CN110964037B - Pyrimidine-fused ring-containing compound and preparation method and application thereof - Google Patents

Pyrimidine-fused ring-containing compound and preparation method and application thereof Download PDF

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CN110964037B
CN110964037B CN201811146769.9A CN201811146769A CN110964037B CN 110964037 B CN110964037 B CN 110964037B CN 201811146769 A CN201811146769 A CN 201811146769A CN 110964037 B CN110964037 B CN 110964037B
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CN110964037A (en
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李淼
杨吉春
孙芹
吴峤
兰杰
刘长令
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Shenyang Sinochem Agrochemicals R&D Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D498/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D498/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D498/04—Ortho-condensed systems
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    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
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Abstract

The invention discloses a pyrimido-ring-containing compound and a preparation method and application thereof, wherein the structure of the pyrimido-ring-containing compound is shown as a general formula I:

Description

Pyrimidine-fused ring-containing compound and preparation method and application thereof
Technical Field
The invention belongs to the field of agricultural bactericides, and particularly relates to a novel pyrimidine-fused ring-containing compound and a preparation method and application thereof.
Background
The article Pest Management Science (2008), 64 (12), 1267-1277 discloses the use of isoxazolo pyrimidines of the following structure as agricultural fungicides.
Figure BDA0001816962790000011
However, the pyrimido-ring-containing compound with the structure shown in the general formula I is not reported.
Disclosure of Invention
The invention aims to provide a pyrimido-ring-containing compound capable of controlling various pathogenic bacteria, a preparation method thereof and application of the pyrimido-ring-containing 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:
a pyrimidine-fused ring-containing compound, the structure of which is shown in general formula I;
Figure BDA0001816962790000012
R 1 selected from hydrogen, C 1 -C 12 Alkyl, halo C 1 -C 12 Alkyl radical, C 3 -C 12 Cycloalkyl, C 1 -C 12 Alkoxy, halo C 1 -C 12 Alkoxy radical, C 1 -C 12 Alkylthio, halo C 1 -C 12 Alkylthio radical, C 1 -C 12 Alkylsulfinyl radical, C 1 -C 12 Alkylsulfonyl radical, C 2 -C 12 Alkenyl, halo C 2 -C 12 Alkenyl radical, C 2 -C 12 Alkynyl, halo C 2 -C 12 Alkynyl, C 3 -C 12 Alkenyloxy, halogeno C 3 -C 12 Alkenyloxy radical, C 3 -C 12 Alkynyloxy, halo C 3 -C 12 Alkynyloxy, C 1 -C 12 Alkylamino radical, di (C) 1 -C 12 Alkyl) amino, C 1 -C 12 Alkylaminocarbonyl, halogeno C 1 -C 12 Alkylaminocarbonyl radical, C 1 -C 12 Alkoxycarbonyl, halo C 1 -C 12 Alkoxycarbonyl group, C 1 -C 12 Alkoxy radical C 1 -C 12 Alkyl radical, C 1 -C 12 Alkylthio group C 1 -C 12 Alkyl radical, C 1 -C 12 Alkylcarbonyl, halo C 1 -C 12 Alkylcarbonyl, unsubstituted or substituted by 1-5R 11 Substituted aryl, arylmethyl, arylcarbonyl, arylmethylcarbonyl, aryloxycarbonyl, heteroaryl, heteroarylmethyl, heteroarylcarbonyl, heteroarylmethylcarbonyl, or heteroaryloxycarbonyl;
R 2 selected from hydrogen, halogen, C 1 -C 12 Alkyl, halo C 1 -C 12 Alkyl radical, C 3 -C 8 Cycloalkyl radical, C 1 -C 12 Alkoxy radical, C 1 -C 12 Alkylthio or C 1 -C 12 An alkylsulfonyl group;
R 3 、R 4 can be combined with each otherIs the same or different and is respectively selected from hydrogen, halogen, hydroxyl, amino and C 1 -C 12 Alkyl radical, C 1 -C 12 Alkoxy radical, C 3 -C 12 Cycloalkyl radical, C 2 -C 12 Alkenyl radical, C 2 -C 12 Alkynyl, halo C 2 -C 12 Alkenyl, halo C 2 -C 12 Alkynyl, C 1 -C 12 Alkoxy radical C 1 -C 12 Alkyl, aryl C unsubstituted or further substituted by 1 to 5 1 -C 6 Alkyl or heteroaryl C 1 -C 6 Alkyl, the following groups are halogen, C 1 -C 6 Alkyl, halo C 1 -C 6 Alkyl radical, C 1 -C 6 Alkoxy or halo C 1 -C 6 An alkoxy group;
said R is 3 、R 4 May also be combined with the carbon to form C 3 -C 8 A ring of (a);
R 5 、R 6 、R 7 、R 8 can be the same or different and are respectively selected from hydrogen, halogen, hydroxyl, nitro, cyano and C 1 -C 12 Alkyl, halo C 1 -C 12 Alkyl radical, C 3 -C 12 Cycloalkyl radical, C 1 -C 12 Alkoxy, halo C 1 -C 12 Alkoxy radical, C 1 -C 12 Alkylthio, halogeno C 1 -C 12 Alkylthio radical, C 2 -C 12 Alkenyl, halo C 2 -C 12 Alkenyl radical, C 2 -C 12 Alkynyl, halo C 2 -C 12 Alkynyl, C 3 -C 12 Alkenyloxy, halogeno C 3 -C 12 Alkenyloxy radical, C 3 -C 12 Alkynyloxy, halo C 3 -C 12 Alkynyloxy, C 1 -C 12 Alkylsulfinyl, halo C 1 -C 12 Alkylsulfinyl radical, C 1 -C 12 Alkylsulfonyl, halo C 1 -C 12 Alkylsulfonyl radical, C 1 -C 12 Alkylcarbonyl, halo C 1 -C 12 Alkylcarbonyl group, C 1 -C 12 Alkylcarbonyloxy, C 1 -C 12 Alkyl carbo groupAmino radical, C 1 -C 12 Alkylsulfonyloxy, C 1 -C 12 Alkoxycarbonyl group, C 1 -C 12 Alkoxycarbonyl radical C 1 -C 12 Alkyl radical, C 1 -C 12 Alkoxycarbonylamino group, C 1 -C 12 Alkoxy radical C 1 -C 12 Alkoxy or C 1 -C 12 Alkoxycarbonyl radical C 1 -C 12 An alkoxy group; and, R 6 、R 7 Not fluorine alone (i.e. R) 6 、R 7 May be both fluorine or not at the same time);
a is selected from NR 10 O or S;
x is selected from NR 10 O or S;
R 10 selected from hydrogen, hydroxy, formyl, C 1 -C 12 Alkyl, halo C 1 -C 12 Alkyl radical, C 1 -C 12 Alkoxy, halo C 1 -C 12 Alkoxy radical, C 3 -C 12 Cycloalkyl radical, C 1 -C 12 Alkylthio radical, C 2 -C 12 Alkenylthio radical, C 2 -C 12 Alkenyl radical, C 2 -C 12 Alkynyl, halo C 2 -C 12 Alkenyl, halo C 2 -C 12 Alkynyl, C 1 -C 12 Alkoxy radical C 1 -C 12 Alkyl, halo C 1 -C 12 Alkoxy radical C 1 -C 12 Alkyl radical, C 1 -C 12 Alkylthio group C 1 -C 12 Alkyl, halo C 1 -C 12 Alkylthio group C 1 -C 12 Alkyl radical, C 1 -C 12 Alkylsulfinyl, halogeno C 1 -C 12 Alkylsulfinyl radical, C 1 -C 12 Alkylsulfonyl, halo C 1 -C 12 Alkylsulfonyl radical, C 1 -C 12 Alkylaminosulfonyl, di (C) 1 -C 12 Alkyl) aminosulfonyl, C 1 -C 12 Alkylsulfonylaminocarbonyl group, C 1 -C 12 Alkylcarbonylaminosulfonyl radical, C 3 -C 12 Cycloalkyloxycarbonyl radical, C 1 -C 12 Alkylcarbonyl, halo C 1 -C 12 Alkylcarbonyl group, C 1 -C 12 Alkoxycarbonyl, halogeno C 1 -C 12 Alkoxycarbonyl group, C 1 -C 12 Alkyl carbonyl group C 1 -C 12 Alkyl radical, C 1 -C 12 Alkoxycarbonyl radical C 1 -C 12 Alkyl radical, C 1 -C 12 Alkylaminocarbonyl, di (C) 1 -C 12 Alkyl) aminocarbonyl, C 2 -C 12 Alkenyloxycarbonyl radical, C 2 -C 12 Alkynyloxycarbonyl group, C 1 -C 12 Alkoxy radical C 1 -C 12 Alkoxycarbonyl group, C 1 -C 12 Alkylamino thio, di (C) 1 -C 12 Alkyl) aminothio, arylcarbonyl C which is unsubstituted or further substituted by 1 to 5 1 -C 6 Alkyl, arylcarbonyl, aryloxycarbonyl, aryl C 1 -C 6 Alkyloxycarbonyl, aryl C 1 -C 6 Alkyl, heteroaryl carbonyl C 1 -C 6 Alkyl, heteroarylcarbonyl, heteroaryloxycarbonyl, heteroaryl C 1 -C 6 Alkyloxycarbonyl, heteroaryl C 1 -C 6 An alkyl group; the following groups are halogen, nitro, cyano, C 1 -C 6 Alkyl, halo C 1 -C 6 Alkyl radical, C 1 -C 6 Alkoxy or halo C 1 -C 6 An alkoxy group;
m is selected from 0 or 1;
q is selected from unsubstituted or substituted by 1-5R 9 Substituted phenyl, pyridyl, pyrimidinyl, pyridazinyl, piperazinyl;
R 9 selected from halogen, hydroxy, amino, cyano, nitro, C 1 -C 12 Alkyl, halo C 1 -C 12 Alkyl radical, C 1 -C 12 Alkoxy, halo C 1 -C 12 Alkoxy radical, C 3 -C 12 Cycloalkyl radical, C 1 -C 12 Alkylamino, halogeno C 1 -C 12 Alkylamino radical, di (C) 1 -C 12 Alkyl) amino, halo-di (C) 1 -C 12 Alkyl) amino, C 1 -C 12 Alkylthio, halo C 1 -C 12 Alkylthio radical, C 2 -C 12 Alkenyl radical, C 2 -C 12 Alkynyl, C 2 -C 12 Alkenyloxy, halogeno C 2 -C 12 Alkenyloxy radical, C 2 -C 12 Alkynyloxy, halo C 2 -C 12 Alkynyloxy, C 1 -C 12 Alkylsulfonyl, halo C 1 -C 12 Alkylsulfonyl radical, C 1 -C 12 Alkylcarbonyl, halo C 1 -C 12 Alkylcarbonyl group, C 1 -C 12 Alkoxycarbonyl, halo C 1 -C 12 Alkoxycarbonyl group, C 1 -C 12 Alkoxy radical C 1 -C 12 Alkyl, halo C 1 -C 12 Alkoxy radical C 1 -C 12 Alkyl radical, C 1 -C 12 Alkylthio group C 1 -C 12 Alkyl, halo C 1 -C 12 Alkylthio group C 1 -C 12 Alkyl radical, C 1 -C 12 Alkoxycarbonyl radical C 1 -C 12 Alkyl, halo C 1 -C 12 Alkoxycarbonyl radical C 1 -C 12 Alkyl radical, C 1 -C 12 Alkylthio carbonyl group C 1 -C 12 Alkyl, halo C 1 -C 12 Alkylthio carbonyl group C 1 -C 12 Alkyl radical, C 1 -C 12 Alkylcarbonyloxy, halo C 1 -C 12 Alkylcarbonyloxy, C 1 -C 12 Alkoxycarbonyloxy, halo C 1 -C 12 Alkoxycarbonyloxy, C 1 -C 12 Alkylsulfonyloxy, halo C 1 -C 12 Alkylsulfonyloxy, C 1 -C 12 Alkoxy radical C 1 -C 12 Alkoxy, halo C 1 -C 12 Alkoxy radical C 1 -C 12 Alkoxy, unsubstituted or substituted by 1 to 5R 11 Substituted aryl, arylmethyl, arylcarbonyl, arylmethylcarbonyl, aryloxycarbonyl, heteroaryl, heteroarylmethyl, heteroarylcarbonyl, heteroarylmethylcarbonyl, or heteroaryloxycarbonyl;
R 11 selected from halogen, hydroxy, amino, cyano, nitro, C 1 -C 12 Alkyl, halo C 1 -C 12 Alkyl radical, C 1 -C 12 Alkoxy, halo C 1 -C 12 Alkoxy radical, C 3 -C 12 Cycloalkyl radical, C 1 -C 12 Alkylamino, halogeno C 1 -C 12 Alkylamino radical, di (C) 1 -C 12 Alkyl) amino, C 1 -C 12 Alkylthio, halo C 1 -C 12 Alkylthio radical, C 2 -C 12 Alkenyl radical, C 2 -C 12 Alkynyl, C 2 -C 12 Alkenyloxy, halogeno C 2 -C 12 Alkenyloxy radical, C 2 -C 12 Alkynyloxy, halo C 2 -C 12 Alkynyloxy, C 1 -C 12 Alkylsulfonyl, halo C 1 -C 12 Alkylsulfonyl radical, C 1 -C 12 Alkylcarbonyl, halo C 1 -C 12 Alkylcarbonyl group, C 1 -C 12 Alkoxycarbonyl, halogeno C 1 -C 12 Alkoxycarbonyl group, C 1 -C 12 Alkoxy radical C 1 -C 12 Alkyl, halo C 1 -C 12 Alkoxy radical C 1 -C 12 Alkyl radical, C 1 -C 12 Alkylthio group C 1 -C 12 Alkyl, halo C 1 -C 12 Alkylthio C 1 -C 12 Alkyl or C 1 -C 12 Alkoxycarbonyl radical C 1 -C 12 An alkyl group;
or a salt of a compound of formula I.
Preferably, in the compounds of the formula I
R 1 Selected from hydrogen, C 1 -C 6 Alkyl, halo C 1 -C 6 Alkyl radical, C 3 -C 6 Cycloalkyl radical, C 1 -C 6 Alkoxy, halo C 1 -C 6 Alkoxy radical, C 1 -C 6 Alkylthio, halo C 1 -C 6 Alkylthio radical, C 1 -C 6 Alkylsulfinyl radical, C 1 -C 6 Alkylsulfonyl radical, C 1 -C 6 Alkenyl, halo C 2 -C 6 Alkenyl radical, C 2 -C 6 Alkynyl, halo C 2 -C 6 Alkynyl, C 3 -C 6 Alkenyloxy, halogeno C 3 -C 6 Alkenyloxy radical, C 3 -C 6 Alkynyloxy, halo C 3 -C 6 Alkynyloxy, C 1 -C 6 Alkylamino radical, di (C) 1 -C 6 Alkyl) amino, C 1 -C 6 Alkylaminocarbonyl, halogeno C 1 -C 6 Alkylaminocarbonyl radical, C 1 -C 6 Alkoxycarbonyl, halo C 1 -C 6 Alkoxycarbonyl group, C 1 -C 6 Alkoxy radical C 1 -C 6 Alkyl radical, C 1 -C 6 Alkylthio C 1 -C 6 Alkyl radical, C 1 -C 6 Alkylcarbonyl, halo C 1 -C 6 Alkylcarbonyl, unsubstituted or substituted by 1-5R 11 Substituted aryl, arylmethyl, arylcarbonyl, arylmethylcarbonyl, aryloxycarbonyl, heteroaryl, heteroarylmethyl, heteroarylcarbonyl, heteroarylmethylcarbonyl, or heteroaryloxycarbonyl;
R 2 selected from hydrogen, halogen, C 1 -C 6 Alkyl, halo C 1 -C 6 Alkyl radical, C 3 -C 6 Cycloalkyl radical, C 1 -C 6 Alkoxy radical, C 1 -C 6 Alkylthio or C 1 -C 6 An alkylsulfonyl group;
R 3 、R 4 can be the same or different and are respectively selected from hydrogen, halogen, hydroxyl, amino and C 1 -C 6 Alkyl radical, C 1 -C 6 Alkoxy radical, C 3 -C 6 Cycloalkyl, C 2 -C 6 Alkenyl radical, C 2 -C 6 Alkynyl, halo C 2 -C 6 Alkenyl, halo C 2 -C 6 Alkynyl, C 1 -C 6 Alkoxy radical C 1 -C 6 Alkyl, aryl C unsubstituted or further substituted by 1 to 5 1 -C 6 Alkyl or heteroaryl C 1 -C 6 Alkyl, the following groups being halogen, C 1 -C 6 Alkyl, halo C 1 -C 6 Alkyl radical, C 1 -C 6 Alkoxy or halo C 1 -C 6 An alkoxy group;
or said R 3 、R 4 May also be combined with the carbon to form C 3 -C 8 A ring of (a);
R 5 、R 6 、R 7 、R 8 can be the same or different and are respectively selected from hydrogen, halogen, hydroxyl, nitro, cyano and C 1 -C 6 Alkyl, halo C 1 -C 6 Alkyl radical, C 3 -C 6 Cycloalkyl radical, C 1 -C 6 Alkoxy, halo C 1 -C 6 Alkoxy radical, C 1 -C 6 Alkylthio, halo C 1 -C 6 Alkylthio radical, C 2 -C 6 Alkenyl, halo C 2 -C 6 Alkenyl radical, C 2 -C 6 Alkynyl, halo C 2 -C 6 Alkynyl, C 3 -C 6 Alkenyloxy, halogeno C 3 -C 6 Alkenyloxy radical, C 3 -C 6 Alkynyloxy, halo C 3 -C 6 Alkynyloxy, C 1 -C 6 Alkylsulfinyl, halogeno C 1 -C 6 Alkylsulfinyl radical, C 1 -C 6 Alkylsulfonyl, halo C 1 -C 6 Alkylsulfonyl radical, C 1 -C 6 Alkylcarbonyl, halo C 1 -C 6 Alkylcarbonyl group, C 1 -C 6 Alkylcarbonyloxy, C 1 -C 6 Alkylcarbonylamino, C 1 -C 6 Alkylsulfonyloxy, C 1 -C 6 Alkoxycarbonyl group, C 1 -C 6 Alkoxycarbonyl radical C 1 -C 6 Alkyl radical, C 1 -C 6 Alkoxycarbonylamino group, C 1 -C 6 Alkoxy radical C 1 -C 6 Alkoxy or C 1 -C 6 Alkoxycarbonyl radical C 1 -C 6 An alkoxy group; and, R 6 、R 7 Not fluorine alone;
a is selected from NR 10 O or S;
x is selected from NR 10 O or S;
R 10 selected from hydrogen, hydroxy, formyl, C 1 -C 6 Alkyl, halo C 1 -C 6 Alkyl radical, C 1 -C 6 Alkoxy, halo C 1 -C 6 Alkoxy radicalBase, C 3 -C 6 Cycloalkyl radical, C 1 -C 6 Alkylthio radical, C 2 -C 6 Alkenylthio radical, C 2 -C 6 Alkenyl radical, C 2 -C 6 Alkynyl, halo C 2 -C 6 Alkenyl, halo C 2 -C 6 Alkynyl, C 1 -C 6 Alkoxy radical C 1 -C 6 Alkyl, halo C 1 -C 6 Alkoxy radical C 1 -C 6 Alkyl radical, C 1 -C 6 Alkylthio group C 1 -C 6 Alkyl, halo C 1 -C 6 Alkylthio C 1 -C 6 Alkyl radical, C 1 -C 6 Alkylsulfinyl, halo C 1 -C 6 Alkylsulfinyl radical, C 1 -C 6 Alkylsulfonyl, halo C 1 -C 6 Alkylsulfonyl radical, C 1 -C 6 Alkylaminosulfonyl, di (C) 1 -C 6 Alkyl) aminosulfonyl, C 1 -C 6 Alkylsulfonylaminocarbonyl group, C 1 -C 6 Alkylcarbonylaminosulfonyl radical, C 3 -C 6 Cycloalkyloxycarbonyl radical, C 1 -C 6 Alkylcarbonyl, halo C 1 -C 6 Alkyl carbonyl, C 1 -C 6 Alkoxycarbonyl, halogeno C 1 -C 6 Alkoxycarbonyl group, C 1 -C 6 Alkyl carbonyl radical C 1 -C 6 Alkyl radical, C 1 -C 6 Alkoxycarbonyl radical C 1 -C 6 Alkyl radical, C 1 -C 12 Alkylaminocarbonyl, di (C) 1 -C 6 Alkyl) aminocarbonyl, C 2 -C 6 Alkenyloxycarbonyl radical, C 2 -C 6 Alkynyloxycarbonyl group, C 1 -C 6 Alkoxy radical C 1 -C 6 Alkoxycarbonyl group, C 1 -C 6 Alkylaminosulfenyl, di (C) 1 -C 6 Alkyl) aminosulfanyl, arylcarbonyl C which is unsubstituted or further substituted by 1 to 5 1 -C 6 Alkyl, arylcarbonyl, aryloxycarbonyl, aryl C 1 -C 6 Alkyloxycarbonyl, aryl C 1 -C 6 Alkyl, heteroaryl carbonyl C 1 -C 6 Alkyl, heteroArylcarbonyl, heteroaryloxycarbonyl, heteroaryl C 1 -C 6 Alkyloxycarbonyl, heteroaryl C 1 -C 6 Alkyl, the following groups are halogen, nitro, cyano, C 1 -C 6 Alkyl, halo C 1 -C 6 Alkyl radical, C 1 -C 6 Alkoxy or halo C 1 -C 6 An alkoxy group;
m is selected from 0 or 1;
q is selected from unsubstituted or substituted by 1-5R 9 Substituted phenyl, pyridyl, pyrimidinyl, pyridazinyl, piperazinyl;
R 9 selected from halogen, hydroxy, amino, cyano, nitro, C 1 -C 6 Alkyl, halo C 1 -C 6 Alkyl radical, C 1 -C 6 Alkoxy, halo C 1 -C 6 Alkoxy radical, C 3 -C 6 Cycloalkyl radical, C 1 -C 6 Alkylamino, halogeno C 1 -C 6 Alkylamino radical, di (C) 1 -C 6 Alkyl) amino, halo-di (C) 1 -C 6 Alkyl) amino, C 1 -C 6 Alkylthio, halogeno C 1 -C 6 Alkylthio radical, C 2 -C 6 Alkenyl radical, C 2 -C 6 Alkynyl, C 2 -C 6 Alkenyloxy, halogeno C 2 -C 6 Alkenyloxy radical, C 2 -C 6 Alkynyloxy, halo C 2 -C 6 Alkynyloxy, C 1 -C 6 Alkylsulfonyl, halo C 1 -C 6 Alkylsulfonyl radical, C 1 -C 6 Alkylcarbonyl, halo C 1 -C 6 Alkylcarbonyl group, C 1 -C 6 Alkoxycarbonyl, halo C 1 -C 6 Alkoxycarbonyl group, C 1 -C 6 Alkoxy radical C 1 -C 6 Alkyl, halo C 1 -C 6 Alkoxy radical C 1 -C 6 Alkyl radical, C 1 -C 6 Alkylthio group C 1 -C 6 Alkyl, halo C 1 -C 6 Alkylthio group C 1 -C 6 Alkyl radical, C 1 -C 6 Alkoxycarbonyl radical C 1 -C 6 Alkyl, halo C 1 -C 6 Alkoxycarbonyl radical C 1 -C 6 Alkyl radical, C 1 -C 6 Alkylthio carbonyl group C 1 -C 6 Alkyl, halo C 1 -C 6 Alkylthio carbonyl group C 1 -C 6 Alkyl radical, C 1 -C 6 Alkylcarbonyloxy, halo C 1 -C 6 Alkylcarbonyloxy, C 1 -C 6 Alkoxycarbonyloxy, halo C 1 -C 6 Alkoxycarbonyloxy, C 1 -C 6 Alkylsulfonyloxy, halo C 1 -C 6 Alkylsulfonyloxy, C 1 -C 6 Alkoxy radical C 1 -C 6 Alkoxy, halo C 1 -C 6 Alkoxy radical C 1 -C 6 Alkoxy, unsubstituted or substituted by 1 to 5R 11 Substituted aryl, arylmethyl, arylcarbonyl, arylmethylcarbonyl, aryloxycarbonyl, heteroaryl, heteroarylmethyl, heteroarylcarbonyl, heteroarylmethylcarbonyl, or heteroaryloxycarbonyl;
R 11 selected from halogen, hydroxy, amino, cyano, nitro, C 1 -C 6 Alkyl, halo C 1 -C 6 Alkyl radical, C 1 -C 6 Alkoxy, halo C 1 -C 6 Alkoxy radical, C 3 -C 6 Cycloalkyl radical, C 1 -C 6 Alkylamino, halogeno C 1 -C 6 Alkylamino radical, di (C) 1 -C 6 Alkyl) amino, C 1 -C 6 Alkylthio, halogeno C 1 -C 6 Alkylthio radical, C 2 -C 6 Alkenyl radical, C 2 -C 6 Alkynyl, C 2 -C 6 Alkenyloxy, halogeno C 2 -C 6 Alkenyloxy radical, C 2 -C 6 Alkynyloxy, halo C 2 -C 6 Alkynyloxy, C 1 -C 6 Alkylsulfonyl, halo C 1 -C 6 Alkylsulfonyl radical, C 1 -C 6 Alkylcarbonyl, halo C 1 -C 6 Alkyl carbonyl, C 1 -C 6 Alkoxycarbonyl, halo C 1 -C 6 Alkoxycarbonyl group, C 1 -C 6 Alkoxy radical C 1 -C 6 Alkyl, halo C 1 -C 6 Alkoxy radicalC 1 -C 6 Alkyl radical, C 1 -C 6 Alkylthio C 1 -C 6 Alkyl or halo C 1 -C 6 Alkylthio group C 1 -C 6 An alkyl group;
or a salt of a compound of formula I.
More preferably, in the formula I
R 1 Selected from hydrogen, C 1 -C 6 Alkyl, halo C 1 -C 6 Alkyl radical, C 3 -C 6 Cycloalkyl radical, C 1 -C 6 Alkoxy, halo C 1 -C 6 Alkoxy radical, C 1 -C 6 Alkylthio, halo C 1 -C 6 Alkylthio radical, C 1 -C 6 Alkylsulfinyl radical, C 1 -C 6 Alkylsulfonyl radical, C 2 -C 6 Alkenyl, halo C 2 -C 6 Alkenyl radical, C 2 -C 6 Alkynyl, halo C 2 -C 6 Alkynyl, unsubstituted or substituted by 1-5R 11 Substituted phenyl, pyridyl, pyrimidinyl, triazolyl, oxazolyl, thiadiazolyl, oxadiazolyl, furanyl, thienyl, thiazolyl, benzyl, picolyl, thienylmethyl, or thiazolylmethyl;
R 2 selected from hydrogen, halogen, C 1 -C 6 Alkyl, halo C 1 -C 6 Alkyl radical, C 3 -C 6 Cycloalkyl radical, C 1 -C 6 Alkoxy radical, C 1 -C 6 Alkylthio or C 1 -C 6 An alkylsulfonyl group;
R 3 、R 4 can be the same or different and are respectively selected from hydrogen, halogen and C 1 -C 6 Alkyl, halo C 1 -C 6 Alkyl radical, C 1 -C 6 Alkoxy or halo C 1 -C 6 An alkoxy group;
R 5 、R 6 、R 7 、R 8 can be the same or different and are respectively selected from hydrogen, halogen, hydroxyl, nitro, cyano and C 1 -C 6 Alkyl, halo C 1 -C 6 Alkyl radical, C 3 -C 6 Cycloalkyl radical, C 1 -C 6 Alkoxy, haloGeneration C 1 -C 6 Alkoxy radical, C 1 -C 6 Alkylthio, halo C 1 -C 6 Alkylthio radical, C 2 -C 6 Alkenyl, halo C 2 -C 6 Alkenyl radical, C 2 -C 6 Alkynyl, halo C 2 -C 6 Alkynyl, C 3 -C 6 Alkenyloxy, halogeno C 3 -C 6 Alkenyloxy radical, C 3 -C 6 Alkynyloxy, halo C 3 -C 6 Alkynyloxy, C 1 -C 6 Alkylsulfinyl, halogeno C 1 -C 6 Alkylsulfinyl radical, C 1 -C 6 Alkylsulfonyl, halo C 1 -C 6 Alkylsulfonyl radical, C 1 -C 6 Alkylcarbonyl, halo C 1 -C 6 Alkylcarbonyl group, C 1 -C 6 Alkylcarbonyloxy, C 1 -C 6 Alkylcarbonylamino, C 1 -C 6 Alkylsulfonyloxy, C 1 -C 6 Alkoxycarbonyl group, C 1 -C 6 Alkoxycarbonyl radical C 1 -C 6 Alkyl radical, C 1 -C 6 Alkoxycarbonylamino group, C 1 -C 6 Alkoxy radical C 1 -C 6 Alkoxy or C 1 -C 6 Alkoxycarbonyl radical C 1 -C 6 An alkoxy group; and R is 6 、R 7 Is not fluorine alone;
a is selected from NR 10 O or S;
x is selected from NR 10 O or S;
R 10 selected from hydrogen, hydroxy, formyl, C 1 -C 6 Alkyl, halo C 1 -C 6 Alkyl radical, C 1 -C 6 Alkoxy, halo C 1 -C 6 Alkoxy radical, C 3 -C 6 Cycloalkyl radical, C 1 -C 6 Alkylthio radical, C 2 -C 6 Alkenylthio radical, C 2 -C 6 Alkenyl radical, C 2 -C 6 Alkynyl, halo C 2 -C 6 Alkenyl, halo C 2 -C 6 Alkynyl, C 1 -C 6 Alkoxy radical C 1 -C 6 Alkyl, halo C 1 -C 6 Alkoxy radical C 1 -C 6 Alkyl radical, C 1 -C 6 Alkylthio group C 1 -C 6 Alkyl, halo C 1 -C 6 Alkylthio group C 1 -C 6 Alkyl radical, C 1 -C 6 Alkylsulfinyl, halogeno C 1 -C 6 Alkylsulfinyl radical, C 1 -C 6 Alkylsulfonyl, halo C 1 -C 6 Alkylsulfonyl radical, C 1 -C 6 Alkylaminosulfonyl, di (C) 1 -C 6 Alkyl) aminosulfonyl;
m is selected from 0 or 1;
when Q is a benzene ring, the structural formula of the general formula I is shown as I-1, wherein n is an integer from 1 to 5; when Q is a pyridine ring, the structural formula of the general formula I is shown as I-2, wherein n is an integer from 1 to 4; when Q is a pyrimidine ring, the structural formula of the general formula I is shown as I-3, and n is selected from an integer from 0 to 3; when Q is a pyridazine ring, the structural formula of the general formula I is shown as I-4, and n is selected from an integer from 0 to 3; when Q is pyrazine ring, the structural formula of the general formula I is shown as I-5, and n is selected from an integer of 0 to 3;
Figure BDA0001816962790000051
R 9 selected from halogen, hydroxy, amino, cyano, nitro, C 1 -C 6 Alkyl, halo C 1 -C 6 Alkyl radical, C 1 -C 6 Alkoxy, halo C 1 -C 6 Alkoxy radical, C 3 -C 6 Cycloalkyl radical, C 1 -C 6 Alkylamino, halogeno C 1 -C 6 Alkylamino radical, di (C) 1 -C 6 Alkyl) amino, halo-di (C) 1 -C 6 Alkyl) amino, C (= O) NR 9 R 10 、C 1 -C 6 Alkylthio, halogeno C 1 -C 6 Alkylthio radical, C 2 -C 6 Alkenyl radical, C 2 -C 6 Alkynyl, C 2 -C 6 Alkenyloxy, halogeno C 2 -C 6 Alkenyloxy radical, C 2 -C 6 Alkynyloxy, halo C 2 -C 6 Alkynyloxy, C 1 -C 6 Alkyl sulfonyl radicalHalogen substituted C 1 -C 6 Alkylsulfonyl radical, C 1 -C 6 Alkylcarbonyl, halo C 1 -C 6 Alkyl carbonyl, C 1 -C 6 Alkoxycarbonyl, halogeno C 1 -C 6 Alkoxycarbonyl group, C 1 -C 6 Alkoxy radical C 1 -C 6 Alkyl, halo C 1 -C 6 Alkoxy radical C 1 -C 6 Alkyl radical, C 1 -C 6 Alkylthio group C 1 -C 6 Alkyl, halo C 1 -C 6 Alkylthio group C 1 -C 6 Alkyl, unsubstituted or substituted by 1-5R 11 Substituted phenyl, pyridyl, pyrimidinyl, triazolyl, oxazolyl, thiadiazolyl, oxadiazolyl, furanyl, thienyl, thiazolyl, benzyl, picolyl, thienylmethyl, or thiazolylmethyl;
R 11 selected from halogen, hydroxy, amino, cyano, nitro, C 1 -C 4 Alkyl, halo C 1 -C 4 Alkyl radical, C 1 -C 4 Alkoxy, halo C 1 -C 4 Alkoxy radical, C 3 -C 4 Cycloalkyl radical, C 1 -C 4 Alkylamino, halogeno C 1 -C 4 Alkylamino radical, di (C) 1 -C 4 Alkyl) amino, C 1 -C 4 Alkylthio, halo C 1 -C 4 Alkylthio radical, C 2 -C 4 Alkenyl radical, C 2 -C 4 Alkynyl, C 2 -C 4 Alkenyloxy, halogeno C 2 -C 4 Alkenyloxy radical, C 2 -C 4 Alkynyloxy, halo C 2 -C 4 Alkynyloxy, C 1 -C 4 Alkylsulfonyl, halo C 1 -C 4 Alkylsulfonyl radical, C 1 -C 4 Alkylcarbonyl, halo C 1 -C 4 Alkyl carbonyl, C 1 -C 4 Alkoxycarbonyl, halogeno C 1 -C 4 Alkoxycarbonyl group, C 1 -C 4 Alkoxy radical C 1 -C 4 Alkyl, halo C 1 -C 4 Alkoxy radical C 1 -C 4 Alkyl radical, C 1 -C 4 Alkylthio group C 1 -C 4 Alkyl or halo C 1 -C 4 Alkylthio group C 1 -C 4 An alkyl group;
or salts of the compounds of the general formula I-1, I-2, I-3, I-4 or I-5 with hydrochloric acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, trifluoroacetic acid, oxalic acid, methanesulfonic acid, p-toluenesulfonic acid, benzoic acid, phthalic acid, maleic acid, fumaric acid, sorbic acid, malic acid or citric acid.
Further preferably, in the compound shown in the general formula I-1, I-2, I-3, I-4 or I-5, A is selected from NR 10 When the temperature of the water is higher than the set temperature,
the structure of the compound shown in the general formula I-1 is as follows: I-1A, I-1B, I-1C or I-1D;
the structure of the compound shown in the general formula I-2 is I-2A, I-2B or I-2C;
the structure of the compound shown in the general formula I-3 is I-3A, I-3B or I-3C;
the structure of the compound shown in the general formula I-4 is I-4A or I-4B;
the structure of the compound shown in the general formula I-5 is I-5A or I-5B;
Figure BDA0001816962790000061
Figure BDA0001816962790000071
in the formula:
R 1 selected from hydrogen, C 1 -C 4 Alkyl, halo C 1 -C 4 Alkyl radical, C 3 -C 6 Cycloalkyl radical, C 1 -C 4 Alkoxy, halo C 1 -C 4 Alkoxy radical, C 1 -C 4 Alkylthio, halogeno C 1 -C 4 Alkylthio radical, C 1 -C 4 Alkylsulfinyl radical, C 1 -C 4 Alkylsulfonyl radical, C 2 -C 4 Alkenyl, halo C 2 -C 4 Alkenyl radical, C 2 -C 4 Alkynyl, halo C 2 -C 4 Alkynyl, unsubstituted or substituted by 1-5R 11 Substituted phenyl, pyridylPyrimidinyl, triazolyl, oxazolyl, thiadiazolyl, oxadiazolyl, furanyl, thienyl, thiazolyl, benzyl, picolyl, thienylmethyl, or thiazolylmethyl;
R 2 selected from hydrogen, halogen, C 1 -C 4 Alkyl, halo C 1 -C 4 Alkyl radical, C 3 -C 6 Cycloalkyl, C 1 -C 4 Alkoxy radical, C 1 -C 4 Alkylthio or C 1 -C 4 An alkylsulfonyl group;
R 3 、R 4 can be the same or different and are respectively selected from hydrogen, halogen and C 1 -C 6 Alkyl, halo C 1 -C 6 Alkyl radical, C 1 -C 6 Alkoxy or halo C 1 -C 6 An alkoxy group;
R 5 、R 6 、R 7 、R 8 can be the same or different and are respectively selected from hydrogen, halogen, hydroxyl, nitro, cyano and C 1 -C 6 Alkyl, halo C 1 -C 6 Alkyl radical, C 3 -C 6 Cycloalkyl radical, C 1 -C 6 Alkoxy, halo C 1 -C 6 Alkoxy radical, C 1 -C 6 Alkylthio, halo C 1 -C 6 Alkylthio radical, C 2 -C 6 Alkenyl, halo C 2 -C 6 Alkenyl radical, C 2 -C 6 Alkynyl, halo C 2 -C 6 Alkynyl, C 3 -C 6 Alkenyloxy, halogeno C 3 -C 6 Alkenyloxy radical, C 3 -C 6 Alkynyloxy, halo C 3 -C 6 An alkynyloxy group; and R is 6 、R 7 Is not fluorine alone;
R 10 selected from hydrogen, hydroxy, formyl, C 1 -C 4 Alkyl, halo C 1 -C 4 Alkyl radical, C 1 -C 4 Alkoxy, halo C 1 -C 4 Alkoxy radical, C 3 -C 6 Cycloalkyl radical, C 1 -C 4 Alkylthio radical, C 2 -C 4 Alkenylthio radical, C 2 -C 4 Alkenyl radical, C 2 -C 4 Alkynyl, halo C 2 -C 4 Alkenyl, halo C 2 -C 4 Alkynyl, C 1 -C 4 Alkoxy radical C 1 -C 4 Alkyl, halo C 1 -C 4 Alkoxy radical C 1 -C 4 Alkyl radical, C 1 -C 4 Alkylthio group C 1 -C 4 Alkyl, halo C 1 -C 4 Alkylthio C 1 -C 4 Alkyl radical, C 1 -C 4 Alkylsulfinyl, halo C 1 -C 4 Alkylsulfinyl radical, C 1 -C 4 Alkylsulfonyl, halo C 1 -C 4 Alkylsulfonyl radical, C 1 -C 4 Alkylaminosulfonyl, di (C) 1 -C 4 Alkyl) aminosulfonyl;
R 9 selected from halogen, hydroxy, amino, cyano, nitro, C 1 -C 4 Alkyl, halo C 1 -C 4 Alkyl radical, C 1 -C 4 Alkoxy, halo C 1 -C 4 Alkoxy radical, C 3 -C 6 Cycloalkyl, C 1 -C 4 Alkylamino, halogeno C 1 -C 4 Alkylamino radical, di (C) 1 -C 4 Alkyl) amino, halo-di (C) 1 -C 4 Alkyl) amino, C 1 -C 4 Alkylthio, halo C 1 -C 4 Alkylthio radical, C 2 -C 4 Alkenyl radical, C 2 -C 4 Alkynyl, C 2 -C 4 Alkenyloxy, halogeno C 2 -C 4 Alkenyloxy radical, C 2 -C 4 Alkynyloxy, halo C 2 -C 4 Alkynyloxy, C 1 -C 4 Alkylsulfonyl, halo C 1 -C 4 Alkylsulfonyl radical, C 1 -C 4 Alkylcarbonyl, halo C 1 -C 4 Alkylcarbonyl group, C 1 -C 4 Alkoxycarbonyl, halogeno C 1 -C 4 Alkoxycarbonyl group, C 1 -C 4 Alkoxy radical C 1 -C 4 Alkyl, halo C 1 -C 4 Alkoxy radical C 1 -C 4 Alkyl radical, C 1 -C 4 Alkylthio C 1 -C 4 Alkyl, halo C 1 -C 4 Alkylthio group C 1 -C 4 Alkyl radicalUnsubstituted or substituted by 1-5R 11 Substituted phenyl, pyridyl, pyrimidinyl, triazolyl, oxazolyl, thiadiazolyl, oxadiazolyl, furanyl, thienyl, thiazolyl, benzyl, picolyl, thienylmethyl, or thiazolylmethyl;
R 11 selected from halogen, hydroxy, amino, cyano, nitro, C 1 -C 4 Alkyl, halo C 1 -C 4 Alkyl radical, C 1 -C 4 Alkoxy, halo C 1 -C 4 Alkoxy radical, C 3 -C 4 Cycloalkyl radical, C 1 -C 4 Alkylamino, halogeno C 1 -C 4 Alkylamino radical, di (C) 1 -C 4 Alkyl) amino, C 1 -C 4 Alkylthio, halo C 1 -C 4 Alkylthio radical, C 2 -C 4 Alkenyl radical, C 2 -C 4 Alkynyl, C 2 -C 4 Alkenyloxy, halogeno C 2 -C 4 Alkenyloxy radical, C 2 -C 4 Alkynyloxy, halo C 2 -C 4 Alkynyloxy, C 1 -C 4 Alkylsulfonyl, halo C 1 -C 4 Alkylsulfonyl radical, C 1 -C 4 Alkylcarbonyl, halo C 1 -C 4 Alkylcarbonyl group, C 1 -C 4 Alkoxycarbonyl, halogeno C 1 -C 4 Alkoxycarbonyl group, C 1 -C 4 Alkoxy radical C 1 -C 4 Alkyl, halo C 1 -C 4 Alkoxy radical C 1 -C 4 Alkyl radical, C 1 -C 4 Alkylthio group C 1 -C 4 Alkyl or halo C 1 -C 4 Alkylthio group C 1 -C 4 An alkyl group;
in the general formula I-1A, I-1B, I-1C or I-1D, n is an integer of 1 to 5; in the general formula I-2A, I-2B or I-2C, n is an integer from 1 to 4; in I-3A, I-3B, I-3C, I-4A, I-4B, I-5A or I-5B, n is an integer from 0 to 3;
salts of compounds of formula I are: salts of compounds of the general formulae I-1A, I-1B, I-1C, I-1D, I-2A, I-2B, I-2C, I-3A, I-3B, I-3C, I-4A, I-4B, I-5A or I-5B with hydrochloric acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, trifluoroacetic acid, oxalic acid, methanesulfonic acid, p-toluenesulfonic acid, benzoic acid, phthalic acid, maleic acid, fumaric acid, sorbic acid, malic acid or citric acid.
Still more preferably, a compound represented by the general formula I-1A, I-1B, I-1C, I-1D, I-2A, I-2B, I-2C, I-3A, I-3B, I-3C, I-4A, I-4B, I-5A or I-5B:
R 1 selected from the group consisting of hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, monofluoromethyl, monochloromethyl, difluoromethyl, trifluoromethyl, trifluoroethyl, cyclopropyl, methoxymethyl, ethoxymethyl, trifluoroethoxymethyl, unsubstituted or substituted with 1-5R 11 Substituted phenyl, pyridyl, furyl, thienyl, thiazolyl or benzyl;
R 2 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;
R 3 、R 4 which may be the same or different, are each selected from hydrogen, fluoro, chloro, bromo, iodo, 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;
R 5 、R 6 、R 7 、R 8 can be the same or different and are respectively selected from hydrogen, halogen, hydroxyl, nitro, cyano and C 1 -C 6 Alkyl, halo C 1 -C 6 Alkyl radical, C 3 -C 6 Cycloalkyl radical, C 1 -C 6 An alkoxy group; and, R 6 、R 7 Not fluorine alone;
R 9 selected from fluorine, chlorine, bromine, iodine, cyano, amino, nitro, methyl, ethyl, n-propyl, isopropyl, n-butyl sec-butyl, isobutyl, tert-butyl, trifluoromethyl trichloromethyl, difluoro chloromethyl, dichloro fluoromethyl,Methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy, trifluoromethoxy, trifluoroethoxy, methoxycarbonyl, ethoxycarbonyl, aminocarbonyl, methylaminocarbonyl, ethylaminocarbonyl, dimethylaminocarbonyl, unsubstituted or substituted with 1-5R 11 Substituted phenyl, pyridyl, furyl, thienyl, thiazolyl or benzyl;
R 11 selected 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, trifluoromethoxy, or trifluoroethoxy;
R 10 selected 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 dimethylaminothio;
in the general formula I-1A, I-1B, I-1C or I-1D, n is an integer of 1 to 5; in the general formula I-2A, I-2B or I-2C, n is an integer from 1 to 4; in I-3A, I-3B, I-3C, I-4A, I-4B, I-5A or I-5B, n is an integer from 0 to 3;
salts of compounds of formula I are: salts of compounds of the general formulae I-1A, I-1B, I-1C, I-1D, I-2A, I-2B, I-2C, I-3A, I-3B, I-3C, I-4A, I-4B, I-5A or I-5B with hydrochloric acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, trifluoroacetic acid, oxalic acid, methanesulfonic acid, p-toluenesulfonic acid, benzoic acid, phthalic acid, maleic acid, fumaric acid, sorbic acid, malic acid or citric acid.
Still more preferably, compounds represented by the general formula I-1A, I-1B, I-1C, I-1D, I-2A, I-2B, I-2C, I-3A, I-3B, I-3C, I-4A, I-4B, I-5A or I-5B:
R 1 selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, trifluoromethyl, cyclopropyl, unsubstituted or substituted by 1-4R 11 Substituted phenyl, pyridyl;
R 2 selected from hydrogen, fluorine, chlorine, bromine, iodine or methyl;
R 3 、R 4 are all selected from hydrogen;
R 5 、R 6 、R 7 、R 8 can be the same or different and are respectively selected from hydrogen, halogen, hydroxyl, nitro, cyano and C 1 -C 6 An alkyl group; and, R 6 、R 7 Not fluorine alone;
R 9 selected 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, trifluoromethoxy, trifluoroethoxy, unsubstituted or substituted with 1-4R 11 Substituted phenyl, pyridyl;
R 11 selected from fluoro, chloro, bromo, iodo, cyano, nitro, methyl, trifluoromethyl, methoxy or trifluoromethoxy;
R 10 selected from hydrogen, methyl, acetyl, trifluoroacetyl, methoxy, methylthio, allyl, methylsulfonyl, methylaminosulfonyl, dimethylaminosulfonyl, methoxycarbonyl, methylaminocarbonyl, dimethylaminocarbonyl, methylaminothio or dimethylaminosulfanyl;
in the general formula I-1A, I-1B, I-1C or I-1D, n is an integer of 1 to 5; in the general formula I-2A, I-2B or I-2C, n is an integer from 1 to 4; in I-3A, I-3B, I-3C, I-4A, I-4B, I-5A or I-5B, n is an integer from 0 to 3;
salts of compounds of formula I are: salts of compounds of the general formulae I-1A, I-1B, I-1C, I-1D, I-2A, I-2B, I-2C, I-3A, I-3B, I-3C, I-4A, I-4B, I-5A or I-5B with hydrochloric acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, trifluoroacetic acid, oxalic acid, methanesulfonic acid, p-toluenesulfonic acid, benzoic acid, phthalic acid, maleic acid, fumaric acid, sorbic acid, malic acid or citric acid.
Most preferably, compounds of formula I-1A, I-1B, I-1C, I-1D, I-2A, I-2B, I-2C, I-3A, I-3B, I-4A, I-5A, or I-5B:
R 1 selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, trifluoromethyl, cyclopropyl;
R 2 selected from hydrogen, fluorine, chlorine, bromine, iodine or methyl;
R 3 、R 4 、R 5 、R 6 、R 7 、R 8 are all selected from hydrogen;
R 9 selected from fluoro, chloro, bromo, iodo, cyano, nitro, methyl, trifluoromethyl, methoxy, or trifluoromethoxy;
R 10 selected from hydrogen, methyl, acetyl, trifluoroacetyl, methoxy, methylthio, allyl, methylsulfonyl, methylaminosulfonyl, dimethylaminosulfonyl, methoxycarbonyl, methylaminocarbonyl, dimethylaminocarbonyl, methylaminothio or dimethylaminosulfanyl;
in the general formula I-1A, I-1B, I-1C or I-1D, n is an integer of 1 to 5; in the general formula I-2A, I-2B or I-2C, n is an integer from 1 to 4; in I-3A, I-3B, I-4A, I-5A or I-5B, n is selected from an integer of 0 to 3;
salts of compounds of formula I are: salts of compounds of the general formulae I-1A, I-1B, I-1C, I-1D, I-2A, I-2B, I-2C, I-3A, I-3B, I-4A, I-5A or I-5B with hydrochloric acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, trifluoroacetic acid, oxalic acid, methanesulfonic acid, p-toluenesulfonic acid, benzoic acid, phthalic acid, maleic acid, fumaric acid, sorbic acid, malic acid or citric acid.
A preparation method of a pyrimido-cyclic compound is disclosed, wherein the compound shown in the general formula I is prepared according to the following reaction formula,
Figure BDA0001816962790000101
an application of a pyrimido-ring-containing compound shown in a general formula I in preparation of bactericide drugs in agriculture or other fields.
A sterilization composition contains a pyrimido-ring-containing compound shown as a general formula I as an active component; wherein, the weight percentage of the active components in the composition is 0.1-99%.
In the definitions given above for compounds of the general formula I, 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. A haloalkyl group: 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. A haloalkylsulfinyl group: a straight-chain or branched alkylsulfinyl group in which hydrogen atoms on the alkyl group may be partially or fully substituted with 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 CH 3 NHS-、C 2 H 5 NHS-. A dialkylaminosulfenyl group: such as (CH) 3 ) 2 NS-、(C 2 H 5 ) 2 NS-. Alkylamino sulfonyl group: alkyl-NH-SO 2 -. Dialkylaminosulfonyl: (alkyl group) 2 -N-SO 2 -. Alkyl sulfonyl radicalAminocarbonyl group: alkyl-SO 2 -NH-CO-. Alkylcarbonylaminosulfonyl: alkyl-CO-NH-SO 2 -. Alkylcarbonylalkyl 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. CF 3 -SO 2 -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. ClCH 2 CH 2 OCO-、CF 3 CH 2 OCO-, etc. An alkoxyalkyl group: alkyl-O-alkyl-, e.g. CH 3 OCH 2 -. Haloalkoxyalkyl groups: the hydrogen atoms of the alkyl group of the alkoxyalkyl group may be partially or fully substituted by halogen atoms, e.g., clCH 2 CH 2 OCH 2 -、CF 3 CH 2 OCH 2 -and the like. An alkoxycarbonylalkyl group: alkoxycarbonyl-alkyl-, e.g. CH 3 OCOCH 2 -. Haloalkoxycarbonylalkyl: the hydrogen atoms of the alkyl group of the alkoxycarbonylalkyl group may be partially or fully substituted by halogen atoms, e.g. CF 3 CH 2 OCOCH 2 -. Alkylcarbonyloxy group: such as CH 3 COO-, etc. Haloalkylcarbonyloxy: the hydrogen atoms of the alkylcarbonyloxy group may be partially or fully substituted by halogen atoms, e.g. CF 3 COO-, etc. Alkoxycarbonyloxy: alkoxycarbonyl-oxy-, e.g. CH 3 OCOO-. Haloalkoxycarbonyl group: the hydrogen atoms of the alkyl group of the alkoxycarbonyloxy group may be partially or wholly substituted by halogen atoms, e.g. CF 3 OCOO-. Alkylthio-carbonylalkyl: alkylthiocarbonyl-alkyl-, e.g. CH 3 SCOCH 2 -. Haloalkylthiocarbonylalkyl: alkyl of alkylthiocarbonylalkylThe hydrogen atoms of which may be partially or wholly replaced by halogen atoms, e.g. CF 3 CH 2 SCOCH 2 -. Alkoxy groups: such as CH 3 OCH 2 O-, etc. Haloalkoxyalkyl: the hydrogen atoms of the alkoxy groups being partly or wholly replaced by halogen atoms, e.g. CF 3 OCH 2 O-is added. An alkoxyalkoxycarbonyl group: such as CH 3 OCH 2 CH 2 OCO-, 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 hydrogen atoms in the alkyl groups may be partially or fully substituted by halogen atoms. For example, chloromethylthio, dichloromethylthio, trichloromethylthio, fluoromethylthio, difluoromethylthio, trifluoromethylthio, chlorofluoromethylthio and the like. Alkylthioalkyl: alkyl-S-alkyl-, e.g. CH 3 SCH 2 -. Haloalkylthioalkyl: the hydrogen atoms of the alkyl group of an alkylthioalkyl group may be partially or fully substituted by halogen atoms, e.g. ClCH 2 CH 2 SCH 2 -、CF 3 CH 2 SCH 2 -and the like. An alkylamino group: straight or branched chain alkyl groups attached 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 ) 2 N-，(CH 3 CH 2 ) 2 N-is provided. Halogenated dialkylamino group: the hydrogen atoms of the alkyl groups being partially or wholly replaced by halogen atoms, e.g. (CF) 3 ) 2 N-，(CF 3 CH 2 ) 2 N-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. An alkenyloxy group: linear or branched alkenes attached to a structure via an oxygen atom bond. Halogenated alkenyloxy group: straight-chain or branched alkenyloxy groups in which the hydrogen atoms may be partially or completely replaced by halogen atoms. Alkenylthio groups: linear or branched alkenes linked to the structure via a sulfur atom bond. Such as CH 2 ＝CHCH 2 S-. Alkenyloxycarbonyl radical: such as CH 2 ＝CHCH 2 OCO-, etc. Alkynyl: straight-chain or branched alkynes, for example 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 fully substituted by halogen atoms. Alkynyloxy: straight or branched alkynes, attached to the structure via oxygen atom bonds. Halogenated alkynyloxy: straight-chain or branched alkynyloxy, in which the hydrogen atoms may be partially or completely replaced by halogen atoms. Alkynyloxycarbonyl group: such as CH ≡ CCH 2 OCO-, 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: a straight-chain or branched alkylsulfonyl group in which the hydrogen atoms of the alkyl group may be partially or fully substituted by halogen atoms. An alkylcarbonyl group: the alkyl radical being bound to the structure via a carbonyl group, e.g. CH 3 CO-，CH 3 CH 2 CO-. 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. CF 3 CO-. An alkoxycarbonyl group: the alkoxy group is attached to the structure via a carbonyl group. Such as CH 3 OCO-，CH 3 CH 2 OCO-. Aminocarbonyl group: such as NH 2 CO-. Alkyl amino carbonyl: alkyl-NH-CO-, e.g. CH 3 NHCO-，CH 3 CH 2 NHCO-. A dialkylaminocarbonyl group: such as (CH) 3 ) 2 NCO-，(CH 3 CH 2 ) 2 NCO-. The aryl moiety in (hetero) aryl, (hetero) arylalkyl, (hetero) arylcarbonyl, (hetero) arylmethylcarbonyl, (hetero) arylcarbonylalkyl, (hetero) aryloxycarbonyl, (hetero) arylalkyloxycarbonyl includes phenyl or naphthyl and the like. 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 benzoyl4-chlorobenzoyl and the like. (hetero) arylmethylcarbonyl: such as PhCH 2 CO-. (hetero) arylcarbonylalkyl: such as PhCOCH 2 -. (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 PhCH 2 OCO-、4-Cl-PhCH 2 OCO-, etc.
In the compounds of the general formula I of the invention R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 、R 9 (substituent on Q) and R 10 (X＝NR 10 ) Specific substituents of (a) are listed in tables 1,2, 3, 4, 5 and 6, respectively, but they are not limited to these substituents.
Figure BDA0001816962790000111
TABLE 1R 1 Substituent group
Figure BDA0001816962790000112
Figure BDA0001816962790000121
TABLE 2R 2 Substituent group
Figure BDA0001816962790000122
TABLE 3R 3 (R 4 ) Substituent group
Figure BDA0001816962790000123
TABLE 4R 5 (R 6 、R 7 、R 8 ) Substituent group
Figure BDA0001816962790000124
Figure BDA0001816962790000131
TABLE 5R 9 Substituent group
Figure BDA0001816962790000132
TABLE 6R 10 Substituent group
Figure BDA0001816962790000133
Figure BDA0001816962790000141
Some of the compounds of the present invention can be illustrated by specific compounds listed in tables 7 to 87, but are not intended to limit the present invention. In the general formula compounds I-1A, I-1B, I-1C, I-1D, I-2A, I-2B, I-2C, I-3A, I-3B, I-4A, I-5A or I-5B referred to in the table, R 2 ＝R 3 ＝R 4 ＝R 5 ＝R 6 ＝R 7 ＝R 8 ＝R 10 ＝H。
In the general formula I-1A,
Figure BDA0001816962790000151
when R is 1 ＝CH 3 When (R) 9 ) n The substituents are shown in Table 7, and represent the compound numbers of 7-1-7-279 in sequence.
TABLE 7
Figure BDA0001816962790000152
Figure BDA0001816962790000161
Table 8: in the general formula I-1A, when R 1 (= H), substituent (R) 9 ) n In agreement with Table 7, the representative compound numbers are in the order of 8-1 to 8-279.
Table 9: in the general formula I-1A, when R 1 ＝C 2 H 5 When (R) is substituted 9 ) n In agreement with Table 7, the representative compound numbers are, in order, 9-1 to 9-279.
Table 10: in the general formula I-1A, when R is 1 ＝i-C 3 H 7 When (R) is substituted 9 ) n In agreement with Table 7, the representative compound numbers are in the order of 10-1 to 10-279.
Table 11: in the general formula I-1A, when R 1 ＝n-C 4 H 9 When (R) is substituted 9 ) n In agreement with Table 7, the representative compound numbers are in the order of 11-1 to 11-279.
Table 12: in the general formula I-1A, when R is 1 ＝C 6 H 5 When (R) is substituted 9 ) n In agreement with Table 7, the representative compound numbers are in the order of 12-1 to 12-279.
Table 13: in the general formula I-1B, when R is 1 ＝CH 3 When (R) is substituted 9 ) n In agreement with Table 7, the representative compound numbers are 13-1 to 13-279 in this order.
Table 14: in the general formula I-1B, when R is 1 When = H, substituent (R) 9 ) n In agreement with Table 7, the representative compound numbers are, in order, 14-1 to 14-279.
Table 15: in the general formula I-1B, when R is 1 ＝C 2 H 5 When (R) is substituted 9 ) n In agreement with Table 7, the representative compound numbers are, in order, 15-1 to 15-279.
Table 16: in the general formula I-1B, when R is 1 ＝i-C 3 H 7 When (R) is substituted 9 ) n In agreement with Table 7, the representative compound numbers are in the order of 16-1 to 16-279.
Table 17: in the general formula I-1B, when R is 1 ＝n-C 4 H 9 When (R) is substituted 9 ) n In agreement with Table 7, the representative compound numbers are, in order, 17-1 to 17-279.
Table 18: in the general formula I-1B, when R is 1 ＝C 6 H 5 When (R) is substituted 9 ) n In agreement with Table 7, the representative compound numbers are in the order of 18-1 to 18-279.
Table 19: in the general formula I-1C, when R 1 ＝CH 3 When (R) is substituted 9 ) n In agreement with Table 7, the representative compound numbers are, in order, 19-1 to 19-279.
Table 20: in the general formula I-1C, when R 1 (= H), substituent (R) 9 ) n In agreement with Table 7, the representative compound numbers are, in order, 20-1 to 20-279.
Table 21: in the general formula I-1C, when R 1 ＝C 2 H 5 When (R) is substituted 9 ) n In agreement with Table 7, the representative compound numbers are, in order, 21-1 to 21-279.
Table 22: in the general formula I-1C, when R is 1 ＝i-C 3 H 7 When (R) is substituted 9 ) n In agreement with Table 7, the representative compound numbers are in the order of 22-1 to 22-279.
Table 23: in the general formula I-1C, when R is 1 ＝n-C 4 H 9 When (R) is substituted 9 ) n In agreement with Table 7, the representative compound numbers are 23-1 to 23-279.
Table 24: in the general formula I-1C, when R 1 ＝C 6 H 5 When (R) is substituted 9 ) n In agreement with Table 7, the representative compound numbers are in the order of 24-1 to 24-279.
Table 25: in the general formula I-1D, when R is 1 ＝CH 3 When (R) is substituted 9 ) n In agreement with Table 7, the representative compound numbers are in the order of 25-1 to 25-279.
Table 26: in the general formula I-1D, when R is 1 When = H, substituent (R) 9 ) n In accordance with Table 7The representative compound numbers are 26-1-26-279 in sequence.
Table 27: in the general formula I-1D, when R is 1 ＝C 2 H 5 When (R) is substituted 9 ) n In agreement with Table 7, the representative compound numbers are, in order, 27-1-27-279.
Table 28: in the general formula I-1D, when R is 1 ＝i-C 3 H 7 When (R) is substituted 9 ) n In agreement with Table 7, the representative compound numbers are, in order, 28-1 to 28-279.
Table 29: in the general formula I-1D, when R is 1 ＝n-C 4 H 9 When (R) is substituted 9 ) n In agreement with Table 7, the representative compound numbers are in the order of 29-1 to 29-279.
Table 30: in the general formula I-1D, when R is 1 ＝C 6 H 5 When (R) is substituted 9 ) n In agreement with Table 7, the representative compound numbers are in the order of 30-1 to 30-279.
In the general formula I-2A,
Figure BDA0001816962790000181
when R is 1 ＝CH 3 When (R) 9 ) n The substituents are shown in Table 31, and represent the compound numbers 31-1-31-69.
Watch 31
No. (R 9 )n No. (R 9 )n No. (R 9 )n
31-1 3-Cl 31-2 4-Cl 31-3 5-Cl
31-4 6-Cl 31-5 3-Br 31-6 4-Br
31-7 5-Br 31-8 6-Br 31-9 5-I
31-10 5-F 31-11 6-F 31-12 3-CH 2 CH 3
31-13 4-CH 2 CH 3 31-14 5-CH 2 CH 3 31-15 6-CH 2 CH 3
31-16 3-CF 3 31-17 4-CF 3 31-18 5-CF 3
31-19 6-CF 3 31-20 3-CN 31-21 4-CN
31-22 5-CN 31-23 6-CN 31-24 3-NO 2
31-25 5-NO 2 31-26 6-NO 2 31-27 5-OCH 3
31-28 6-OCH 3 31-29 3,5-2Cl 31-30 3,5-2Br
31-31 3,5,6-3Cl 31-32 3-Cl-5-CH 3 31-33 3-Cl-5-CF 3
31-34 3-Cl-5-CN 31-35 3-Br-5-NO 2 31-36 3-Br-5-CH 3
31-37 3-OCH 2 Ph 31-38 3-CO 2 CH 3 31-39 5-CO 2 CH 3
31-40 5-Br-6-CH 3 31-41 5-CF 3 -6-Cl 31-42 3-CN-6-Cl
31-43 3-CH 3 -5-Br 31-44 3-NO 2 -5-Cl 31-45 3-NO 2 -5-Br
31-46 3-NO 2 -4-CH 3 31-47 3-CF 3 -6-Cl 31-48 3-CH 3 -5-NO 2
31-49 4-NO 2 -6-CH 3 31-50 4-CH 3 -5-NO 2 31-51 3-NO 2 -5-CH 3
31-52 5-CN-6-CH 3 31-53 5-NO 2 -6-CH 3 31-54 4-CH 3 -5-Br
31-55 5-CN-6-CF 3 31-56 3-CN-4,6-2Cl 31-57 3,5-2Br-6-CH 3
31-58 3-CN-4-CH 3 -6-Cl 31-59 3-CN-4-CF 3 -6-Cl 31-60 4-CH 3 -5-CN-6-Cl
31-61 4-CF 3 -5-CN-6-Cl 31-62 3-CO 2 CH 3 -6-Cl 31-63 5-CO 2 CH 3 -6-Cl
31-64 3,6-2Cl-5-CF 3 31-65 3-CONH 2 -4,6-2Cl 31-66 3-Br-4-CH 3 -5-NO 2
31-67 3,5-2Cl-6-OCH 3 31-68 3,5-2Cl-6-OCF 3 31-69 3,5-2Cl-6-(OPh-4-Cl)
Table 32: in the general formula I-2A, when R is 1 (= H), substituent (R) 9 ) n In agreement with Table 31, represents the compound numberIn the order of 32-1 to 32-69.
Table 33: in the general formula I-2A, when R is 1 ＝C 2 H 5 When (R) is substituted 9 ) n In agreement with Table 31, the representative compound numbers are 33-1 to 33-69 in this order.
Table 34: in the general formula I-2A, when R is 1 ＝i-C 3 H 7 When (R) is substituted 9 ) n In agreement with Table 31, the representative compound numbers are in the order of 34-1 to 34-69.
Table 35: in the general formula I-2A, when R is 1 ＝n-C 4 H 9 When (R) is substituted 9 ) n In agreement with Table 31, the representative compound numbers are, in order, 35-1 to 35-69.
Table 36: in the general formula I-2A, when R is 1 ＝C 6 H 5 When (R) is substituted 9 ) n In agreement with Table 31, the representative compound numbers are in the order of 36-1 to 36-69.
In the general formula I-2B,
Figure BDA0001816962790000191
when R is 1 ＝CH 3 When (R) 9 ) n The substituents are shown in Table 37, and represent the numbers of the compounds in the order of 37-1 to 37-33.
Watch 37
Figure BDA0001816962790000192
Table 38: in the general formula I-2B, when R 1 When = H, substituent (R) 9 ) n In agreement with Table 37, the numbers of the representative compounds are 38-1 to 38-33 in this order.
Table 39: in the general formula I-2B, when R 1 ＝C 2 H 5 When (R) is substituted 9 ) n In agreement with Table 37, the numbers of the representative compounds were 39-1 to 39-33 in this order.
Table 40: in the general formula I-2B, when R 1 ＝i-C 3 H 7 When (R) is substituted 9 ) n In agreement with Table 37, the numbers of the representative compounds were 40-1 to 40-33 in this order.
Table 41: in the general formula I-2B, when R is 1 ＝n-C 4 H 9 When (R) is substituted 9 ) n In agreement with Table 37, the representative compound numbers were 41-1 to 41-33 in this order.
Table 42: in the general formula I-2B, when R is 1 ＝C 6 H 5 When (R) is substituted 9 ) n In agreement with Table 37, the representative compound numbers are in the order of 42-1 to 42-33.
In the general formula I-2C,
Figure BDA0001816962790000193
when R is 1 ＝CH 3 When (R) 9 ) n The substituents are shown in Table 43, which represent the numbers of the compounds in the order of 43-1 to 43-11.
Watch 43
No. (R 9 )n No. (R 9 )n No. (R 9 )n
43-1 2-Cl 43-2 3-Cl 43-3 2-OCH 3
43-4 2-Br 43-5 2-I 43-6 2,6-2OCH 3
43-7 2,6-2Cl 43-8 2-CN 43-9 2-NHCH 3 -6-Cl
43-10 6-OPh 43-11 2-OCH 3 -6-Cl
Table 44: in the general formula I-2C, when R 1 (= H), substituent (R) 9 ) n In agreement with Table 43, the numbers of the representative compounds are 44-1 to 44-11 in this order.
Table 45: in the general formula I-2C, when R 1 ＝C 2 H 5 When (R) is substituted 9 ) n In agreement with Table 43, the representative compound numbers are in the order of 45-1 to 45-11.
Table 46: in the general formula I-2C, when R is 1 ＝i-C 3 H 7 When (R) is substituted 9 ) n In accordance with Table 43, generationThe compounds in the table are numbered in order 46-1 to 46-11.
Table 47: in the general formula I-2C, when R 1 ＝n-C 4 H 9 When (R) is substituted 9 ) n In agreement with Table 43, the numbers of the representative compounds are 47-1 to 47-11 in this order.
Table 48: in the general formula I-2C, when R 1 ＝C 6 H 5 When (R) is substituted 9 ) n In agreement with Table 43, the representative compound numbers are in the order of 48-1 to 48-11.
In the general formula I-3A,
Figure BDA0001816962790000201
when R is 1 ＝CH 3 When (R) 9 ) n The substituents are shown in Table 49, and represent the numbers of the compounds 49-1-49-48 in sequence.
Watch 49
No. (R 9 )n No. (R 9 )n No. (R 9 )n
49-1 H 49-2 2-CN-6-CH 3 49-3 2-SCH 3 -6-CH 3
49-4 6-C 3 H 7 49-5 2-SCH 3 -5-Br 49-6 2-CN-5,6-2CH 3
49-7 6-Cl 49-8 5-NH 2 -6-Cl 49-9 2-PhNH-6-CF 3
49-10 2-Cl 49-11 2-SCH 3 -5-Cl 49-12 2-SO 2 CH 3 -6-CF 3
49-13 6-OH 49-14 2-SCH 3 -6-Cl 49-15 2-SO 2 CH 3 -6-CH 3
49-16 5-CH 3 49-17 2-Ph-4-CH 3 49-18 2-CF 3 -5,6-2CH 3
49-19 2-NH 2 49-20 2-NH 2 -6-CH 3 49-21 2-CF 3 -5-CO 2 C 2 H 5
49-22 2-Ph 49-23 6-Cl-2-PhCH 2 49-24 2-CN-5-CH 3 -6-Cl
49-25 2,6-2NH 2 49-26 2-NH 2 -6-CF 3 49-27 2-SCH 3 -5-OH-6-Cl
49-28 2-CN-6-Cl 49-29 2-NH 2 -6-OCH 3 49-30 2-(3-CH 3 -Ph)-6-OH
49-31 2-CN-6-CF 3 49-32 2-SCH 3 -6-NH 2 49-33 2-CONH 2 -6-CH 3
49-34 5-Cl-2-NH 2 49-35 2-SCH 3 -6-CF 3 49-36 2-CONH 2 -6-CF 3
49-37 2-(Cyclopropyl)NH-6-CF 3 49-38 2-(3,4-2Cl-Ph)NH-6-CF 3 49-39 2-(4-Cl-Ph)NH-6-CF 3
49-40 2-(2-Cl-Ph)NH-6-CF 3 49-41 2-(2,4-2F-Ph)NH-6-CF 3 49-42 2-(2,3,4-3Cl-Ph)NH-6-CF 3
49-43 2-(2,3-2Cl-Ph)NH-6-CF 3 49-44 2-(4-F-Ph)NH-6-CF 3 49-45 2-(2,6-2Cl-Ph)NH-6-CF 3
49-46 2-(2,4-2Cl-Ph)NH-6-CF 3 49-47 2-(2-F-Ph)NH-6-CF 3 49-48 2-(2,6-2F-Ph)NH-6-CF 3
TABLE 50: in the general formula I-3A, when R is 1 When = H, substituent (R) 9 ) n In agreement with Table 49, the numbers of the representative compounds are, in order, 50-1 to 50-48.
Table 51: in the general formula I-3A, when R 1 ＝C 2 H 5 When (R) is substituted 9 ) n In agreement with Table 49, the representative compound numbers are, in order, 51-1 to 51-48.
Table 52: in the general formula I-3A, when R is 1 ＝i-C 3 H 7 When (R) is substituted 9 ) n In agreement with Table 49, the numbers of the representative compounds are 52-1 to 52-48 in this order.
Table 53: in the general formula I-3A, when R is 1 ＝n-C 4 H 9 When (R) is substituted 9 ) n In agreement with Table 49, the representative compound numbers are in the order of 53-1 to 53-48.
Table 54: in the general formula I-3A, when R is 1 ＝C 6 H 5 When (R) is substituted 9 ) n In agreement with Table 49, the representative compound numbers are, in order, 54-1 to 54-48.
In the general formula I-3B,
Figure BDA0001816962790000211
when R is 1 ＝CH 3 When (R) 9 ) n The substituents are shown in Table 55, and represent the compound numbers of 55-1-55-20 in sequence.
Watch 55
No. (R 9 )n No. (R 9 )n No. (R 9 )n
55-1 H 55-2 4,6-2CH 3 55-3 4-CO 2 CH 3
55-4 5-Br 55-5 4-thienyl 55-6 4,6-2OCH 3
55-7 4-CH 3 55-8 4,6-2Cl 55-9 4,5,6-3Cl
55-10 4-furyl 55-11 6-Ph 55-12 4-Cl-5-Br
55-13 4-(4-Cl-Ph) 55-14 4-NH 2 -5-CN 55-15 4-CH 3 -6-CO 2 C 2 H 5
55-16 5-CO 2 CH 3 55-17 4-Cl-6-CH 3 55-18 4-CF 3 -5-CO 2 CH 3
55-19 4-CH 3 -6-CO 2 CH 3 55-20 2-Pyridyl-5-Cl-6-CH 3
Table 56: in the general formula I-3B, when R is 1 (= H), substituent (R) 9 ) n In agreement with Table 55, the representative compound numbers are in the order of 56-1 to 56-20.
Table 57: in the general formula I-3B, when R is 1 ＝C 2 H 5 When (R) is substituted 9 ) n In agreement with Table 55, the representative compound numbers are in the order of 57-1 to 57-20.
Table 58: in the general formula I-3B, when R is 1 ＝i-C 3 H 7 When (R) is substituted 9 ) n In agreement with Table 55, the representative compound numbers are in the order of 58-1 to 58-20.
Table 59: in the general formula I-3B, when R is 1 ＝n-C 4 H 9 When (R) is substituted 9 ) n In agreement with Table 55, the representative compound numbers are, in order, 59-1 to 59-20.
Table 60: in the general formula I-3B, when R is 1 ＝C 6 H 5 When (R) is substituted 9 ) n In agreement with Table 55, the representative compound numbers are 60-1 to 60-20 in this order.
In the general formula I-4A,
Figure BDA0001816962790000212
when R is 1 ＝CH 3 When (R) 9 ) n The substituents are shown in Table 61 and represent the compound numbers 61-1-61-11 in sequence.
Watch 61
No. (R 9 )n No. (R 9 )n No. (R 9 )n
61-1 H 61-2 6-Cl 61-3 6-Br
61-4 6-CH 3 61-5 6-NH 2 61-6 6-OCH 3
61-7 6-CF 3 61-8 6-OPh 61-9 6-SCH 3
61-10 4-CH 3 -6-Cl 61-11 6-NHCH 3
Table 62: in the general formula I-4A, when R is 1 When = H, substituent (R) 9 ) n Corresponding to Table 61, the numbers of the compounds are 62-1 to 62-11.
Table 63: in the general formula I-4A, when R is 1 ＝C 2 H 5 When (R) is substituted 9 ) n In agreement with Table 61, the numbers of the representative compounds are 63-1 to 63-11 in this order.
Table 64: in the general formula I-4A, when R 1 ＝i-C 3 H 7 When (R) is substituted 9 ) n In agreement with Table 61, the numbers of the representative compounds are 64-1 to 64-11 in this order.
Table 65: in the general formula I-4A, when R is 1 ＝n-C 4 H 9 When (R) is substituted 9 ) n In agreement with Table 61, the representative compound numbers are 65-1 to 65-11 in that order.
Table 66: in the general formula I-4A, when R is 1 ＝C 6 H 5 When (R) is substituted 9 ) n In agreement with Table 61, the representative compound numbers are 66-1 to 66-11 in that order.
In the general formula I-5A,
Figure BDA0001816962790000221
when R is 1 ＝CH 3 When (R) 9 ) n The substituents are shown in Table 67, and represent the numbers of the compounds in sequence 67-1 to 67-16.
Watch 67
No. (R 9 )n No. (R 9 )n No. (R 9 )n
67-1 H 67-2 5-Cl 67-3 6-Cl
67-4 5-NH 2 67-5 5-CN 67-6 6-CN
67-7 3-Cl 67-8 5-CH 3 67-9 6-OCH 3
67-10 5-OCH 3 67-11 5-SCH 3 67-12 6-SCH 3
67-13 6-OPh 67-14 5-OPh 67-15 5-SPh
67-16 5,6-(CH＝CCl-CH＝CH-)
Table 68: in the general formula I-5A, when R is 1 When = H, substituent (R) 9 ) n In agreement with Table 67, the representative compound numbers were 68-1 to 68-16 in this order.
Table 69: in the general formula I-5A, when R is 1 ＝C 2 H 5 When (R) is substituted 9 ) n In agreement with Table 67, the representative compound numbers were 69-1 to 69-16 in this order.
Table 70: in the general formula I-5A, when R is 1 ＝i-C 3 H 7 When (R) is substituted 9 ) n In agreement with Table 67, the representative compound numbers are 70-1 to 70-16 in that order.
Table 71: in the general formula I-5A, when R is 1 ＝n-C 4 H 9 When (R) is substituted 9 ) n In agreement with Table 67, the numbers of the representative compounds are 71-1 to 71-16 in this order.
Table 72: in the general formula I-5A, when R is 1 ＝C 6 H 5 When (R) is substituted 9 ) n In agreement with Table 67, the numbers of the representative compounds are 72-1 to 72-16 in this order.
Table 73: in the general formula I-5B, when R 1 ＝CH 3 When (R) is substituted 8 ) n In agreement with Table 67, the numbers of the representative compounds are 73-1 to 73-16 in this order.
Table 74: in the general formula I-5B, when R is 1 When = H, substituent (R) 9 ) n Corresponding to Table 67, the numbers of the compounds are 74-1 to 74-16.
Table 75: in the general formula I-5B, when R is 1 ＝C 2 H 5 When (R) is substituted 9 ) n In agreement with Table 67, the numbers of the representative compounds are 75-1 to 75-16 in this order.
Table 76: in the general formula I-5B, when R is 1 ＝i-C 3 H 7 When (R) is substituted 9 ) n In agreement with Table 67, the representative compound numbers were 76-1 to 76-16 in this order.
Table 77: in the general formula I-5B, when R 1 ＝n-C 4 H 9 When (R) is substituted 9 ) n In agreement with Table 67, the representative compound numbers are 77-1 to 77-16 in that order.
Table 78: in the general formula I-5B, when R is 1 ＝C 6 H 5 When (R) is substituted 9 ) n In agreement with Table 67, the representative compound numbers were 78-1 to 78-16 in this order.
In the general formula I-1A, when R is 1 ＝CH 3 、(R 9 ) n When = H, substituent R 10 (not hydrogen) are different substituents as shown in Table 79, representing compounds with numbers of 79-1-79-140.
TABLE 79
Figure BDA0001816962790000231
Figure BDA0001816962790000241
Table 80: in the general formula I-1A, when R 1 ＝CH 3 、(R 9 ) n When =2-Cl, the substituent R 10 In agreement with Table 79, the numbers of the representative compounds were 80-1 to 80-140 in this order.
Table 81: in the general formula I-1A, when R is 1 ＝CH 3 、(R 9 ) n When =4-Cl, the substituent R 10 In agreement with Table 79, the numbers of the representative compounds were 81-1 to 81-140 in this order.
Table 82: in the general formula I-1A, when R 1 ＝CH 3 、(R 9 ) n When =2,4-2Cl, the substituent R 10 In agreement with Table 79, the numbers of the representative compounds are 82-1 to 82-140 in this order.
Table 83: in the general formula I-1A, when R 1 ＝CH 3 、(R 9 ) n ＝2,5-2CH 3 When the substituent R is 10 In agreement with Table 79, the representative compound numbers are, in order, 83-1 to 83-140.
Table 84: in the general formula I-1A, when R is 1 ＝CH 3 、(R 9 ) n When =2,6-2F, the substituent R 10 In agreement with Table 79, the representative compound numbers are 84-1 to 84-140 in this order.
Table 85: in the general formula I-1A, when R is 1 ＝CH 3 、(R 9 ) n ＝2-CH 3 When the substituent R is 10 In agreement with Table 79, the representative compound numbers are, in order, 85-1 to 85-140.
Table 86: in the general formula I-1A, when R is 1 ＝CH 3 、(R 9 ) n ＝4-CH 3 When the substituent R is 10 In agreement with Table 79, the representative compound numbers were 86-1 to 86-140 in this order.
The salts of some of the compounds of the present invention can be illustrated by the salts of the specific compounds listed in Table 87, but are not intended to limit the present invention.
Table 87 partial Compound salts
Figure BDA0001816962790000251
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 compound of the general formula I is prepared by the following method:
Figure BDA0001816962790000261
in formula VI, M is a leaving group selected from chlorine or bromine; the other groups are as defined above.
And reacting the intermediate IV with the intermediate VII in a suitable solvent under basic conditions to generate an intermediate V, and then reacting with the intermediate VI in a suitable solvent under basic conditions to obtain the compound of the general formula I.
Suitable bases in the above two reaction processes may be the same or different and are selected from, for example, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, triethylamine, pyridine, sodium methoxide, sodium ethoxide, sodium hydride, potassium tert-butoxide or sodium tert-butoxide, etc.
Suitable solvents for the two-stage reaction process can be the same or different and are selected from, for example, tetrahydrofuran, 1, 4-dioxane, acetonitrile, toluene, xylene, benzene, N-dimethylformamide, N-methylpyrrolidone, dimethylsulfoxide, acetone, butanone, and the like.
Both reaction steps can be carried out at temperatures between room temperature and the boiling point of the appropriate solvent, typically from 20 ℃ to 100 ℃.
The reaction time of the two steps is 30 minutes to 20 hours, usually 1 to 10 hours.
The intermediate IV is a key intermediate for preparing the compound with the general formula I, and is prepared according to the following method:
Figure BDA0001816962790000262
taking II as a raw material to synthesize an intermediate III, and further synthesizing an intermediate IV, and referring to the following documents: WO2008057402, WO2004087056 and the like.
Intermediates VI and VII are both commercially available.
Although the compounds of formula I of the present invention are also pyrimido-ring containing compounds, as compared to certain compounds disclosed in the prior art, there are still significant differences in structural characteristics. And the compound of the present invention has better bactericidal activity due to the difference in these structures.
The compound of the general formula I shows excellent activity on various pathogenic bacteria in agriculture or other fields. Therefore, the technical scheme of the invention also comprises the application of the compound shown in the general formula I in preparing bactericides 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.; <xnotran> , ( , , , , , , , , , , , , , , , ), ( , , , , , , ), ( , , , , ), ( , , , , , , , , , , , , , , , , ), ( , , , , ), ( , , ), ( , , , , , , , ), ( , , , , , , , , , ), ( , </xnotran> Black spot of rape, black spot of sesame, black spot of sunflower, black spot of castor, black spot of tomato, black spot of pepper, black spot of eggplant, black spot of bean, black spot of cucumber, black spot of celery, black rot of carrot, black spot of apple, black spot of peanut), 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-breaking disease, rice blast, sheath blight, sugarcane eye spot, cotton boll aspergillosis, peanut crown rot, soybean stem blight, soybean black spot, melon northern leaf spot, peanut net blotch, tea red leaf spot, pepper white spot, wax gourd leaf spot, celery black rot, spinach heart rot, kenaf leaf mold, kenaf spot, jute stem spot, soybean violet spot, sesame leaf spot, castor gray spot, tea brown leaf spot, brown round spot, kidney red spot, balsam pear white spot, watermelon spot, jute rot, sunflower root rot, kidney bean rot, soybean target, eggplant rod spore leaf spot, cucumber target spot, tomato leaf mold, eggplant leaf mold, broad bean red spot, etc.); 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 head, sorghum head smut, sorghum stalk smut, kernel smut, sugarcane head smut, bean rust) and others (such as wheat sharp eyespot, rice sheath blight and the like); 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 and farm animals of agricultural and horticultural importance, and the environment customary for humans, against harmful bacteria.
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 composition using the compound shown in the general formula I as an active component. The weight percentage of the active components in the sterilization composition is between 0.5 and 99 percent. The bactericidal composition also comprises a carrier which is acceptable in agriculture, forestry and sanitation.
The compositions of the present invention may be administered in the form of a formulation. The compounds of formula I are dissolved or dispersed as active ingredients in carriers or formulated to be more easily dispersed for use as fungicides. For example: the chemical preparations can be prepared into wettable powder, oil suspension, water suspension, emulsion in water, aqua, 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, which comprises the following steps: the bactericidal composition is applied to the germs or the growth medium thereof. Preferably, an effective amount of from 10 grams per hectare to 1000 grams per hectare is generally selected, and preferably an effective amount of from 20 grams per hectare to 500 grams per hectare is selected.
For certain applications, for example, agriculture, one or more other fungicides, insecticides, acaricides, herbicides, plant growth regulators or fertilizers, etc., can be added to the fungicidal compositions of the present invention, thereby providing additional advantages and effects.
It should be understood that various changes and modifications may be made within the scope of the present invention as defined by the claims. The invention has the advantages that: the compound has novel structure and broad-spectrum bactericidal activity, has the control effect of more than 80 percent on cucumber downy mildew of 6.25ppm, and is a lead structure with great optimization value.
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 2- ((3-methylisoxazolo [5,4-d ] pyrimidin-4-yl) amino) ethanol
1) Preparation of 5-amino-3-methylisoxazole-4-cyano
Figure BDA0001816962790000281
14g (0.2 mol) of hydroxylamine hydrochloride was dissolved in 80mL of 10% sodium hydroxide, 27.2g (0.2 mol) of (1-ethoxyethylene) malononitrile was added, a small amount of ice was added to keep the temperature at 50 ℃ or lower, the mixture was stirred at room temperature for 1.5 hours, and the solid was filtered, washed with water, and recrystallized from absolute ethanol to obtain 16.5g of a solid product.
2) Preparation of 4-chloro-3-methylisoxazolo [5,4-d ] pyrimidine
Figure BDA0001816962790000282
Phosphorus oxychloride (POCl) 3 ) 40mL and 1mL of N, N-dimethylformamide were added to a reaction flask, and stirred at room temperature for 1 hour, 5-amino-3-methylisoxazole-4-cyano (451mg, 3.66mmol) was added thereto, the temperature was raised to 160 ℃ to react for 15 to 36 hours, and the reaction mixture was distilled under reduced pressure to give a pale yellow solid having a melting point of 110.5 ℃.
3) Preparation of 4- (2- ((3-methylisoxazolo [5,4-d ] pyrimidin-4-yl) amino) ethyl) phenol
Figure BDA0001816962790000283
1.69g (0.01 mol) of 4-chloro-3-methylisoxazolo [5,4-d ] pyrimidine and 2.74g (0.02 mol) of p-hydroxyphenylethylamine were added to 50ml of tetrahydrofuran, 4.45g (0.022 mol) of triethylamine was added, the reaction was carried out at room temperature for 4 to 10 hours, and after completion of the reaction, TLC was carried out to monitor that the solvent was distilled off under reduced pressure, water was added to precipitate a solid, and the solid was filtered to obtain an intermediate.
Example 2: preparation of Compound 7-1
Figure BDA0001816962790000291
0.54g (2 mmol) of 4- (2- ((3-methylisoxazolo [5,4-d ] pyrimidin-4-yl) amino) ethyl) phenol and 0.25g (2 mmol) of benzyl chloride were added to 5 ml of N, N-dimethylformamide, 0.41g (3 mmol) of potassium carbonate was added, the mixture was heated to 80 ℃ and reacted for 4 to 10 hours, and after completion of the reaction monitored by TLC, the reaction mixture was poured into 50ml of saturated saline, extracted three times with 100 ml of ethyl acetate and dried. After desolventizing, the product is purified by column chromatography to obtain 0.45 g, namely the compound 7-1 with the melting point of 123.0 ℃.
1 H-NMR (300 MHz, internal standard TMS, solvent CDCl 3 )δ(ppm):8.50(s,1H),7.35-7.42(m,5H),7.15(d,2H),6.97(d,1H),5.16(s,1H),5.07(s,2H),3.87(q,2H),2.93(t,2H),2.37(s,3H)。
Example 3: preparation of Compounds 31-33
Figure BDA0001816962790000292
0.16g of 60% sodium hydride was charged into a reaction flask, washed with petroleum ether, and 5 ml of N, N-dimethylformamide was added, followed by 0.54g (2 mmol) of 4- (2- ((3-methylisoxazolo [5,4-d ] pyrimidin-4-yl) amino) ethyl) phenol, stirring at room temperature for 2 minutes, then 0.43g (2 mmol) of intermediate 2, 3-dichloro-5-trifluoromethylpyridine was added, and the reaction was stirred at 60 ℃ for 2 hours. After completion of the reaction monitored by TLC, the reaction mixture was poured into 50ml of saturated brine, extracted three times with 100 ml of ethyl acetate, and dried. After exsolution, the product is purified by column chromatography to obtain 0.58 g, namely the compound 31-33. Melting Point 141.7 ℃.
1 H-NMR (300 MHz, internal standard TMS, solvent CDCl 3 )δ(ppm):8.53(s,1H),8.25(s,1H),7.99(s,1H),7.32(d,2H),7.16(d,2H),5.25(s,1H),3.96(q,2H),3.05(t,2H),2.48(s,3H)。
Other compounds of the invention may be prepared by reference to the above examples.
Physical data and Nuclear magnetic data of some Compounds: ( 1 HNMR,300MHz, internal standard TMS, ppm) as follows:
compounds 31-18: melting point 132.2 ℃. Delta (CDCl) 3 )8.53(s,1H),8.41(d,1H),7.92(dd,1H),7.30(d,2H),7.14(dd,2H),7.04(d,1H),5.30(s,1H),3.95(q,2H),3.04(t,2H),2.47(s,3H)。
Compounds 7-168: melting Point 115.0 ℃. Delta (CDCl) 3 )8.51(s,1H),7.35-7.44(dd,4H),7.15(d,2H),6.97(d,1H),5.30(s,1H),5.03(s,2H),3.87(q,2H),2.93(t,2H),2.38(s,3H),1.33(s,9H)。
Compounds 31-22: delta (CDCl) 3 )8.52(s,1H),8.44(d,1H),7.94(dd,1H),7.32(d,2H),7.13(d,2H),7.05(d,1H),5.30(s,1H),3.95(q,2H),3.04(t,2H),2.48(s,3H)。
Compounds 7 to 8: melting point 155.6 deg.C。δ(CDCl 3 )8.51(s,1H),7.34(m,1H),7.16(d,2H),6.99(d,2H),6.94(m,2H),5.18(s,1H),5.12(s,2H),3.88(q,2H),2.95(t,2H),2.40(s,3H)。
Compounds 7-17: melting point 163.7 ℃. Delta (CDCl) 3 )8.50(s,1H),7.54(m,1H),7.40(m,1H),7.27(m,2H),7.16(d,2H),6.97(d,2H),5.17(s,3H),3.88(q,2H),2.94(t,2H),2.39(s,3H)。
Compounds 7-55: melting point 148.9 ℃. Delta (CDCl) 3 )8.51(s,1H),7.40(m,1H),7.25(m,1H),7.21(m,2H),7.15(d,2H),6.97(d,2H),5.17(s,1H),5.04(s,2H),3.88(q,2H),2.95(t,2H),2.39(s,3H),2.38(s,3H)。
7-230 parts of compound, and the melting point is 158.3 ℃. Delta (CDCl) 3 )8.51(s,1H),7.30(m,1H),7.25(m,1H),7.17(d,2H),7.05(m,1H),7.02(d,2H),5.18(s,3H),3.90(q,2H),2.95(t,2H),2.41(s,3H)。
7-21 parts of compound, melting point 157.1 ℃. Delta (CDCl) 3 )8.51(s,1H),7.48(m,1H),7.43(m,1H),7.27(m,1H),7.18(d,2H),6.95(d,2H),5.17(s,1H),5.12(s,2H),3.88(q,2H),2.94(t,2H),2.41(s,3H)。
7-60 of compound, and the melting point is 134.0 ℃. Delta (CDCl) 3 )8.51(s,1H),7.22(s,1H),7.16(d,2H),7.09(m,2H),6.98(d,2H),5.17(s,1H),4.99(s,2H),3.90(q,2H),2.95(t,2H),2.40(s,3H),2.33(s,6H)。
82-111 melting point 146.7 ℃. Delta (CDCl) 3 )8.54(s,1H),7.47(m,2H),7.42(m,1H),7.25(m,1H),7.22(m,1H),7.12(d,2H),7.05(d,1H),6.89(m,2H),5.10(s,2H),4.79(s,2H),3.89(q,2H),2.97(t,2H),2.34(s,3H)。
83-114 melting point 209.6 ℃. Delta (CDCl) 3 )8.55(s,1H),7.22(s,1H),7.10(m,4H),7.05(m,2H),6.91(d,2H),6.80(s,1H),4.97(s,2H),4.60(s,2H),3.86(q,2H),2.98(t,2H),2.32(s,6H),2.27(s,3H),2.26(s,3H),2.12(s,3H)。
Other compounds of formula I can also be obtained as described in the above preparation methods.
Examples of measurement of biological Activity
The compound of the invention shows good activity to various germs in the agricultural field.
Example 4: measurement of fungicidal Activity
The compound sample of the invention is used for carrying out in vitro bacteriostatic activity or in vivo protection effect test on a plurality of fungal diseases of plants. The results of the bactericidal activity measurements are given in the examples below.
(1) In vitro bactericidal Activity assay
The measurement method is as follows: a high-throughput screening method is adopted, namely 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) to prepare a liquid to be detected with the required concentration. Under an ultra-clean 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 in vitro bacteriostatic activity (expressed as inhibition) of some compounds was tested as follows:
inhibition rate against rice blast germs:
under the dosage of 25ppm, the inhibition rate of the compounds 31-18, 31-33 and the like on rice blast is more than 80 percent;
(2) Living body protecting Activity assay
The measurement method is as follows: the living potted plant assay method is adopted, i.e., a sample of a compound to be tested is dissolved in a small amount of solvent (the type of solvent is acetone, methanol, DMF, etc., and is selected according to the dissolving capacity of the solvent for the sample, and the volume ratio of the amount of the solvent to the amount of sprayed liquid is equal to or less than 0.05), and diluted with water containing 0.1% Tween 80 to prepare a solution to be tested with a 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 control effect of the compounds 7-1, 7-8, 7-17, 7-55, 7-168, 7-230, 31-18, 31-22, 31-33, 83-114 and the like on cucumber downy mildew is more than 80 percent;
under the dosage of 100ppm, the control effect of the compounds 7-1, 7-8, 7-17, 7-55, 7-230, 31-18, 31-22, 31-33 and the like on cucumber downy mildew is more than 80 percent;
under the dosage of 25ppm, the control effect of the compounds 7-1, 7-8, 31-18, 31-22 and the like on cucumber downy mildew is more than 80 percent;
under the dosage of 6.25ppm, the control effect of the compounds 7-1, 31-18, 31-22 and the like on cucumber downy mildew is more than 80 percent;
in vivo protective activity against wheat powdery mildew:
under the dosage of 400ppm, the control effect of the compounds 7-1, 31-18, 31-22, 31-33 and the like on the wheat powdery mildew is more than 80 percent;
in vivo protective activity against corn rust:
under the dosage of 400ppm, the control effect of the compounds 7-1, 7-8, 7-17, 7-55, 31-18, 31-22 and the like on the corn rust is more than 80 percent.
In vivo protective activity against cucumber anthracnose:
under the dosage of 400ppm, the control effect of the compounds 7-1, 7-8, 7-17, 7-55, 7-168, 7-230, 31-18 and the like on cucumber anthracnose is more than 80 percent.
Test results (% control) for Compound 7-1 and control Agents
Figure BDA0001816962790000311

Claims (5)

1. A pyrimido-ring-containing compound characterized by:
has a structure of I-1A
Figure FDF0000020306900000011
In the formula:
R 1 is selected from C 1 -C 4 An alkyl group;
R 2 selected from hydrogen;
R 3 、R 4 are respectively selected from hydrogen;
R 5 、R 6 、R 7 、R 8 are respectively selected from hydrogen;
R 10 selected from hydrogen;
R 9 selected from halogen, C 1 -C 4 An alkyl group;
in the general formula I-1A, n is selected from an integer from 1 to 5;
or a salt of a compound of formula I-1A: salts of the compounds of the general formula I-1A with hydrochloric acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, trifluoroacetic acid, oxalic acid, methanesulfonic acid, p-toluenesulfonic acid, benzoic acid, phthalic acid, maleic acid, fumaric acid, sorbic acid, malic acid or citric acid.
2. A pyrimido-ring-containing compound characterized by:
has the structure I-1A
Figure FDF0000020306900000012
In the formula:
R 1 is selected from methyl;
R 2 selected from hydrogen;
R 3 、R 4 are respectively selected from hydrogen;
R 5 、R 6 、R 7 、R 8 are respectively selected from hydrogen;
R 10 selected from hydrogen;
R 9 selected from hydrogen.
3. A pyrimido-ring-containing compound according to claim 1, wherein: in the compounds of formula I-1A:
R 1 is selected from methyl;
R 2 selected from hydrogen;
R 3 、R 4 are respectively selected from hydrogen;
R 5 、R 6 、R 7 、R 8 are respectively selected from hydrogen;
R 9 selected from fluorine, chlorine, methyl, n-butyl;
in the general formula I-1A, n is selected from an integer from 1 to 5;
or a salt of a compound of formula I-1A: salts of the compounds of the general formula I-1A with hydrochloric acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, trifluoroacetic acid, oxalic acid, methanesulfonic acid, p-toluenesulfonic acid, benzoic acid, phthalic acid, maleic acid, fumaric acid, sorbic acid, malic acid or citric acid.
4. Use of a pyrimido-ring containing compound according to any of claims 1 to 3 for the preparation of a fungicide medicament in the agricultural field.
5. A germicidal composition, characterized by: containing a pyrimido-ring containing compound according to any one of claims 1 to 3 as an active ingredient; wherein, the weight percentage of the active components in the composition is 0.1 to 99 percent.
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