journal of Chemical Society (1955), p.3478-3481.
Intermediate III is a key intermediate for preparing the compound of the general formula I-1 of the invention and is prepared by the following method:
Figure BDA0001147669920000262
intermediate M1 was reacted with dimethyl carbonate at a suitable temperature in a suitable solvent for 30 minutes to 20 hours, typically 1-10 hours, to give intermediate M2, which was carried out according to Tetrahedron: Asymmetry,24(15-16), 925-936; 2013 and Angewandte Chemie, International Edition,53(45), 12210-; 2014; m2 was subjected to electrophilic substitution to obtain M3, which was performed in the manner described in Pest Management science,66(1),2010, 107-112; m3 and X1 react to obtain M4, which is described in Pest Management science,66(1),2010, 107-112; finally, M4 was reacted with the corresponding halide to give III, which was carried out in accordance with U.S. Pat. Nos. 20100158860, WO2011133444 and Bioorganic & Medicinal Chemistry,20(20), 6109-.
Although the compounds of the general formula I of the invention also belong to the substituted pyrazoles containing pyrimidine, compared with certain compounds disclosed in the prior art, the structural characteristics still have significant difference. And due to the structural difference, the compound of the invention has better bactericidal and insecticidal and acaricidal activity.
The compound of the general formula I shows excellent activity on various germs in agriculture or other fields, and also shows better activity on pests and mites. Therefore, the technical scheme of the invention also comprises the application of the compound shown in the general formula I in preparing bactericides, insecticides and acaricides in agriculture or other fields.
The examples of diseases mentioned below are intended only to illustrate the invention, but in no way limit it.
The compounds of the general formula I can be used for controlling the following diseases: oomycete diseases such as downy mildew (cucumber downy mildew, rape downy mildew, soybean downy mildew, beet downy mildew, sugarcane downy mildew, tobacco downy mildew, pea downy mildew, loofah downy mildew, wax gourd downy mildew, melon downy mildew, Chinese cabbage downy mildew, spinach downy mildew, radish downy mildew, grape downy mildew, onion downy mildew), white rust (rape white rust, Chinese cabbage white rust), damping-off (rape damping-off, tobacco damping-off, tomato damping-off, pepper damping-off, eggplant damping-off, cucumber damping-off, cotton seedling damping-off), cotton rot (hot pepper rot, loofah sponge rot, wax gourd blight), epidemic diseases (broad bean blight, cucumber blight, pumpkin blight, melon blight, hot pepper, leek blight, garlic blight, cotton blight, tomato blight, etc.; fungi imperfecti diseases such as wilt (sweet potato wilt, cotton wilt, sesame wilt, castor wilt, tomato wilt, bean wilt, cucumber wilt, pumpkin wilt, winter melon wilt, watermelon wilt, sweet melon wilt, hot pepper wilt, broad bean wilt, rape wilt, soybean wilt), root rot (hot pepper root rot, eggplant root rot, bean rot, cucumber root rot, bitter gourd root rot, cotton black root rot, broad bean root rot), damping off (seedling blight of cotton, sesame seedling blight, hot pepper seedling blight, cucumber damping off, cabbage stalk rot), anthracnose (sorghum anthracnose, cotton anthracnose, kenaf anthracnose, jute anthracnose, flax anthracnose, tobacco anthracnose, mulberry leaf, hot pepper, bean disease, cucumber anthracnose, red sesame anthracnose, jute anthracnose, flax anthracnose, tobacco anthracnose, eggplant disease, hot pepper anthracnose, vegetable bean disease, and cucumber blight, Balsam pear anthracnose, pumpkin anthracnose, wax gourd anthracnose, watermelon anthracnose, melon anthracnose, litchi anthracnose), verticillium wilt (cotton verticillium wilt, sunflower verticillium wilt, tomato verticillium wilt, hot pepper verticillium wilt, eggplant verticillium wilt), scab (pumpkin scab, wax gourd scab, melon scab), gray mold (boll gray mold, red ramie gray mold, tomato gray mold, hot pepper gray mold, bean gray mold, celery gray mold, spinach gray mold, kiwi gray mold), brown spot (cotton brown spot, jute brown spot, beet brown spot, peanut brown spot, pepper brown spot, wax gourd brown spot, soybean brown spot, sunflower brown spot, pea brown spot, broad bean brown spot), black spot (flax brown spot, rape black spot, sesame black spot, sunflower black spot, castor black spot, tomato black spot, pepper black spot, eggplant black spot, bean black spot, cucumber black spot, celery black spot, carrot black rot, carrot black spot, apple black spot, peanut black spot), spot blight (tomato spot blight, pepper spot blight, celery spot blight), early blight (tomato early blight, pepper early blight, eggplant early blight, potato early blight, celery early blight), ring spot (soybean ring spot, sesame ring spot, bean ring spot), leaf blight (sesame leaf blight, sunflower leaf blight, watermelon leaf blight, melon leaf blight), stem base rot (tomato stem base rot, bean stem base rot), and others (corn round spot, kenaf waist fold, rice blast, black sheath blight, sugarcane eye spot, cotton boll aspergillosis, peanut crown rot, soybean stem blight, soybean black spot, melon big spot, peanut net spot, tea leaf spot, red leaf spot, black leaf spot, peanut net spot, tea leaf spot, tomato black spot, potato leaf spot, potato black spot, tomato leaf, Pepper white spot disease, white gourd leaf spot disease, celery black rot disease, spinach heart rot disease, kenaf leaf mold disease, kenaf spot disease, jute stem spot disease, soybean purple spot disease, sesame leaf spot disease, castor gray spot disease, tea brown leaf spot disease, eggplant brown orbicular spot disease, kidney bean red spot disease, bitter gourd leukoderma, watermelon spot disease, jute bottom rot disease, sunflower root stem rot disease, kidney bean carbon rot disease, soybean target spot disease, eggplant rod spore leaf spot disease, cucumber target spot disease, tomato leaf mold, eggplant leaf mold, broad bean red spot disease and the like); basidiomycete diseases such as rust (wheat stripe rust, wheat stalk rust, wheat leaf rust, peanut rust, sunflower rust, sugarcane rust, leek rust, onion rust, chestnut rust, soybean rust), smut (maize head smut, maize smut, sorghum head smut, sorghum loose smut, sorghum stalk smut, chestnut kernel smut, sugarcane head smut, kidney bean rust) and others (such as wheat sharp eyespot, rice sheath blight, etc.); ascomycetous diseases, such as powdery mildew (wheat powdery mildew, rape powdery mildew, sesame powdery mildew, sunflower powdery mildew, beet powdery mildew, eggplant powdery mildew, pea powdery mildew, towel gourd powdery mildew, pumpkin powdery mildew, wax gourd powdery mildew, melon powdery mildew, grape powdery mildew, broad bean powdery mildew), sclerotinia rot (flax sclerotinia rot, rape sclerotinia rot, soybean sclerotinia rot, peanut sclerotinia rot, tobacco sclerotinia rot, pepper sclerotinia rot, eggplant sclerotinia rot, kidney bean sclerotinia rot, pea sclerotinia rot, cucumber sclerotinia rot, bitter gourd sclerotinia rot, wax gourd sclerotinia rot, watermelon sclerotinia rot, celery sclerotinia rot), scab (apple scab, pear scab) and the like.
Owing to their positive properties, the abovementioned compounds can be used advantageously for protecting crops, domestic animals and breeding animals of agricultural and horticultural importance, as well as the environment in which humans are often exposed, against harmful germs, pests and mites.
The amount of the compound used to achieve the desired effect will vary depending on factors such as the compound used, the crop to be protected, the type of pest, the extent of infection, the climatic conditions, the method of application, and the dosage form employed.
A dose of 10 g to 5 kg of compound per hectare provides adequate control.
The invention also discloses a bactericidal, insecticidal and acaricidal composition which takes the compound shown as the general formula I as an active component. The weight percentage of the active components in the composition for killing bacteria, insects and mites is between 0.5 and 99 percent. The composition also comprises a carrier acceptable in agriculture, forestry and sanitation.
The compositions of the present invention may be administered in the form of a formulation. The compound shown in the general formula I is used as an active component to be dissolved or dispersed in a carrier or prepared into a preparation so as to be easier to disperse when being used for sterilization and disinsection. For example: the chemical preparations can be prepared into wettable powder, oil suspension, water suspension, aqueous emulsion, aqueous solution or missible oil and the like. In these compositions, at least one liquid or solid carrier is added, and when necessary, a suitable surfactant may be added.
The technical scheme of the invention also comprises a method for preventing and controlling germs, pests and mites, which comprises the following steps: the sterilizing, insecticidal and acaricidal composition is applied to the pathogenic bacteria or the growth medium thereof. Preferably, an effective amount of 10 to 1000 grams per hectare is generally selected, with an effective amount of 20 to 500 grams per hectare being preferred.
For certain applications, for example in agriculture, one or more other fungicides, insecticides, acaricides, herbicides, plant growth regulators or fertilizers and the like can be added to the fungicidal, insecticidal and acaricidal compositions of the present invention, whereby additional advantages and effects can be produced.
It should be understood that various changes and modifications may be made within the scope of the present invention as defined by the claims.
Detailed Description
The following specific examples are intended to further illustrate the invention, but the invention is in no way limited to these examples (all materials are commercially available unless otherwise indicated).
Synthetic examples
Example 1: preparation of intermediate 4, 5-dichloro-6-methylpyrimidine
1) Preparation of 4-hydroxy-5-chloro-6-methylpyrimidine
Figure BDA0001147669920000281
To a solution of 11.30g (0.11mol) formamidine acetate in 50ml methanol was slowly added dropwise, while stirring at room temperature, a solution of 8.80g (0.16mol) sodium methoxide in methanol, and stirring was continued for 2 hours at room temperature after completion of the addition. Then, 11.17g (0.068mol) of intermediate ethyl 2-chloroacetoacetate was added dropwise to the above solution, and the reaction was continued with stirring at room temperature for 5 to 7 hours. After TLC monitoring reaction, decompressing and distilling off solvent, adjusting pH to 5-6 with hydrochloric acid, filtering to obtain orange yellow solid, extracting water phase with (3X 50ml) ethyl acetate, drying with anhydrous magnesium sulfate, filtering and desolventizing. The residue was dissolved in 50ml of ethyl acetate, left overnight and filtered to give 6.48g of an orange-yellow solid. The yield is 66 percent, and the melting point is 181-184 ℃.
2) Preparation of 4, 5-dichloro-6-methylpyrimidine
Figure BDA0001147669920000282
14.5g (0.1mol) of 4-hydroxy-5-chloro-6-methylpyrimidine is dissolved in 50ml of toluene solution, 50ml of phosphorus oxychloride is dripped into a reaction bottle under stirring, and the temperature is increased after dripping for reflux reaction for 5 to 7 hours. After completion of the TLC monitoring reaction, toluene and excess phosphorus oxychloride were distilled off under reduced pressure, the reaction was poured into ice water with stirring, the aqueous phase was extracted with (3X 50ml) ethyl acetate, the organic phases were combined, dried over anhydrous magnesium sulfate, filtered and desolventized. The residue was subjected to column chromatography (eluent ethyl acetate and petroleum ether at a volume ratio of 1:5) to give 14.43g of a yellow liquid with a yield of 88.5%.
Example 2: preparation of 4, 5-dichlorothieno [2,3-d ] pyrimidine
Figure BDA0001147669920000291
Taking 2-amino-3-cyano-4-oxo-5, 5-dihydrothiophene and 250ml of phosphorus oxychloride (POCl)3) In the reaction flask, 38ml of N, N-dimethylformamide was slowly dropped at room temperature over about 30 minutes. The reaction was carried out at room temperature for 1 hour and then at 75 ℃ for 3 hours. After cooling to room temperature, the reaction solution was poured into crushed ice and filtered to obtain 89.1g of dark gray solid with a yield of 86.9% and a melting point of 160-.
Example 3: preparation of intermediate 4-chloroquinazoline
1) Preparation of quinazolin-4 (3H) -ones
Figure BDA0001147669920000292
13.7g (0.1mol) of anthranilic acid and 20ml of formamide are taken in a 250ml three-necked flask and heated to 140 ℃ for reaction for 5-8 hours. After the completion of the TLC monitoring reaction, the reaction solution was cooled to 100 ℃ and 80ml of water was added dropwise with stirring, followed by cooling to room temperature, filtration and washing of the filter cake with anhydrous ether to obtain 10.96g of reddish brown with a yield of 75.1%.
2) Preparation of 4-chloroquinazoline
Figure BDA0001147669920000293
14.6g (0.1mol) of quinazolin-4 (3H) -one is taken in a 250ml single-neck bottle, 50ml of thionyl chloride is taken as a solvent, and the temperature is increased to reflux reaction for 4 to 6 hours. After the completion of the TLC monitoring reaction, the reaction solution was cooled and poured into water and stirred for 30min, filtered and washed with anhydrous ether to obtain a reddish brown solid 10.96g, yield 92.7%.
Example 4: synthesis of intermediate 2- (1- (4-chlorophenyl) -1H-pyrazole-3-oxy) ethylamine hydrochloride
1) Preparation of N-Boc-2-bromoethylamine
Figure BDA0001147669920000294
20.5g (0.1mol) of bromoethylamine bromate was placed in 80ml of tetrahydrofuran, 10.08g (0.12mol) of sodium bicarbonate and 50ml of water were sequentially added, 21.80g (0.1mol) of di-tert-butyl dicarbonate was added dropwise under stirring at room temperature, and the reaction was continued for 4 to 10 hours after completion of the dropwise addition. After the reaction, the solvent was distilled off under reduced pressure, ethyl acetate (3X 50ml) was added for extraction, and the organic phase was washed with 50ml of saturated brine, followed by desolventizing to obtain 21.68g of a colorless oily liquid with a yield of 96.8%.
2) Preparation of N-Boc-2- (3- (4-chlorophenyl) -1-methyl-pyrazol-5-yloxy) ethylamine
Figure BDA0001147669920000301
2.24g (0.01mol) of N-Boc-2-bromoethylamine and 2.09g (0.01mol) of 2- (3- (4-chlorophenyl) -1-methyl-5-hydroxypyrazole (preparation method is referred to Pest Manag Sci (2010),66(1), p.107-112) were added to 50ml of butanone, 2.76g (0.02mol) of potassium carbonate were added, the mixture was heated to reflux with stirring, the reaction was carried out for 4 to 10 hours, after the completion of the TLC monitoring reaction, the solvent was distilled off under reduced pressure, 3X 50ml of ethyl acetate was added and extracted, the organic phase was washed with 50ml of saturated saline, and after the precipitation, column chromatography was carried out on the residue (eluent, ethyl acetate and petroleum ether, volume ratio: 1:6) to obtain 2.96g of a yellow solid with a yield of 83.8%.
3) Preparation of 2- (1- (4-chlorophenyl) -1H-pyrazol-3-oxy) ethylamine hydrochloride
Figure BDA0001147669920000302
3.51g (0.01mol) of N-Boc-2- (3- (4-chlorophenyl) -1-methyl-pyrazol-5-oxyl) ethylamine was added to 50ml of ethyl acetate, 6ml of concentrated hydrochloric acid was added dropwise with stirring at room temperature to dissolve the solid, stirring was continued for 4 to 5 hours, after the completion of the TLC monitoring reaction, the solvent was distilled off under reduced pressure, 10ml of dichloromethane was added and stirring was carried out for half an hour, filtration was carried out, and the filter cake was washed with dichloromethane to obtain 2.33g of a white solid.
Example 5: preparation of Compounds 11-19
Figure BDA0001147669920000303
1.77g (0.01mol) of 4, 5-dichloro-6-ethylpyrimidine and 2.88g (0.01mol) of 2- (3- (4-chlorophenyl) -1-methyl-pyrazol-5-yloxy) ethylamine hydrochloride are added to 50ml of toluene. 4.45g (0.022mol) of triethylamine is added, the mixture is heated to reflux and reacted for 4 to 10 hours, after TLC monitoring the reaction is finished, the solvent is evaporated under reduced pressure, ethyl acetate (3X 50ml) is added for extraction, an organic phase is washed by 50ml of saturated saline solution, and after desolventization, column chromatography is carried out on a residue (eluent is ethyl acetate and petroleum ether (boiling range is 60 to 90 ℃) with the volume ratio of 1:4) to obtain 3.12g of white solid with the yield of 79.6 percent.
1H-NMR (600MHz, internal standard TMS, solvent CDCl3)δ(ppm):8.46(s,1H,Pyrimidine-H),7.64-7.65(d,2H,Ph-2,6-2H),7.32-7.34(d,2H,Ph-3,5-2H),5.82(s,1H,Pyrazole-4-H),5.77(s,1H,NH),4.30((t,2H,O-CH2),3.97-4.00(m,2H,N-CH2),3.70(s,3H,N-CH3),2.80-2.84(m,2H,CH2),1.27(t,3H,CH3).
Example 6: preparation of Compounds 19-19
Figure BDA0001147669920000304
1.64g (0.01mol) of 4-chloroquinazoline and 2.88g (0.01mol) of 2- (3- (4-chlorophenyl) -1-methyl-pyrazol-5-yloxy) ethylamine hydrochloride are added to 50ml of toluene. 4.45g (0.022mol) of triethylamine is added, the mixture is heated to reflux and reacted for 4 to 10 hours, after the TLC monitoring reaction is finished, the solvent is evaporated under reduced pressure, ethyl acetate (3X 50ml) is added for extraction, an organic phase is washed by 50ml of saturated saline solution, and after desolventization, column chromatography is carried out on a residue (eluent is ethyl acetate and petroleum ether (boiling range is 60 to 90 ℃) with the volume ratio of 1:4) to obtain 2.98g of white solid, the yield is 78.6 percent, and the melting point is 197.2 ℃.
1H-NMR (600MHz, internal standard TMS, solvent CDCl3)δ(ppm):8.65(s,1H,Quinazoline-3-H),7.73(d,J＝2.4Hz,1H,Pyrazole-5-H),7.40-7.72(m,5H,Ph-3,4,5,6-5H),7.40-7.72(m,4H,Quinazoline-5,6,7,8-4H),5.97(d,J＝2.4Hz,1H,Pyrazole-4-H),5.90(s,1H,NH),4.63(t,2H,O-CH2),4.06(m,2H,N-CH2)。
Example 7: preparation of Compounds 21-19
Figure BDA0001147669920000311
0.41g (0.002mol) of 4, 5-dichlorothieno [2,3-d ] pyrimidine and 0.58g (0.002mol) of 2- (3- (4-chlorophenyl) -1-methyl-pyrazol-5-yloxy) ethylamine hydrochloride were added to 50ml of toluene. Adding 0.45g (0.0022mol) triethylamine, heating to reflux, reacting for 4-10 hours, after TLC monitoring reaction, decompressing and distilling off solvent, adding (3X 50ml) ethyl acetate for extraction, washing organic phase with 50ml saturated saline, after exsolution, carrying out column chromatography on residue (eluent is ethyl acetate and petroleum ether (60-90 ℃), volume ratio is 1:4) to obtain 0.64g white solid, yield is 75.8%, melting point is 167.9 ℃.
1H-NMR (600MHz, internal standard TMS, solvent CDCl3)δ(ppm):8.46(s,1H,Pyrimidine-H),8.22-8.24(d,2H,Ph-2,6-2H),7.85-7.88(d,2H,Ph-3,5-2H),5.94(s,1H,Pyrazole-4-H),5.71(s,1H,NH),4.33(t,2H,O-CH2),3.97-4.02(m,2H,N-CH2),3.74(s,3H,N-CH3),2.79-2.82(m,2H,CH2),1.27(t,3H,CH3).
Other compounds of the invention may be prepared by reference to the above examples.
Physical property data of partial compoundAnd nuclear magnetic data (1HNMR, 600MHz, internal standard TMS, ppm) as follows:
compound 10-1 melting point 117.8 ℃. Delta (CDCl)3):8.41(s,1H,Pyrimidine-H),7.70-7.73(d,2H,Ph-2,6-2H),7.37(t,2H,Ph-3,5-2H),7.28(t,1H,Ph-4-H),5.85(s,1H,Pyrazole-4-H),5.75(s,1H,NH),4.30(t,2H,O-CH2),3.95-4.00(m,2H,N-CH2),3.71(s,3H,N-CH3),2.48(s,3H,CH3)。
Compound 10-4: delta (CDCl)3):8.41(s,1H,Pyrimidine-H),7.67(t,2H,Ph-2,6-2H),7.06(t,2H,Ph-3,5-2H),5.80(s,1H,Pyrazole-4-H),5.79(s,1H,NH),4.30((t,2H,O-CH2),3.95-4.00(m,2H,N-CH2),3.70(s,3H,N-CH3),2.48(s,3H,CH3)。
Compounds 10-17 oil. delta. (CDCl)3):8.40(s,1H,Pyrimidine-H),7.74(dd,1H,Ph-6-1H),7.40(dd,1H,Ph-3-1H),7.28(td,1H,Ph-5-1H),7.23(td,1H,Ph-4-1H),6.09(s,1H,Pyrazole-4-H),5.74(s,1H,NH),4.31(t,2H,O-CH2),3.96-3.99(m,2H,N-CH2),3.72(s,3H,N-CH3),2.48(s,3H,CH3).
Compounds 10-19 oil. delta. (CDCl3):8.41(s,1H, Pyrimidine-H),7.64-7.66(d,2H, Ph-2,6-2H),7.32-7.35(d,2H, Ph-3,5-2H),5.82(s,1H, Pyrazole-4-H),5.77(s,1H, NH),4.30(t,2H, O-CH2),3.95-4.00(m,2H, N-CH2),3.68(s,3H, N-CH3),2.48(s,3H, CH 3).
10-21 of compound, melting point 87.8 ℃. Delta (CDCl)3):8.41(s,1H,Pyrimidine-H),7.72(d,1H,Ph-6-1H),7.43(s,1H,Ph-3-1H),7.26(dd,1H,Ph-5-1H),6.09(s,1H,Pyrazole-4-H),5.73(s,1H,NH),4.31(t,2H,O-CH2),3.96-3.99(m,2H,N-CH2),3.72(s,3H,N-CH3),2.49(s,3H,CH3).
10-34 of compound, melting point 155.0 ℃. Delta (CDCl)3):8.41(s,1H,Pyrimidine-H),7.58-7.60(d,2H,Ph-2,6-2H),7.48-7.50(d,2H,Ph-3,5-2H),5.82(s,1H,Pyrazole-4-H),5.77(s,1H,NH),4.29(t,2H,O-CH2),3.95-4.00(m,2H,N-CH2),3.70(s,3H,N-CH3),2.48(s,3H,CH3).
Compound 10-52 melting point 192.0 ℃. Delta (CDCl)3):8.41(s,1H,Pyrimidine-H),8.22-8.24(d,2H,Ph-2,6-2H),7.85-7.88(d,2H,Ph-3,5-2H),5.94(s,1H,Pyrazole-4-H),5.71(s,1H,NH),4.32(t,2H,O-CH2),3.97-4.02(m,2H,N-CH2),3.74(s,3H,N-CH3),2.48(s,3H,CH3).
Compounds 10-57: delta (CDCl)3):8.41(s,1H,Pyrimidine-H),7.59-7.62(d,2H,Ph-2,6-2H),7.16-7.19(d,2H,Ph-3,5-2H),5.82(s,1H,Pyrazole-4-H),5.78(s,1H,NH),4.30(t,2H,O-CH2),3.95-4.00(m,2H,N-CH2),3.70(s,3H,N-CH3),2.48(s,3H,Pyrimidine-CH3),2.88(s,3H,Ph-CH3).
Compound 10-68, melting point 120.6 ℃. Delta (CDCl)3):8.41(s,1H,Pyrimidine-H),7.97(s,1H,Ph-2-1H),7.89(d,1H,Ph-6-1H),7.53(d,1H,Ph-4-1H),7.48(t,1H,Ph-5-1H),5.90(s,1H,Pyrazole-4-H),5.73(s,1H,NH),4.31(t,2H,O-CH2),3.97-4.00(m,2H,N-CH2),3.72(s,3H,N-CH3),2.48(s,3H,CH3).
Compound 11-1 oil. delta. (CDCl)3):8.46(s,1H,Pyrimidine-H),7.70-7.73(d,2H,Ph-2,6-2H),7.37(t,2H,Ph-3,5-2H),7.28(t,1H,Ph-4-H),5.85(s,1H,Pyrazole-4-H),5.75(s,1H,NH),4.30(t,2H,O-CH2),3.96-4.00(m,2H,N-CH2),3.65(s,3H,N-CH3),2.79-2.82(m,2H,CH2),1.27(t,3H,CH3)。
Compound 11-1-1: delta (CDCl3):8.42(s,1H, Pyrimidine-H),7.45-7.47(d,2H, Ph-2,6-2H),7.43(t,1H, Ph-4-H),7.32(t,2H, Ph-3,5-2H),6.43(s,1H, NH),4.47(t,2H, O-CH)2),3.89-3.94(m,2H,N-CH2),3.62(s,3H,N-CH3),2.75-2.83(m,2H,CH2),1.88(s,3H,Pyrazole-4-CH3),1.26(t,3H,CH3)。
Compound 11-4: delta (CDCl)3):8.46(s,1H,Pyrimidine-H),7.67(d,2H,Ph-2,6-2H),7.05(d,2H,Ph-3,5-2H),5.80(s,1H,Pyrazole-4-H),5.79(s,1H,NH),4.30((t,2H,O-CH2),3.95-4.00(m,2H,N-CH2),3.70(s,3H,N-CH3),2.79-2.82(m,2H,CH2),1.27(t,3H,CH3).
Compounds 11-17 oil. delta. (CDCl)3):8.44(s,1H,Pyrimidine-H),7.74(dd,1H,Ph-6-1H),7.40(dd,1H,Ph-3-1H),7.28(td,1H,Ph-5-1H),7.23(td,1H,Ph-4-1H),6.09(s,1H,Pyrazole-4-H),5.75(s,1H,NH),4.30(t,2H,O-CH2),3.96-3.99(m,2H,N-CH2),3.72(s,3H,N-CH3),2.78-2.82(m,2H,CH2),1.26(t,3H,CH3).
Compound 11-21, melting point 138.9 ℃. Delta (CDCl)3):8.45(s,1H,Pyrimidine-H),7.72(d,1H,Ph-6-1H),7.43(s,1H,Ph-3-1H),7.27(dd,1H,Ph-5-1H),7.73(t,1H,CH),6.09(s,1H,Pyrazole-4-H),5.73(s,1H,NH),4.31(t,2H,O-CH2),4.02-4.05(m,2H,N-CH2),3.72(s,3H,N-CH3),2.79-2.83(m,2H,CH2),1.27(t,3H,CH3).
11-34 of the compound, melting point 133.3 ℃. Delta (CDCl)3):8.45(s,1H,Pyrimidine-H),7.58-7.60(d,2H,Ph-2,6-2H),7.47-7.49(d,2H,Ph-3,5-2H),5.82(s,1H,Pyrazole-4-H),5.77(s,1H,NH),4.30(t,2H,O-CH2),3.95-4.00(m,2H,N-CH2),3.70(s,3H,N-CH3),2.79-2.82(m,2H,CH2),1.27(t,3H,CH3)。
Compound 11-52 melting point 166.8 ℃. Delta (CDCl)3):8.41(s,1H,Pyrimidine-H),8.22-8.24(d,2H,Ph-2,6-2H),7.85-7.88(d,2H,Ph-3,5-2H),5.94(s,1H,Pyrazole-4-H),5.71(s,1H,NH),4.32(t,2H,O-CH2),3.97-4.02(m,2H,N-CH2),3.74(s,3H,N-CH3),2.79-2.83(m,2H,CH2),1.27(t,3H,CH3).
Compounds 11-57: delta (CDCl)3):8.45(s,1H,Pyrimidine-H),7.59-7.62(d,2H,Ph-2,6-2H),7.16-7.19(d,2H,Ph-3,5-2H),5.82(s,1H,Pyrazole-4-H),5.74(s,1H,NH),4.30(t,2H,O-CH2),3.95-4.00(m,2H,N-CH2),3.70(s,3H,N-CH3),2.77-2.84(m,2H,Pyrimidine-CH2),2.31(s,3H,Ph-CH3),1.24(t,3H,-CH2CH3)。
The melting point of the compound is 11-68 ℃ and 99.8 ℃. Delta (CDCl)3):8.46(s,1H,Pyrimidine-H),7.97(s,1H,Ph-2-1H),7.89(d,1H,Ph-6-1H),7.53(d,1H,Ph-4-1H),7.48(t,1H,Ph-5-1H),5.90(s,1H,Pyrazole-4-H),5.73(s,1H,NH),4.32(t,2H,O-CH2),3.97-4.00(m,2H,N-CH2),3.73(s,3H,N-CH3),2.79-2.83(m,2H,CH2),1.27(t,3H,CH3).
Compound 11-75, melting point 127.8 ℃. Delta (CDCl)3):8.45(s,1H,Pyrimidine-H),7.63-7.64(d,2H,Ph-2,6-2H),7.25-7.26(d,2H,Ph-3,5-2H),5.82(s,1H,Pyrazole-4-H),5.73(s,1H,NH),4.30(t,2H,O-CH2),3.97-3.99(m,2H,N-CH2),3.70(s,3H,N-CH3),2.79-2.83(m,2H,CH2),2.50(s,3H,S-CH3),1.27(t,3H,CH3).
Compounds 11-78: Delta (CDCl)3):8.50(s,1H,Pyrimidine-H),7.71-7.74(d,2H,Ph-2,6-2H),7.20-7.23(d,2H,Ph-3,5-2H),5.83(s,1H,Pyrazole-4-H),5.74(s,1H,NH),4.31(t,2H,O-CH2),3.95-4.01(m,2H,N-CH2),3.71(s,3H,N-CH3),2.77-2.84(m,2H,CH2),1.26(t,3H,CH3)。
Compound 12-1, melting point 115.4 ℃. Delta (CDCl)3):8.59(s,1H,Pyrimidine-H),7.70-7.73(d,2H,Ph-2,6-2H),7.37(t,2H,Ph-3,5-2H),7.28(t,1H,Ph-4-H),6.73(t,1H,CH),6.00(s,1H,NH),5.85(s,1H,Pyrazole-4-H),4.32(t,2H,O-CH2),4.01-4.06(m,2H,N-CH2),3.71(s,3H,N-CH3).
The compounds 12-1-1: delta (CDCl3):8.55(s,1H, Pyrimidine-H),7.45-7.48(d,2H, Ph-2,6-2H),7.44(t,1H, Ph-4-H),7.30(t,2H, Ph-3,5-2H),7.02(s,1H, NH),6.73(s,1H, CH),4.51(t,2H, O-CH2),3.92-3.97(m,2H, N-CH2),3.62(s,3H, N-CH3),1.87(s,3H, Pyrazole-4-CH 3).
Compound 12-4: delta (CDCl)3):8.59(s,1H,Pyrimidine-H),7.67(t,2H,Ph-2,6-2H),7.06(t,2H,Ph-3,5-2H),6.73(t,1H,CH),6.00(s,1H,NH),5.80(s,1H,Pyrazole-4-H),4.32(t,2H,O-CH2),4.02-4.05(m,2H,N-CH2),3.70(s,3H,N-CH3).
Compounds 12-17 oil. delta. (CDCl)3):8.59(s,1H,Pyrimidine-H),7.75(dd,1H,Ph-6-1H),7.41(dd,1H,Ph-3-1H),7.28(td,1H,Ph-5-1H),7.24(td,1H,Ph-4-1H),6.73(t,1H,CH),6.10(s,1H,Pyrazole-4-H),6.01(s,1H,NH),4.33(t,2H,O-CH2),4.02-4.05(m,2H,N-CH2),3.73(s,3H,N-CH3).
Compounds 12-19, mp 143.2 ℃. Delta (CDCl)3):8.59(s,1H,Pyrimidine-H),7.63-7.66(d,2H,Ph-2,6-2H),7.32-7.35(d,2H,Ph-3,5-2H),6.73(t,1H,CH),6.00(s,1H,NH),5.82(s,1H,Pyrazole-4-H),4.32(t,2H,O-CH2),4.01-4.06(m,2H,N-CH2),3.70(s,3H,N-CH3).
Compounds 12-21, melting point 116.3 ℃. Delta (CDCl)3):8.59(s,1H,Pyrimidine-H),7.72(d,1H,Ph-6-1H),7.43(s,1H,Ph-3-1H),7.26(dd,1H,Ph-5-1H),7.73(t,1H,CH),6.10(s,1H,Pyrazole-4-H),6.00(s,1H,NH),4.33(t,2H,O-CH2),4.02-4.05(m,2H,N-CH2),3.72(s,3H,N-CH3).
Compound 12-34, mp 149.5 ℃. Delta (CDCl)3):8.59(s,1H,Pyrimidine-H),7.57-7.60(d,2H,Ph-2,6-2H),7.47-7.50(d,2H,Ph-3,5-2H),6.73(t,1H,CH),6.00(s,1H,NH),5.82(s,1H,Pyrazole-4-H),4.32(t,2H,O-CH2),4.01-4.06(m,2H,N-CH2),3.70(s,3H,N-CH3)。
Compound 12-52 melting point 215.1 ℃. Delta (CDCl)3):8.60(s,1H,Pyrimidine-H),8.22-8.24(d,2H,Ph-2,6-2H),7.85-7.88(d,2H,Ph-3,5-2H),6.72(t,1H,CH),6.00(s,1H,NH),5.94(s,1H,Pyrazole-4-H),4.33(t,2H,O-CH2),4.04-4.07(m,2H,N-CH2),3.74(s,3H,N-CH3).
Compounds 12-57: delta (CDCl)3):8.59(s,1H,Pyrimidine-H),7.59-7.62(d,2H,Ph-2,6-2H),7.16-7.19(d,2H,Ph-3,5-2H),6.73(t,1H,CH),6.02(s,1H,NH),5.82(s,1H,Pyrazole-4-H),4.32(t,2H,O-CH2),4.00-4.06(m,2H,N-CH2),3.70(s,3H,N-CH3),2.88(s,3H,Ph-CH3)。
Compounds 12-66 oil. delta. (CDCl)3):8.59(s,1H,Pyrimidine-H),7.63-7.64(d,2H,Ph-2,6-2H),7.20-7.22(d,2H,Ph-3,5-2H),6.73(t,1H,CH),6.03(s,1H,NH),5.82(s,1H,Pyrazole-4-H),4.31(t,2H,O-CH2),4.02-4.04(m,2H,N-CH2),3.70(s,3H,N-CH3),2.64-2.68(m,2H,CH2),1.25(t,3H,CH3).
Compound 12-68, melting point 118.3 ℃. Delta (CDCl)3):8.59(s,1H,Pyrimidine-H),7.97(s,1H,Ph-2-1H),7.89(d,1H,Ph-6-1H),7.53(d,1H,Ph-4-1H),7.48(t,1H,Ph-5-1H),6.73(t,1H,CH),6.02(s,1H,NH),5.90(s,1H,Pyrazole-4-H),4.33(t,2H,O-CH2),4.03-4.06(m,2H,N-CH2),3.72(s,3H,N-CH3).
Compound 12-75, melting point 130.4 ℃. Delta (CDCl)3):8.59(s,1H,Pyrimidine-H),7.63-7.64(d,2H,Ph-2,6-2H),7.25-7.26(d,2H,Ph-3,5-2H),6.75(t,1H,CH),6.00(s,1H,NH),5.82(s,1H,Pyrazole-4-H),4.30(t,2H,O-CH2),3.97-4.00(m,2H,N-CH2),3.70(s,3H,N-CH3),2.50(s,3H,S-CH3).
Compounds 12-78: Delta (CDCl)3):8.60(s,1H,Pyrimidine-H),7.72-7.74(d,2H,Ph-2,6-2H),7.20-7.23(d,2H,Ph-3,5-2H),6.73(t,1H,CH),6.00(s,1H,NH),5.83(s,1H,Pyrazole-4-H),4.32(t,2H,O-CH2),4.01-4.06(m,2H,N-CH2),3.71(s,3H,N-CH3)。
Compound 19-1: delta (CDCl)3):8.71(s,1H,Quinazoline-3-H),7.88-7.91(d,1H,Quinazoline-5-H),7.77-7.80(d,2H,Ph-2,6-2H),7.71(t,2H,Quinazoline-6,7-2H),7.49(t,1H,Ph-4-H),7.36(d,2H,Ph-3,5-2H),7.28-7.30(d,1H,Quinazoline-7-H),6.38(s,1H,NH),5.85(s,1H,Pyrazole-4-H),4.40(t,2H,O-CH2),4.12-4.16(m,2H,N-CH2),3.70(s,3H,N-CH3)。
Compounds 19-17: delta (CDCl)3):8.71(s,1H,Quinazoline-3-H),8.31-8.32(d,1H,Quinazoline-5-H),7.88-7.90(d,1H,Ph-6-H),7.55(t,2H,Quinazoline-6,7-2H),7.50(t,1H,Ph-3-H),7.40-7.41(d,1H,Ph-5-H),7.28-7.29(d,1H,Quinazoline-8-H),7.23(t,1H,Ph-4-H),6.12(s,1H,Pyrazole-4-H),6.09(s,1H,NH),4.43(t,2H,O-CH2),4.15-4.17(m,2H,N-CH2),3.74(s,3H,N-CH3)。
19-21 of compound, melting point 160.8 ℃. Delta (CDCl)3):8.68(s,1H,Quinazoline-2-H),7.77(d,1H,Quinazoline-5-H),7.74(d,1H,Ph-6-H),7.86(d,1H,Quinazoline-8-H),7.77(t,1H,Ph-5-H),7.72(d,1H,Ph-6-H),7.52(t,1H,Quinazoline-6-H),7.51(d,1H,Ph-4-H),7.47(t,1H,Quinazoline-7-H),6.07(s,1H,NH),5.91(s,1H,Pyrazole-4-H),4.43(t,2H,O-CH2),4.15-4.18(m,2H,N-CH2),3.73(s,3H,N-CH3).
Compound 19-68, mp 154.9 ℃. Delta (CDCl)3):8.71(s,1H,Quinazoline-2-H),7.96(s,1H,Ph-6-H),7.89(d,1H,Quinazoline-5-H),7.86(d,1H,Quinazoline-8-H),7.77(t,1H,Ph-5-H),7.72(d,1H,Ph-6-H),7.52(t,1H,Quinazoline-6-H),7.51(d,1H,Ph-4-H),7.47(t,1H,Quinazoline-7-H),6.07(s,1H,NH),5.91(s,1H,Pyrazole-4-H),4.43(t,2H,O-CH2),4.15-4.18(m,2H,N-CH2),3.73(s,3H,N-CH3).
Compound 21-1, melting point 146.4 ℃. Delta (CDCl)3):8.50(s,1H,Pyrimidine-H),7.70-7.73(d,2H,Ph-2,6-2H),7.37(t,2H,Ph-3,5-2H),7.28(t,1H,Ph-4-H),7.11(s,1H,Pyrazole-4-H),6.90(s,1H,NH),5.87(s,1H,Thiophene-H),4.37(t,2H,O-CH2),3.09-4.12(m,2H,N-CH2),3.72(s,3H,N-CH3).
Compound 21-4: delta (CDCl)3):8.49(s,1H,Pyrimidine-H),7.67(d,2H,Ph-2,6-2H),7.11(s,1H,Pyrazole-4-H),7.05(d,2H,Ph-3,5-2H),6.89(s,1H,NH),5.82(s,1H,Thiophene-H),4.37(t,2H,O-CH2),4.08-4.13(m,2H,N-CH2),3.71(s,3H,N-CH3).
Compounds 21-17, melting point 114.7 ℃. Delta (CDCl)3):8.50(s,1H,Pyrimidine-H),7.75(dd,1H,Ph-6-1H),7.41(dd,1H,Ph-3-1H),7.28(td,1H,Ph-5-1H),7.24(td,1H,Ph-4-1H),7.12(s,1H,Pyrazole-4-H),6.91(s,1H,NH),6.12(s,1H,Thionphene-H),4.38(t,2H,O-CH2),4.10-4.12(m,2H,N-CH2),3.74(s,3H,N-CH3).
Compounds 21-21, melting point 127.3 ℃. Delta (CDCl)3):8.49(s,1H,Pyrimidine-H),7.72(d,1H,Ph-6-1H),7.43(s,1H,Ph-3-1H),7.26(dd,1H,Ph-5-1H),7.12(s,1H,Pyrazole-4-H),6.90(s,1H,NH),6.11(s,1H,Thiophene-H),4.38(t,2H,O-CH2),4.09-4.12(m,2H,N-CH2),3.73(s,3H,N-CH3).
Compounds 21-34, mp 168.0 ℃. Delta (CDCl)3):8.49(s,1H,Pyrimidine-H),7.57-7.59(d,2H,Ph-2,6-2H),7.47-7.50(d,2H,Ph-3,5-2H),7.11(s,1H,Pyrazole-4-H),6.89(s,1H,NH),5.84(s,1H,Thiophene-H),4.36(t,2H,O-CH2),4.08-4.13(m,2H,N-CH2),3.68(s,3H,N-CH3)。
Compounds 21-52 melting point 214.3 ℃. Delta (CDCl)3):8.38(s,1H,Pyrimidine-H),8.20-8.23(d,2H,Ph-2,6-2H),7.92-7.95(d,2H,Ph-3,5-2H),7.56(s,1H,Pyrazole-4-H),7.40(s,1H,NH),6.36(s,1H,Thiophene-H),4.38((t,2H,O-CH2),4.00-4.03(m,2H,N-CH2),3.64(s,3H,N-CH3).
Compound 21-68, melting point 160.0 ℃. Delta (CDCl)3):8.50(s,1H,Pyrimidine-H),7.97(s,1H,Ph-2-1H),7.89(d,1H,Ph-6-1H),7.53(d,1H,Ph-4-1H),7.48(t,1H,Ph-5-1H),7.11(s,1H,Pyrazole-4-H),6.89(s,1H,NH),5.91(s,1H,Thiophene-H),4.38(t,2H,O-CH2),4.10-4.13(m,2H,N-CH2),3.73(s,3H,N-CH3).
Compounds 21-78: Delta (CDCl)3):8.50(s,1H,Pyrimidine-H),7.71-7.73(d,2H,Ph-2,6-2H),7.20-7.23(d,2H,Ph-3,5-2H),7.11(s,1H,Pyrazole-4-H),6.89(s,1H,NH),5.84(s,1H,Thiophene-H),4.37(t,2H,O-CH2),4.09-4.12(m,2H,N-CH2),3.72(s,3H,N-CH3).
Meanwhile, other compounds represented by the general formula I of the present invention can be obtained by substituting the corresponding raw materials according to the contents described in the above synthetic examples.
In addition, the compound obtained above is reacted with an acid in a conventional manner to obtain the corresponding salt.
Examples of measurement of biological Activity
The compound of the invention has good activity to various germs in the agricultural field.
Example 8: measurement of fungicidal Activity
The compound sample of the invention is used for carrying out in vitro bacteriostatic activity or in vivo protection effect tests on various fungal diseases of plants. The results of the bactericidal activity measurement are shown in the following examples.
(1) In vitro bactericidal activity assay
The measurement method is as follows: the high-throughput screening method is adopted, i.e. a compound sample to be detected is dissolved by using a proper solvent (the type of the solvent is acetone, methanol, DMF, and the like, and is selected according to the dissolving capacity of the solvent on the sample), and a liquid to be detected with the required concentration is prepared. Under an ultraclean working environment, adding a solution to be detected into micropores of a 96-hole culture plate, adding a pathogen propagule suspension into the micropore, and placing the treated culture plate in a constant-temperature incubator for culture. And (4) after 24 hours, carrying out investigation, visually observing the germination or growth condition of the pathogen propagules during the investigation, and evaluating the bacteriostatic activity of the compound according to the germination or growth condition of the control treatment.
The results of the in vitro bacteriostatic activity (expressed as inhibition) test of some compounds are as follows:
inhibition rate against rice blast germs:
at the dosage of 25ppm, the inhibition rate of the compounds 10-19, 11-19, 19-19, 21-19, 11-1-1, 12-1-1 and the like on rice blast is more than 80 percent; the inhibition ratios of the control drugs CK1, CK2, CK3, CK4 and CK5 on rice blast were 0.
(2) Living body protecting Activity assay
The measurement method is as follows: the living potted plant determination method is adopted, i.e. a sample of the compound to be tested is dissolved by a small amount of solvent (the type of the solvent is acetone, methanol, DMF, etc., and is selected according to the dissolving capacity of the solvent to the sample, and the volume ratio of the solvent amount to the liquid spraying amount is equal to or less than 0.05), and diluted by water containing 0.1 percent of Tween 80 to prepare the liquid to be tested with the required concentration. The solution to be tested is sprayed on diseased host plants (the host plants are standard potted seedlings cultured in a greenhouse) on a crop sprayer, and disease inoculation is carried out after 24 hours. According to the characteristics of diseases, inoculating the disease plants needing temperature and moisture control culture, then culturing in an artificial climate chamber, transferring into a greenhouse for culture after the diseases are infected, and directly inoculating and culturing the disease plants without moisture control culture in the greenhouse. The compound disease control effect evaluation is carried out after the control is sufficiently ill (usually, one week).
The results of the in vivo protective activity test of some compounds are as follows:
in vivo protective activity against cucumber downy mildew:
under the dosage of 400ppm, the compounds 11-19, 11-1-1, 12-1-1 and the like have the control effect on cucumber downy mildew of 80 percent
The above step (1); under the dosage of 100ppm, the compound 11-1-1, 12-1-1 and the like has the control effect on cucumber downy mildew of over 80 percent.
In vivo protective activity against corn rust:
at a dose of 400ppm, the compounds were: 10-19, 11-1-1, 12-1-1 and the like, and the control effect on the corn rust is more than 80 percent.
Other compounds of formula I of the present invention, which may also have corresponding activity, were tested accordingly in the manner described above for biological activity assays.

Claims (7)

1. A pyrimidine-containing substituted pyrazole compound is characterized in that: the pyrimidine-containing substituted pyrazole compound is a compound shown as a general formula I-1;
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the structural formula of the compound is shown as the general formula I-1
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-1A、
Figure 991614DEST_PATH_IMAGE003
-1B or I-1C;
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in the formula:
R4、R5selected from hydrogen;
R6、R7selected from hydrogen;
m is selected from 1;
R8、R9same or different are respectively selected from hydrogen and C1-C4Alkyl, halo C1-C4An alkyl group;
R10selected from halogen, cyano, nitro, C1-C4Alkyl, halo C1-C4An alkyl group;
n is an integer of 0 to 5, and when n is 0, no substituent is arranged on a benzene ring; when n is greater than 1, R10The same or different;
w is selected from hydrogen;
and, when the compound is of the formula I-1A,
R1is selected from C1-C4Alkyl or halo C1-C4An alkyl group;
R2selected from halogens;
when the compounds are of the general formulae I-1A, I-1B and I-1C,
R3selected from hydrogen;
when the compound is of the general formula I-1B,
R13、R14、R15or R16Are respectively selected from hydrogen;
when the compound is of the formula I-1C,
R17、R18are each selected from hydrogen.
2. The pyrimidine-containing substituted pyrazole compound according to claim 1, wherein: general formula (VII)
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-1A、
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-1B, I-1C wherein:
R4、R5selected from hydrogen;
R6、R7selected from hydrogen;
R8、R9the same or different are respectively selected from hydrogen, methyl, ethyl or trifluoromethyl;
R10selected from the group consisting of fluoro, chloro, bromo, iodo, cyano, nitro, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, trifluoromethyl, trichloromethyl, difluorochloromethyl, dichlorofluoromethyl;
n is selected from the group consisting of integers of 0 to 5When n is 0, no substituent is on the benzene ring; when n is greater than 1, R10May be the same or different;
w is selected from hydrogen;
and, when the compound is of the formula I-1A,
R1selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, monofluoromethyl, monochloromethyl, difluoromethyl, trifluoromethyl, trifluoroethyl;
R2selected from fluorine, chlorine, bromine, iodine;
when the compounds are of the general formulae I-1A, I-1B and I-1C,
R3selected from hydrogen;
when the compound is of the general formula I-1B,
R13、R14、R15or R16Are respectively selected from hydrogen;
when the compound is of the formula I-1C,
R17、R18are each selected from hydrogen.
3. The pyrimidine-containing substituted pyrazole compound according to claim 2, wherein: general formula (VII)
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-1A、
Figure 124338DEST_PATH_IMAGE003
-1B, I-1C wherein:
R4、R5selected from hydrogen;
R6、R7are all selected from hydrogen;
R8is hydrogen;
R9 is selected from methyl;
R10selected from fluorine, chlorine, bromine, iodine, cyano, nitro, methyl, ethyl, trifluoromethyl;
n is an integer of 0 to 5, and when n is 0, no substituent is arranged on a benzene ring; when n is greater than 1, R10Can be the sameOr different;
w is selected from hydrogen;
and, when the compound is of the formula I-1A,
R1selected from methyl, ethyl or difluoromethyl;
R2selected from hydrogen, fluorine, chlorine, bromine, iodine;
when the compounds are of the general formulae I-1A, I-1B and I-1C,
R3selected from hydrogen;
when the compound is of the general formula I-1B,
R13、R14、R15or R16Are respectively selected from hydrogen;
when the compound is of the formula I-1C,
R17、R18are each selected from hydrogen.
4. The pyrimidine-containing substituted pyrazole compound according to claim 3, wherein: general formula (VII)
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-1A、
Figure 861054DEST_PATH_IMAGE003
-1B, I-1C wherein:
R4、R5selected from hydrogen;
R6、R7are all selected from hydrogen;
R8is hydrogen;
R9 is selected from methyl;
R10selected from fluorine, chlorine, bromine, iodine, cyano, nitro, methyl, ethyl, trifluoromethyl;
n is an integer of 1 to 5, and when n is greater than 1, R10May be the same or different;
w is selected from hydrogen;
and, when the compound is of the formula I-1A,
R1selected from methyl, ethyl or difluoromethyl;
R2selected from fluorine, chlorine, bromine, iodine;
when the compounds are of the general formulae I-1A, I-1B and I-1C,
R3selected from hydrogen;
when the compound is of the general formula I-1B,
R13、R14、R15、R16are all selected from hydrogen;
when the compound is of the formula I-1C,
R17selected from hydrogen;
R18selected from chlorine.
5. A process for preparing pyrimidine-containing substituted pyrazoles according to claim 1, characterized in that:
the preparation method of the compound shown in the general formula I-1 comprises the following steps:
Figure DEST_PATH_IMAGE009
;
q is selected from unsubstituted or substituted by n R10Substituted phenyl, the other substituents being as defined in claim 1.
6. Use of the pyrimidine-containing substituted pyrazole compound according to claim 1 for preparing a bactericide drug in agriculture or other fields.
7. A germicidal composition, characterized by: the composition takes the pyrimidine-containing substituted pyrazole compound as claimed in claim 1 as an active component; wherein, the weight percentage of the active components in the composition is 0.1 to 99 percent.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995007278A1 (en) * 1993-09-09 1995-03-16 E.I. Du Pont De Nemours And Company Fungicidal, miticidal and arthropodicidal aminopyrimidines
CN1308065A (en) * 1994-07-06 2001-08-15 巴斯福股份公司 2-[(dihydro)pyrazole-3'-oxymethylene] aniline amide and its preparation and use
CN104710436A (en) * 2013-12-13 2015-06-17 中国中化股份有限公司 Pyrazolyl pyrilamine compound and use thereof
CN105777717A (en) * 2014-12-19 2016-07-20 沈阳中化农药化工研发有限公司 Pyrazolyl pyrimidinyl ether compound and use thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995007278A1 (en) * 1993-09-09 1995-03-16 E.I. Du Pont De Nemours And Company Fungicidal, miticidal and arthropodicidal aminopyrimidines
CN1308065A (en) * 1994-07-06 2001-08-15 巴斯福股份公司 2-[(dihydro)pyrazole-3'-oxymethylene] aniline amide and its preparation and use
CN104710436A (en) * 2013-12-13 2015-06-17 中国中化股份有限公司 Pyrazolyl pyrilamine compound and use thereof
CN105777717A (en) * 2014-12-19 2016-07-20 沈阳中化农药化工研发有限公司 Pyrazolyl pyrimidinyl ether compound and use thereof

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