CN112047895B - Triazole compound, and preparation method and application thereof - Google Patents

Triazole compound, and preparation method and application thereof Download PDF

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CN112047895B
CN112047895B CN201910493139.7A CN201910493139A CN112047895B CN 112047895 B CN112047895 B CN 112047895B CN 201910493139 A CN201910493139 A CN 201910493139A CN 112047895 B CN112047895 B CN 112047895B
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alkyl
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phenyl
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CN112047895A (en
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李义涛
林健
伍阳
赵致远
刘庆容
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Dongguan Hec Pesticides R&d Co ltd
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Dongguan Hec Pesticides R&d Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/647—Triazoles; Hydrogenated triazoles
    • A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/06—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms

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  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
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  • Plant Pathology (AREA)
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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention provides a triazole compound, a preparation method and application thereof; specifically, the invention relates to triazole compounds shown in formula (I) or stereoisomers, nitrogen oxides and salts thereof, a preparation method thereof, application thereof as bactericides, forms of bactericidal compositions thereof and a method for preventing and treating plant diseases in agriculture or gardens by using the compounds or the compositions; wherein R1、R2、R3、R4、R5、R6、R7、Ra、Rb、Rc、Rd、Re、X and n have the meaning as described in the present invention.

Description

Triazole compound, and preparation method and application thereof
Technical Field
The invention relates to the field of agriculture, in particular to a triazole fungicide, a preparation method thereof and application thereof in agriculture as a pathogenic fungus control agent.
Background
Triazole bactericides are known plant disease control agents, and with the development of the times, green, broad-spectrum, low-toxicity and high-efficiency bactericides become important indexes for evaluating pesticides, so that new control agents with excellent controllability on various plant diseases are required to be continuously developed.
Disclosure of Invention
The invention provides a novel triazole fungicide which has excellent control effect on diseases caused by plant pathogenic fungi.
Specifically:
In one aspect, the present invention provides a compound which is a compound having the formula (I) or a stereoisomer, oxynitride or salt thereof of a compound of the formula (I):
Wherein,
R 1 and R 2 are each independently hydrogen or C 1-6 alkyl;
R 3 is OR 33;R33 is hydrogen, C 1-6 alkyl, C 2-6 alkenyl, C 2-6 alkynyl, C 3-8 cycloalkyl, C 3-8 cycloalkyl-C 1-6 alkyl, phenyl OR phenyl-C 1-6 alkyl;
R 5 is OR 55;R55 is hydrogen, C 1-6 alkyl, C 2-6 alkenyl, C 2-6 alkynyl, C 3-8 cycloalkyl, C 3-8 cycloalkyl-C 1-6 alkyl, phenyl OR phenyl-C 1-6 alkyl;
R 4 and R 6 are each independently hydrogen or C 1-6 alkyl;
Or R 5、R6 and the carbon atom to which it is attached form c=o;
or R 5、R3 and the carbon atom to which it is attached form ethylene oxide;
Or R 3、R2 and the carbon atom to which it is attached form a carbon-carbon double bond;
n is 0,1,2 or 3;
R 7 is halogen, cyano, hydroxy, nitro, amino, C 1-6 alkyl, C 1-6 alkoxy, halogenated C 1-6 alkyl or halogenated C 1-6 alkoxy;
X is-O-, -S-or-CH 2 O-;
R a、Rb、Rc、Rd and R e are each independently hydrogen, halogen, cyano, hydroxy, mercapto, nitro, carboxy (-COOH), C 1-6 alkyl, C 1-6 alkoxy, halo C 1-6 alkyl, halo C 1-6 alkoxy, C 2-6 alkenyl, C 2-6 alkynyl, halo C 2-6 alkenyl, halo C 2-6 alkynyl, C 2-6 alkenyloxy, C 2-6 alkynyloxy, C 3-8 cycloalkyl, halo C 3-8 cycloalkyl, C 3-8 cycloalkyloxy, C 3-8 cycloalkyl-C 1-6 alkyl, -S (=O) x-C1-6 alkyl, -C (=O) -C 1-6 alkyl, -C (=O) O-C 1-6 alkyl, -NR 8R9、-C(＝O)NR10R11, phenyl, benzyl or phenoxy;
r 8、R9、R10 and R 11 are each independently hydrogen, C 1-6 alkyl, C 3-8 cycloalkyl, C 3-8 cycloalkyl-C 1-6 alkyl, phenyl or phenyl-C 1-6 alkyl;
x is 0,1 or 2;
Or R a and R b、Rb and R c、Rc and R d or R d and R e form -O-(CH2)o-O-、-(CH2)p-O-、-(CH2)q-O-(CH2)r- or- (CH 2)s -;
o, p, q, r and s are each independently 1, 2,3 or 4;
Or R a and R b、Rb and R c、Rc form a benzene ring with the carbon atom to which R d or R d and R e are respectively attached; the benzene ring is optionally substituted with 1,2, 3 or 4 substituents selected from halogen, cyano, hydroxy, nitro, C 1-6 alkyl, C 1-6 alkoxy, halo C 1-6 alkyl or halo C 1-6 alkoxy.
Wherein, after R 5、R6 and the carbon atom connected with it form c=o, the corresponding structural formula is:
Wherein ,R1、R2、R3、R4、R7、n、Ra、Rb、Rc、Rd、Re and X have the meaning described in the present invention.
Wherein, after R 5、R3 and the carbon atom connected with R 5、R3 form ethylene oxide, the corresponding structural formula is as follows:
Wherein ,R1、R2、R4、R6、R7、n、Ra、Rb、Rc、Rd、Re and X have the meaning described in the present invention.
Wherein, after R 3、R2 and the carbon atom connected with R 3、R2 form a carbon-carbon double bond, the corresponding structural formula is:
Wherein ,R1、R4、R5、R6、R7、n、Ra、Rb、Rc、Rd、Re and X have the meaning described in the present invention.
In some embodiments, X is-O-or-CH 2 O-.
In other embodiments, X is-O-.
In some embodiments, R 1 and R 2 are each independently hydrogen or C 1-4 alkyl.
In other embodiments, R 1 and R 2 are each independently hydrogen 、-CH3、-CH2CH3、-CH2CH2CH3、-CH(CH3)2、-CH2CH2CH2CH3、-CH(CH3)CH2CH3、-CH2CH(CH3)CH3 or-C (CH 3)3.
In still other embodiments, R 1 and R 2 are each independently hydrogen.
In some embodiments, R 3 is OR 33;R33 is hydrogen, C 1-4 alkyl, C 2-4 alkenyl, C 2-4 alkynyl, C 3-6 cycloalkyl, C 3-6 cycloalkyl-C 1-4 alkyl, phenyl, OR phenyl-C 1-4 alkyl.
In other embodiments, R 3 is OR 33;R33 is hydrogen 、-CH3、-CH2CH3、-CH2CH2CH3、-CH(CH3)2、-CH2CH2CH2CH3、-CH(CH3)CH2CH3、-CH2CH(CH3)CH3、-C(CH3)3、-CH＝CH2、-CH2CH＝CH2、-CH＝CH-CH3、-CH2CH2CH＝CH2、-CH2CH＝CHCH3、-CH＝CHCH2CH3、-C≡CH、-CH2-C≡CH、-CH2CH2-C≡CH、 cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl, OR benzyl.
In still other embodiments, R 3 is OR 33;R33 is hydrogen 、-CH3、-CH2CH3、-CH2CH2CH3、-CH(CH3)2、-CH2CH2CH2CH3、-CH(CH3)CH2CH3、-CH2CH(CH3)CH3 OR-C (CH 3)3.
In still other embodiments, R 3 is OR 33;R33 is hydrogen.
In some embodiments, R 4 is hydrogen or C 1-4 alkyl.
In other embodiments, R 4 is hydrogen 、-CH3、-CH2CH3、-CH2CH2CH3、-CH(CH3)2、-CH2CH2CH2CH3、-CH(CH3)CH2CH3、-CH2CH(CH3)CH3 or —c (CH 3)3).
In some embodiments, R 5 is OR 55;R55 is hydrogen, C 1-4 alkyl, C 2-4 alkenyl, C 2-4 alkynyl, C 3-6 cycloalkyl, C 3-6 cycloalkyl-C 1-4 alkyl, phenyl, OR phenyl-C 1-4 alkyl.
In other embodiments, R 5 is OR 55;R55 is hydrogen 、-CH3、-CH2CH3、-CH2CH2CH3、-CH(CH3)2、-CH2CH2CH2CH3、-CH(CH3)CH2CH3、-CH2CH(CH3)CH3、-C(CH3)3、-CH＝CH2、-CH2CH＝CH2、-CH＝CH-CH3、-CH2CH2CH＝CH2、-CH2CH＝CHCH3、-CH＝CHCH2CH3、-C≡CH、-CH2-C≡CH、-CH2CH2-C≡CH、 cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl, OR benzyl.
In still other embodiments, R 5 is OR 55;R55 is hydrogen 、-CH3、-CH2CH3、-CH2CH2CH3、-CH(CH3)2、-CH2CH2CH2CH3、-CH(CH3)CH2CH3、-CH2CH(CH3)CH3 OR-C (CH 3)3.
In still other embodiments, R 5 is OR 55;R55 is hydrogen.
In some embodiments, R 6 is hydrogen or C 1-4 alkyl.
In other embodiments, R 6 is hydrogen 、-CH3、-CH2CH3、-CH2CH2CH3、-CH(CH3)2、-CH2CH2CH2CH3、-CH(CH3)CH2CH3、-CH2CH(CH3)CH3 or —c (CH 3)3).
In still other embodiments, R 6 is hydrogen.
In some embodiments, n is 0,1, 2, or 3;
R 7 is halogen, cyano, hydroxy, nitro, amino, C 1-4 alkyl, C 1-4 alkoxy, halogenated C 1-4 alkylhalogenated C 1-4 alkoxy.
In other embodiments, n is 0, 1,2, or 3;
R 7 is fluorine, chlorine, bromine, iodine, cyano, hydroxy, nitro, amino 、-CH3、-CH2CH3、-CH2CH2CH3、-CH(CH3)2、-CH2CH2CH2CH3、-CH(CH3)CH2CH3、-CH2CH(CH3)CH3、-C(CH3)3、-OCH3、-OCH2CH3、-OCH2CH2CH3、-OCH(CH3)2、-CF3 or-OCF 3.
In some embodiments, R a、Rb、Rc、Rd and R e are each independently hydrogen, halogen, cyano, hydroxy, mercapto, nitro, carboxy, C 1-4 alkyl, C 1-4 alkoxy, halo C 1-4 alkyl, halo C 1-4 alkoxy, C 2-4 alkenyl, C 2-4 alkynyl, halo C 2-4 alkenyl, halo C 2-4 alkynyl, C 2-4 alkenyloxy, C 2-4 alkynyloxy, C 3-6 cycloalkyl, halo C 3-6 cycloalkyl, C 3-6 cycloalkyloxy, C 3-6 cycloalkyl-C 1-4 alkyl, -S (=o) x-C1-4 alkyl, -C (=o) -C 1-4 alkyl, -C (=o) O-C 1-4 alkyl, -NR 8R9、-C(＝O)NR10R11, phenyl, benzyl, or phenoxy;
R 8、R9、R10 and R 11 are each independently hydrogen, C 1-4 alkyl, C 3-6 cycloalkyl, C 3-6 cycloalkyl-C 1-4 alkyl, phenyl or phenyl-C 1-4 alkyl;
x is 0,1 or 2.
In other embodiments, R a、Rb、Rc、Rd and R e are each independently hydrogen, fluoro, chloro, bromo, iodo, cyano, hydroxy, mercapto, nitro, carboxy (-COOH)、-CH3、-CH2CH3、-CH2CH2CH3、-CH(CH3)2、-CH2CH2CH2CH3、-CH(CH3)CH2CH3、-CH2CH(CH3)CH3、-C(CH3)3、-OCH3、-OCH2CH3、-OCH2CH2CH3、-OCH(CH3)2、-OCH2CH2CH2CH3、-OCH(CH3)CH2CH3、-OCH2CH(CH3)CH3、-OC(CH3)3、-CF3、-OCF3、-CH＝CH2、-CH2CH＝CH2、-CH＝CH-CH3、-CH2CH2CH＝CH2、-CH2CH＝CHCH3、-CH＝CHCH2CH3、-C≡CH、-CH2-C≡CH、-CH2CH2-C≡CH、 cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl 、-SCH3、-SCH2CH3、-S(＝O)2CH3、-S(＝O)2CH2CH3、-C(＝O)CH3、-C(＝O)CH2CH3、-C(＝O)OCH3、-C(＝O)OCH2CH3、-NH2、-NH(CH3)、-N(CH3)2、-NH(CH2CH3)、-N(CH2CH3)2、 phenyl, benzyl, or phenoxy.
In some embodiments, the present invention provides a compound that is a stereoisomer, nitroxide, or salt thereof having or a compound of formula (I-A):
Wherein ,R1、R2、R3、R4、R5、R6、Ra、Rb、Rc、Rd、Re and X have the meaning described in the present invention.
In some embodiments, the present invention provides a compound that is a stereoisomer, nitroxide, or salt thereof having or a compound of formula (II):
Wherein R 4、R6、Ra、Rb、Rc、Rd、Re and X have the meaning described in the present invention.
In some embodiments, the present invention provides a compound that is a stereoisomer, nitroxide, or salt thereof having or a compound of formula (II):
Wherein R 4 is hydrogen or C 1-4 alkyl;
R 6 is hydrogen or C 1-4 alkyl;
x is-O-or-CH 2 O-;
R a、Rb、Rc、Rd and R e are each independently hydrogen, halogen, cyano, hydroxy, mercapto, nitro, amino, C 1-4 alkyl, C 1-4 alkoxy, halogenated C 1-4 alkyl, halogenated C 1-4 alkoxy or phenyl.
In still other embodiments, R 4 is hydrogen or-CH 3;
R 6 is hydrogen;
x is-O-or-CH 2 O-;
R a、Rb、Rc、Rd and R e are each independently hydrogen, fluorine, chlorine, bromine, iodine, cyano, hydroxy, mercapto, nitro, amino 、-CH3、-CH2CH3、-CH2CH2CH3、-CH(CH3)2、-CH2CH2CH2CH3、-CH(CH3)CH2CH3、-CH2CH(CH3)CH3、-C(CH3)3、 phenyl, -CF 3 or-OCF 3.
In some embodiments, the present invention provides a compound that is a stereoisomer, oxynitride or salt thereof having a compound of formula (II-1) or a compound of formula (II-1):
Wherein R a、Rb、Rc、Rd and R e have the meaning described in the present invention.
In some embodiments, the present invention provides a compound that is a stereoisomer, oxynitride or salt thereof having a compound of formula (II-1) or a compound of formula (II-1):
Wherein R a、Rb、Rc、Rd and R e are each independently hydrogen, halogen, cyano, hydroxy, mercapto, nitro, amino, C 1-4 alkyl, C 1-4 alkoxy, halogenated C 1-4 alkyl, halogenated C 1-4 alkoxy or phenyl.
In some embodiments, R a、Rb、Rc、Rd and R e are each independently hydrogen, fluoro, chloro, bromo, iodo, cyano, hydroxy, mercapto, nitro 、-CH3、-CH2CH3、-CH2CH2CH3、-CH(CH3)2、-CH2CH2CH2CH3、-CH(CH3)CH2CH3、-CH2CH(CH3)CH3、-C(CH3)3、 phenyl, -CF 3, or-OCF 3.
In some embodiments, the present invention provides a compound that is a stereoisomer, oxynitride or salt thereof having a compound of formula (II-1) or a compound of formula (II-1):
wherein R a、Rb、Rd and R e are each independently hydrogen;
R c is hydrogen, halogen, cyano, hydroxy, mercapto, nitro, C 1-4 alkyl, C 1-4 alkoxy, halo C 1-4 alkyl, halo C 1-4 alkoxy or phenyl.
In some embodiments, R c is hydrogen, fluoro, chloro, bromo, iodo, cyano, hydroxy, mercapto, nitro 、-CH3、-CH2CH3、-CH2CH2CH3、-CH(CH3)2、-CH2CH2CH2CH3、-CH(CH3)CH2CH3、-CH2CH(CH3)CH3、-C(CH3)3, or phenyl.
In some embodiments, the present invention provides a compound that is a stereoisomer, oxynitride or salt thereof having a compound of formula (II-1) or a compound of formula (II-1):
wherein, R a、Rb、Rc、Rd and R e are as shown in Table 1:
TABLE 1
In some embodiments, the present invention provides a compound that is a stereoisomer, oxynitride or salt thereof having a compound represented by formula (II-2) or a compound represented by formula (II-2):
wherein, R a、Rb、Rc、Rd and R e are as shown in Table 2:
TABLE 2
Ra Rb Rc Rd Re
H H H H H
Cl H H H H
H Cl H H H
H H Cl H H
Br H H H H
H Br H H H
H H Br H H
H H I H H
In some embodiments, the present invention provides a compound that is a stereoisomer, oxynitride or salt thereof having a compound represented by formula (II-3) or a compound represented by formula (II-3):
wherein, R a、Rb、Rc、Rd and R e are as shown in Table 3:
TABLE 3 Table 3
Ra Rb Rc Rd Re
Cl H H H H
H Cl H H H
H H Cl H H
H H Br H H
In some embodiments, the present invention provides a compound that is a stereoisomer, nitroxide, or salt thereof having or a compound of formula (III):
Wherein R 4、Ra、Rb、Rc、Rd、Re and X have the meaning described in the present invention.
In some embodiments, the present invention provides a compound that is a stereoisomer, nitroxide, or salt thereof having or a compound of formula (III):
Wherein R 4 is hydrogen or C 1-4 alkyl;
x is-O-or-CH 2 O-;
R a、Rb、Rc、Rd and R e are each independently hydrogen, halogen, cyano, hydroxy, mercapto, nitro, amino, C 1-4 alkyl, C 1-4 alkoxy, halogenated C 1-4 alkyl, halogenated C 1-4 alkoxy or phenyl.
In still other embodiments, R 4 is hydrogen or-CH 3;
x is-O-or-CH 2 O-;
R a、Rb、Rc、Rd and R e are each independently hydrogen, fluorine, chlorine, bromine, iodine, cyano, hydroxy, mercapto, nitro, amino 、-CH3、-CH2CH3、-CH2CH2CH3、-CH(CH3)2、-CH2CH2CH2CH3、-CH(CH3)CH2CH3、-CH2CH(CH3)CH3、-C(CH3)3、 phenyl, -CF 3 or-OCF 3.
In some embodiments, the present invention provides a compound that is a stereoisomer, oxynitride or salt thereof having a compound of formula (III-1) or a compound of formula (III-1):
Wherein R a、Rb、Rc、Rd and R e are each independently hydrogen, halogen, cyano, hydroxy, mercapto, nitro, amino, C 1-4 alkyl, C 1-4 alkoxy, halogenated C 1-4 alkyl, halogenated C 1-4 alkoxy, or phenyl;
x is-O-or-CH 2 O-.
In some embodiments, R a、Rb、Rc、Rd and R e are each independently hydrogen, fluoro, chloro, bromo, iodo, cyano, hydroxy, mercapto, nitro, amino 、-CH3、-CH2CH3、-CH2CH2CH3、-CH(CH3)2、-CH2CH2CH2CH3、-CH(CH3)CH2CH3、-CH2CH(CH3)CH3、-C(CH3)3、-OCH3、-CF3、-OCF3, or phenyl.
In some embodiments, the present invention provides a compound that is a stereoisomer, oxynitride or salt thereof having a compound of formula (III-2) or a compound of formula (III-2):
wherein, R a、Rb、Rc、Rd and R e are as shown in Table 4:
TABLE 4 Table 4
In some embodiments, the present invention provides a compound that is a stereoisomer, oxynitride or salt thereof having a compound of formula (III-3) or a compound of formula (III-3):
Wherein, R a、Rb、Rc、Rd and R e are as shown in Table 5:
TABLE 5
In some embodiments, the present invention provides a compound that is a stereoisomer, oxynitride or salt thereof having a compound of formula (III-4) or a compound of formula (III-4):
Wherein, R a、Rb、Rc、Rd and R e are as shown in Table 6:
TABLE 6
Ra Rb Rc Rd Re
H H H H H
H Cl H H H
H H Cl H H
H OCF3 H H H
H H H F H
In some embodiments, the present invention provides a compound that is a stereoisomer, nitroxide, or salt thereof having or a compound of formula (IV):
Wherein R 4、R6、Ra、Rb、Rc、Rd、Re and X have the meaning described in the present invention.
In some embodiments, the present invention provides a compound that is a stereoisomer, nitroxide, or salt thereof having a compound of formula (IV-1) or a compound of formula (IV-1):
Wherein R 4 is hydrogen or C 1-4 alkyl;
R 6 is hydrogen or C 1-4 alkyl;
R a、Rb、Rc、Rd and R e are each independently hydrogen, halogen, cyano, hydroxy, mercapto, nitro, amino, C 1-4 alkyl, C 1-4 alkoxy, halogenated C 1-4 alkyl, halogenated C 1-4 alkoxy or phenyl.
In some embodiments, R 4 is hydrogen or-CH 3;
R 6 is hydrogen or-CH 3;
R a、Rb、Rc、Rd and R e are each independently hydrogen, fluorine, chlorine, bromine, iodine, cyano, hydroxy, mercapto, nitro, amino 、-CH3、-CH2CH3、-CH2CH2CH3、-CH(CH3)2、-CH2CH2CH2CH3、-CH(CH3)CH2CH3、-CH2CH(CH3)CH3、-C(CH3)3、-CF3、-OCF3 or phenyl.
In some embodiments, the present invention provides a compound that is a stereoisomer, nitroxide, or salt thereof having a compound of formula (IV-2) or a compound of formula (IV-2):
Wherein, R a、Rb、Rc、Rd and R e are as shown in Table 7:
TABLE 7
Ra Rb Rc Rd Re
H H H H H
H H Cl H H
H Cl H H H
Cl H H H H
Cl H Cl H H
H CH3 H H H
H H C(CH3)3 H H
F H H H H
H H OCH3 H H
H Br H H H
H H Br H H
H H I H H
H H Ph H H
In some embodiments, the present invention provides a compound that is a stereoisomer, nitroxide, or salt thereof having a compound of formula (IV-3) or a compound of formula (IV-3):
wherein, R a、Rb、Rc、Rd and R e are as shown in Table 8:
TABLE 8
Ra Rb Rc Rd Re
H H H H H
Cl H H H H
H Cl H H H
H H Cl H H
Br H H H H
H Br H H H
H H Br H H
H H I H H
In some embodiments, the present invention provides a compound that is a stereoisomer, nitroxide, or salt thereof having a compound of formula (IV-4) or a compound of formula (IV-4):
wherein, R a、Rb、Rc、Rd and R e are as shown in Table 9:
TABLE 9
Ra Rb Rc Rd Re
Cl H H H H
H H Cl H H
H H Br H H
In some embodiments, the present invention provides a compound that is a stereoisomer, nitroxide, or salt thereof having or a compound of formula (V):
wherein R a、Rb、Rc、Rd、Re and X have the meaning described in the present invention.
In some embodiments, the present invention provides a compound that is a stereoisomer, nitroxide, or salt thereof having or a compound of formula (V):
Wherein R 4 is hydrogen or C 1-4 alkyl;
R 6 is hydrogen or C 1-4 alkyl;
x is-O-or-CH 2 O-;
R a、Rb、Rc、Rd and R e are each independently hydrogen, halogen, cyano, hydroxy, mercapto, nitro, amino, C 1-4 alkyl, C 1-4 alkoxy, halogenated C 1-4 alkyl, halogenated C 1-4 alkoxy or phenyl.
In still other embodiments, R 4 is hydrogen or-CH 3;
R 6 is hydrogen or-CH 3;
x is-O-or-CH 2 O-;
R a、Rb、Rc、Rd and R e are each independently hydrogen, fluorine, chlorine, bromine, iodine 、-CH3、-CH2CH3、-CH2CH2CH3、-CH(CH3)2、-CH2CH2CH2CH3、-CH(CH3)CH2CH3、-CH2CH(CH3)CH3 or-C (CH 3)3).
In some embodiments, the present invention provides a compound that is a stereoisomer, a nitroxide, or a salt thereof having the formula (V-1) or the formula (V-1):
Wherein R a、Rb、Rc、Rd and R e have the meaning described in the present invention.
In some embodiments, the present invention provides a compound that is a stereoisomer, a nitroxide, or a salt thereof having the formula (V-1) or the formula (V-1):
Wherein R a、Rb、Rc、Rd and R e are each independently hydrogen, halogen, C 1-4 alkyl, C 1-4 alkoxy, halogenated C 1-4 alkyl or halogenated C 1-4 alkoxy.
In some embodiments, R a、Rb、Rc、Rd and R e are each independently hydrogen, fluorine, chlorine, bromine, iodine 、-CH3、-CH2CH3、-CH2CH2CH3、-CH(CH3)2、-CH2CH2CH2CH3、-CH(CH3)CH2CH3、-CH2CH(CH3)CH3, or-C (CH 3)3.
In some embodiments, the present invention provides a compound that is a stereoisomer, a nitroxide, or a salt thereof having the formula (V-2) or the formula (V-2):
Wherein R a、Rb、Rc、Rd and R e have the meaning described in the present invention.
In some embodiments, the present invention provides a compound that is a stereoisomer, a nitroxide, or a salt thereof having the formula (V-2) or the formula (V-2):
Wherein R a、Rb、Rc、Rd and R e are each independently hydrogen or halogen.
In some embodiments, the present invention provides a compound that is a stereoisomer, a nitroxide, or a salt thereof having the formula (V-1) or the formula (V-1):
Wherein, R a、Rb、Rc、Rd and R e are as shown in Table 10:
table 10
Ra Rb Rc Rd Re
H H H H H
H H Cl H H
Cl H H H H
H H Br H H
H H CH3 H H
H F H H H
H Br H H H
H H OCH3 H H
Cl H Cl H H
H H C(CH3)3 H H
In some embodiments, the present invention provides a compound that is a stereoisomer, a nitroxide, or a salt thereof having the formula (V-2) or the formula (V-2):
wherein, R a、Rb、Rc、Rd and R e are as shown in Table 11:
TABLE 11
Ra Rb Rc Rd Re
H H H H H
H F H H H
In some embodiments, the present invention provides a compound that is a stereoisomer, nitroxide, or salt thereof having or a compound of formula (VI):
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wherein, R a、Rb、Rc、Rd and R e are as shown in Table 12:
Table 12
Ra Rb Rc Rd Re
H H H H H
Cl H H H H
H Cl H H H
H H Cl H H
Br H H H H
H Br H H H
H H Br H H
H H I H H
In some embodiments, the present invention provides a compound that is a stereoisomer, nitroxide, or salt thereof, of a compound having one of the following structures:
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In another aspect, the invention provides a composition comprising at least one compound of the invention.
Further, the composition of the invention further comprises an agropharmaceutically acceptable surfactant and/or carrier.
In another aspect, the invention provides the use of a compound of the invention or a composition of the invention for controlling plant diseases.
In another aspect, the invention provides methods of using the compounds of the invention or the compositions of the invention in controlling plant diseases.
Detailed description of the invention
Definitions and general terms
Reference will now be made in detail to certain embodiments of the application, examples of which are illustrated in the accompanying structural and chemical formulas. The application is intended to cover all alternatives, modifications and equivalents, which may be included within the scope of the application as defined by the appended claims. Those skilled in the art will recognize that many methods and materials similar or equivalent to those described herein can be used in the practice of the present application. The present application is in no way limited to the methods and materials described herein. In the event of one or more of the incorporated references, patents and similar materials differing from or contradictory to the present application (including but not limited to defined terms, term application, described techniques, etc.), the present application controls.
It should further be appreciated that certain features of the invention, which are, for clarity, described in the context of separate embodiments, may also be provided in combination in a single embodiment. Conversely, various features of the invention, which are, for brevity, described in the context of a single embodiment, may also be provided separately or in any suitable sub-combination.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. All patents and publications referred to herein are incorporated by reference in their entirety.
The following definitions as used herein should be applied unless otherwise indicated. For the purposes of the present invention, chemical elements are in accordance with CAS version of the periodic Table of the elements, and handbook of chemistry and physics, 75 th edition, 1994. In addition, the general principles of organic chemistry may be found in the descriptions of "Organic Chemistry", thomas Sorrell, university Science Books, sausalato 1999, and "March's Advanced Organic Chemistry"by Michael B.Smith and Jerry March,John Wiley&Sons,New York:2007, the entire contents of which are incorporated herein by reference.
The articles "a," "an," and "the" are intended to include "at least one" or "one or more" unless the context clearly dictates otherwise or otherwise. Thus, as used herein, the articles refer to articles of manufacture that include one or more than one (i.e., at least one) object. For example, "a component" refers to one or more components, i.e., more than one component is contemplated as being employed or used in embodiments of the described embodiments.
The term "comprising" is an open-ended expression, i.e., including what is indicated by the invention, but not excluding other aspects.
"Stereoisomers" refer to compounds having the same chemical structure but different arrangements of atoms or groups in space. Stereoisomers include enantiomers, diastereomers, conformational isomers (rotamers), geometric isomers (cis/trans), atropisomers, and the like.
"Enantiomer" refers to two isomers of a compound that do not overlap but are in mirror image relationship to each other.
"Diastereoisomers" refers to stereoisomers which have two or more chiralities and whose molecules are not mirror images of each other. Diastereomers have different physical properties, such as melting point, boiling point, spectral properties, and reactivity. The diastereomeric mixture may be separated by high resolution analytical procedures such as electrophoresis and chromatography, e.g., HPLC.
The stereochemical definitions and rules used in the present invention generally follow the description in S.P.Parker,Ed.,McGraw-Hill Dictionary of Chemical Terms(1984)McGraw-Hill Book Company,New York;and Eliel,E.and Wilen,S.,"Stereochemistry of Organic Compounds",John Wiley&Sons,Inc.,New York,1994.
Many organic compounds exist in optically active form, i.e., they have the ability to rotate the plane of plane polarized light. In describing optically active compounds, the prefixes D and L or R and S are used to represent the absolute configuration of the molecule with respect to one or more of its chiral centers. The prefixes d and l or (+) and (-) are symbols for specifying the rotation of plane polarized light by a compound, where (-) or l indicates that the compound is left-handed. The compound prefixed with (+) or d is dextrorotatory. One particular stereoisomer is an enantiomer, and a mixture of such isomers is referred to as an enantiomeric mixture. A50:50 mixture of enantiomers is referred to as a racemic mixture or racemate, which can occur when there is no stereoselectivity or stereospecificity in a chemical reaction or process.
Any asymmetric atom (e.g., carbon, etc.) of the disclosed compounds may exist in racemic or enantiomerically enriched form, such as in the (R) -, (S) -or (R, S) -configuration. In certain embodiments, each asymmetric atom has at least 50% enantiomeric excess, at least 60% enantiomeric excess, at least 70% enantiomeric excess, at least 80% enantiomeric excess, at least 90% enantiomeric excess, at least 95% enantiomeric excess, or at least 99% enantiomeric excess in the (R) -or (S) -configuration.
Depending on the choice of starting materials and methods, the compounds of the invention may be present in the form of one of the possible isomers or mixtures thereof, for example racemates and non-corresponding isomer mixtures, depending on the number of asymmetric carbon atoms. Optically active (R) -or (S) -isomers can be prepared using chiral synthons or chiral reagents, or resolved using conventional techniques. If the compound contains a double bond, the substituent may be in the E or Z configuration; if the compound contains a disubstituted cycloalkyl group, the substituents of the cycloalkyl group may have cis or trans configuration.
The resulting mixture of any stereoisomers may be separated into pure or substantially pure geometric isomers, enantiomers, diastereomers, e.g., by chromatography and/or fractional crystallization, depending on the differences in the physicochemical properties of the components.
Any of the resulting racemates of the end products or intermediates can be resolved into the optical enantiomers by methods familiar to those skilled in the art, e.g., by separation of the diastereoisomeric salts thereof obtained, using known methods. The racemic product can also be separated by chiral chromatography, e.g., high Performance Liquid Chromatography (HPLC) using chiral adsorbents. In particular, enantiomers may be prepared by asymmetric synthesis.
The compounds of the invention may be optionally substituted with one or more substituents, as described in the present invention, such as the compounds of the general formula above, or as specific examples within the examples, subclasses, and classes of compounds encompassed by the invention. It is to be understood that the term "optionally substituted" may be used interchangeably with the term "substituted or unsubstituted". In general, the term "substituted" means that one or more hydrogen atoms in a given structure are replaced with a specific substituent. An optional substituent group may be substituted at each substitutable position of the group unless otherwise indicated. When more than one position in a given formula can be substituted with one or more substituents selected from a particular group, then the substituents may be the same or different at each position. Specifically, examples of "one or more" refer to 1,2,3,4, 5, 6, 7, 8, 9, or 10. Wherein the substituents may be, but are not limited to, deuterium, fluorine, chlorine, bromine, iodine, cyano, hydroxyl, nitro, amino, carboxyl, alkyl, alkoxy, alkoxyalkyl, alkoxyalkoxy, alkoxyalkylamino, aryloxy, heteroaryloxy, heterocyclyloxy, arylalkoxy, heteroarylalkoxy, heterocyclylalkoxy, cycloalkylalkoxy, alkylamino alkyl, alkylamino, cycloalkylamino, cycloalkylalkylamino, alkylthio, haloalkyl, haloalkoxy, hydroxyl-substituted alkyl, hydroxyl-substituted alkylamino, cyano-substituted alkyl, cyano-substituted alkoxy, cyano-substituted alkylamino, amino-substituted alkyl, alkanoyl, heteroalkyl, cycloalkyl, cycloalkenyl, cycloalkylalkyl, heterocyclyl, heterocyclylalkyl, heterocyclylacyl, aryl, arylalkyl, arylamino, heteroaryl, heteroarylalkyl, heteroarylamino, amido, sulfonyl, aminosulfonyl, and the like.
In addition, unless explicitly indicated otherwise, the description used in this disclosure of the manner in which "each … is independently" and "… is independently" and "… is independently" are to be understood in a broad sense as meaning that the particular choices expressed between the same symbols in different groups do not affect each other, or that the particular choices expressed between the same symbols in the same groups do not affect each other.
In the various parts of the present specification, substituents of the presently disclosed compounds are disclosed in terms of the type or scope of groups. It is specifically noted that the present invention includes each individual subcombination of the individual members of these group classes and ranges. For example, the term "C 1-C6 alkyl" or "C 1-6 alkyl" refers specifically to independently disclosed methyl, ethyl, C 3 alkyl, C 4 alkyl, C 5 alkyl, and C 6 alkyl.
The term "alkyl" or "alkyl group" as used herein, means a saturated straight or branched monovalent hydrocarbon group containing 1 to 20 carbon atoms; wherein the alkyl group is optionally substituted with one or more substituents described herein. Unless otherwise specified, alkyl groups contain 1 to 20 carbon atoms. In one embodiment, the alkyl group contains 1 to 12 carbon atoms; in one embodiment, the alkyl group contains 1 to 8 carbon atoms; in another embodiment, the alkyl group contains 1 to 6 carbon atoms; in yet another embodiment, the alkyl group contains 1 to 4 carbon atoms; in yet another embodiment, the alkyl group contains 1 to 3 carbon atoms.
Examples of alkyl groups include, but are not limited to, methyl (Me, -CH 3), ethyl (Et, -CH 2CH3), n-propyl (n-Pr, -CH 2CH2CH3), isopropyl (i-Pr, -CH (CH 3)2), n-butyl (n-Bu, -CH 2CH2CH2CH3), isobutyl (i-Bu, -CH 2CH(CH3)2), sec-butyl (s-Bu, -CH (CH 3)CH2CH3), tert-butyl (t-Bu, -C (CH 3)3), n-pentyl (-CH 2CH2CH2CH2CH3), 2-pentyl (-CH (CH 3)CH2CH2CH3), 3-pentyl (-CH (CH 2CH3)2), 2-methyl-2-butyl (-C (CH 3)2CH2CH3), 3-methyl-2-butyl (-CH (CH 3)CH(CH3)2), 3-methyl-1-butyl (-CH 2CH2CH(CH3)2), 2-methyl-1-butyl (-CH 2CH(CH3)CH2CH3), and the like.
The term "alkoxy" means that the alkyl group is attached to the remainder of the molecule through an oxygen atom, wherein the alkyl group has the meaning as described herein. Examples of alkoxy groups include, but are not limited to, methoxy (MeO, -OCH 3), ethoxy (EtO, -OCH 2CH3), 1-propoxy (n-PrO, n-propoxy, -OCH 2CH2CH3), 2-propoxy (i-PrO, i-propoxy, -OCH (CH 3)2), and the like.
The term "alkenyl" denotes a straight or branched chain monovalent hydrocarbon radical containing 2 to 12 carbon atoms, wherein there is at least one site of unsaturation, i.e. one carbon-carbon sp 2 double bond, wherein the alkenyl group may be optionally substituted with one or more substituents as described herein, including the positioning of "cis" and "tans", or the positioning of "E" and "Z". In one embodiment, the alkenyl group contains 2 to 8 carbon atoms; in another embodiment, the alkenyl group comprises 2 to 6 carbon atoms; in yet another embodiment, the alkenyl group contains 2 to 4 carbon atoms. Examples of alkenyl groups include, but are not limited to, vinyl (-ch=ch 2), allyl (-CH 2CH＝CH2), propenyl (CH 3 -ch=ch-), oxo-butenyl (CH 3 -C (=o) -ch=ch-), and the like.
The term "alkynyl" denotes a straight or branched chain monovalent hydrocarbon radical containing 2 to 12 carbon atoms, wherein there is at least one carbon-carbon sp triple bond, wherein the alkynyl group may be optionally substituted with one or more substituents described herein. In one embodiment, the alkynyl group contains 2 to 10 carbon atoms; in one embodiment, the alkynyl group contains 2 to 8 carbon atoms; in another embodiment, the alkynyl group contains 2 to 6 carbon atoms; in yet another embodiment, the alkynyl group contains 2 to 4 carbon atoms. Examples of alkynyl groups include, but are not limited to ,-C≡CH、-C≡CCH3、-CH2-C≡CH、-CH2-C≡CCH3、-CH2CH2-C≡CH、-CH2-C≡CCH2CH3、-CH2CH2-C≡CH2CH3 and the like.
The term "alkenyloxy" means that the alkenyl group is attached to the remainder of the molecule through an oxygen atom, wherein the alkenyl group has the meaning as described herein.
The term "alkynyloxy" means an alkynyl group attached to the remainder of the molecule through an oxygen atom, wherein the alkynyl group has the meaning as described herein.
The term "cycloalkyl" denotes a monovalent or polyvalent saturated monocyclic, bicyclic or tricyclic ring system containing 3 to 12 carbon atoms. In one embodiment, cycloalkyl groups contain 3 to 10 carbon atoms; in another embodiment, cycloalkyl groups contain 3 to 8 carbon atoms; in yet another embodiment, cycloalkyl groups contain 3 to 6 carbon atoms. The cycloalkyl group is optionally substituted with one or more substituents described herein. Examples include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl, cyclododecyl, and the like.
The term "cycloalkyl-alkyl" means that the alkyl group is substituted with one or more cycloalkyl groups, wherein alkyl and cycloalkyl groups have the meaning as described herein.
The term "cycloalkyloxy" means that the cycloalkyl group is attached to the remainder of the molecule through an oxygen atom, wherein the cycloalkyl group has the meaning as described herein.
The term "phenyl-alkyl" means that an alkyl group is substituted with one or more phenyl groups, wherein the alkyl group has the meaning as described herein.
The term "halogen" refers to fluorine (F), chlorine (Cl), bromine (Br) or iodine (I).
The term "mercapto" refers to-SH.
The term "carboxy" refers to-COOH.
The term "haloalkyl" means an alkyl group substituted with one or more halogen atoms, examples of which include, but are not limited to ,-CF3,-CHF2,-CH2Cl,-CH2CF3,-CH2CHF2,-CH2CH2CF3 and the like.
The term "haloalkoxy" means that the alkoxy group is substituted with one or more halogen atoms, examples of which include, but are not limited to ,-OCF3,-OCHF2,-OCHCl2,-OCH2CHF2,-OCH2CHCl2,-OCH(CH3)CHF2 and the like.
The term "haloalkenyl" means that the alkenyl group is substituted with one or more halogen atoms.
The term "haloalkynyl" means that the alkynyl group is substituted with one or more halogen atoms.
The term "halocycloalkyl" means that the cycloalkyl group is substituted with one or more halogen atoms.
Salts of the compounds of the present invention include those derived from alkali metals or alkaline earth metals, as well as those derived from ammonia and amines. Preferred cations include sodium, potassium, magnesium and ammonium cations of formula N +(RAARBBRCCRDD) wherein R AA、RBB、RCC and R DD are independently selected from the group consisting of hydrogen, C 1-C6 alkyl and C 1-C6 hydroxyalkyl. Salts of compounds of formula (I), formula (I-a), formula (II), formula (III), formula (IV) or formula (V) may be prepared by treating a compound of formula (I), formula (I-a), formula (II), formula (III), formula (IV) or formula (V) with a metal hydroxide (e.g. sodium hydroxide) or an amine (e.g. ammonia, trimethylamine, diethanolamine, 2-methylthiopropylamine, bis-allylamine, 2-butoxyethylamine, morpholine, cyclododecamine or benzylamine).
When the compounds of the present invention contain a base moiety, acceptable salts may be formed with organic and inorganic acids, such as acetic, propionic, lactic, citric, tartaric, succinic, fumaric, maleic, malonic, mandelic, malic, phthalic, hydrochloric, hydrobromic, phosphoric, nitric, sulfuric, methanesulfonic, naphthalenesulfonic, benzenesulfonic, toluenesulfonic, camphorsulfonic, and similarly known acceptable acids.
Compositions and formulations of the compounds of the invention
The compounds of the present invention are generally useful as fungicide active ingredients in compositions, i.e., formulations, which have at least one additional component, typically further comprising an agropharmaceutically acceptable surfactant and a carrier. The formulation or composition ingredients are selected to be compatible with the physical characteristics of the active ingredient, the mode of application, and environmental factors such as soil type, humidity and temperature.
The surfactant may be any of various surfactants known in the art of agricultural chemical formulation, and the present invention is preferably one or more of an emulsifier, a dispersant and a wetting agent.
Other carriers besides the above surfactants may be various carriers well known in the art of agricultural chemical formulation, including various silicates, carbonates, sulfates, oxides, phosphates, plant carriers, synthetic carriers. Specifically, for example: white carbon black, kaolin, diatomaceous earth, clay, talc, organic bentonite, pumice, titanium dioxide, dextrin, cellulose powder, light calcium carbonate, soluble starch, corn starch, sawdust powder, urea, an amine fertilizer, a mixture of urea and an amine fertilizer, glucose, maltose, sucrose, anhydrous potassium carbonate, anhydrous sodium carbonate, anhydrous potassium bicarbonate, anhydrous sodium bicarbonate, attapulgite, a mixture of anhydrous potassium carbonate and anhydrous potassium bicarbonate, and a mixture of anhydrous sodium carbonate and anhydrous sodium bicarbonate.
The emulsifier may be various emulsifiers known in the field of pesticide formulation, and specifically, the emulsifier may be one or more of calcium dodecyl benzene sulfonate, triphenyl ethyl phenol polyoxyethylene ether phosphate, fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene polyoxypropylene ether, fatty amine, ethylene oxide adduct of fatty amide, fatty acid polyoxyethylene ester, rosin acid ethylene oxide adduct, polyol fatty acid ester and ethylene oxide adduct thereof, styrylphenyl polyoxyethylene ether, alkylphenol formaldehyde resin polyoxyethylene ether, hydroxyl-terminated polyoxyethylene polyoxypropylene ether, styrylphenol formaldehyde resin polyoxyethylene polyoxypropylene ether and castor oil polyoxyethylene ether.
The dispersing agent can be various dispersing agents known in the pesticide formulation field, and specifically, the dispersing agent is one or more of acrylic acid homopolymer sodium salt, maleic acid disodium salt, naphthalene sulfonic acid formaldehyde condensate sodium salt, rosin block polyoxyethylene ether polyoxypropylene ether sulfonate, hydroxyl-terminated polyoxyethylene polyoxypropylene ether block copolymer, triphenyl ethyl phenol polyoxyethylene ether phosphate, fatty alcohol polyoxyethylene ether phosphate and p-hydroxyphenyl lignin sulfonic acid sodium salt.
The wetting agent can be various wetting agents known in the pesticide formulation field, and concretely, the wetting agent can be one or more of sodium dodecyl sulfate, secondary sodium alkyl sulfate, sodium dodecyl benzene sulfonate, fatty alcohol polyoxyethylene ether, alkyl naphthalene sulfonate and alkylphenol polyoxyethylene ether sulfate.
The bactericide composition according to the present invention may further contain various adjuvants for formulation commonly used in the field of agricultural chemical formulation, and specifically, the adjuvants for formulation may be one or more of solvents, co-solvents, thickeners, antifreezes, encapsulating materials, protective agents, antifoaming agents, disintegrants, stabilizers, preservatives and binders.
The above solvent may be various solvents well known in the field of agricultural chemical formulation, and specifically, the solvent may be one or more of organic solvents, vegetable oils, mineral oils, solvent oils and water.
Wherein the organic solvent comprises one or more of N-methylpyrrolidone, tetrahydrofuran, dimethyl sulfoxide, N-dimethyl capramide, N-dimethylformamide, trimethylbenzene, tetramethylbenzene, xylene, toluene, octane, heptane, methanol, isopropanol, N-butanol, tetrahydrofurfuryl alcohol, tributyl phosphate, 1, 4-dioxane and cyclohexanone.
The vegetable oil comprises one or more of methylated vegetable oil, turpentine-based vegetable oil, turpentine, epoxidized soybean oil, peanut oil, rapeseed oil, castor oil, corn oil and pine seed oil.
The mineral oil includes one or more of liquid wax, engine oil, kerosene, and lubricating oil.
Meanwhile, the solvent can also be used as a cosolvent.
The above antifreezing agent may be various antifreezing agents known in the field of agricultural chemical formulation, and the present invention is preferably one or more of ethylene glycol, propylene glycol, glycerin and urea.
The thickener may be various thickeners known in the field of pesticide dosage forms, and specifically, the thickener may be one or more of xanthan gum, polyvinyl alcohol, polyacrylate alcohol, polyethylene glycol, white carbon black, diatomaceous earth, kaolin, clay, sodium alginate, aluminum magnesium silicate, aluminum sodium silicate, carboxymethyl cellulose, hydroxypropyl cellulose sodium, and organic bentonite.
The capsule wall material can be various capsule wall materials known in the pesticide formulation field, and the invention is preferably one or more of polyurethane, polyurea and urea-formaldehyde resin.
The protective agent may be any of various protective agents known in the field of agricultural chemical formulations, and the present invention is preferably polyvinyl alcohol and/or polyethylene glycol.
The above defoamer may be various defoamers known in the field of pesticide formulation, and the present invention is preferably one or more of organosiloxane, tributyl phosphate and silicone.
The stabilizer is one or more selected from triphenyl phosphite, epichlorohydrin and acetic anhydride.
The preservative is selected from one or more of benzoic acid, sodium benzoate, 1, 2-benzisothiazolin-3-one (BIT for short), pinocembrane and potassium sorbate.
The invention also provides a preparation prepared from the bactericide composition, wherein the preparation formulation of the preparation is emulsifiable concentrate, aqueous emulsion, microemulsion, soluble liquid, aqueous suspension, suspension emulsion, ultra-low volume spray, oil suspension, microcapsule suspension, water surface spreading oil, wettable powder, water dispersible granules, dry suspension, soluble powder, soluble granules, emulsifiable powder, emulsifiable granules, solid microcapsule preparation, effervescent tablets, effervescent granules, water floating dispersible granules or seed coating. The above dosage forms can be prepared by methods conventional in the art.
The preparation method of the emulsifiable concentrate preparation can comprise, for example, mixing and stirring the active components, the solvent, the cosolvent and the emulsifier to form a uniform transparent oil phase, thus obtaining the emulsifiable concentrate preparation.
The above aqueous emulsion preparation method may include, for example, mixing the active ingredient, the emulsifier, the cosolvent and the solvent to form a homogeneous oil phase; water, thickener, antifreeze, etc. are mixed to make it into a uniform aqueous phase. Under high-speed shearing, adding the water phase into the oil phase or adding the oil phase into the water phase to form the aqueous emulsion with good dispersibility.
The microemulsion may be prepared by mixing and stirring the active ingredient, the emulsifier and the solvent into a uniform transparent oil phase. Under stirring, water was gradually added to form a uniform transparent microemulsion.
The preparation method of the water/oil suspending agent comprises the following steps: for example, water or oil is used as a medium, and additives such as active components, surfactants and the like are added into a sanding kettle, ground to a certain particle size, and filtered. And adding the metered thickener into the ground mother solution, and shearing and dispersing uniformly. Making into oil suspension or water suspension.
The preparation method of the water-dispersible granule and the soluble granule comprises the following steps: for example, the water-dispersible granule or soluble granule can be obtained by uniformly mixing the active components, the dispersing agent, the wetting agent, the carrier and the like, then crushing the mixture to a certain particle size by air flow, adding water for kneading, finally adding the mixture into a granulator for granulating, and drying the mixture.
The preparation method of the soluble powder and the wettable powder comprises the following steps: for example, the active ingredients, various auxiliary agents, and other fillers such as carriers may be thoroughly mixed and pulverized by a pulverizer.
The fungicide composition of the present invention may be provided in the form of a finished formulation, i.e. the materials of the composition have been mixed; or in the form of separate preparations which are self-mixed in a tank or can before use and optionally diluted with water depending on the desired concentration of active substance.
For additional information regarding the formulation art, see T.S. woods "The Formulator's Toolbox-Product Forms for Modern Agriculture",Pesticide Chemistry and Bioscience,The Food-Environment Challenge,T.Brooks and T.R. Roberts edit ,Proceedings of the 9th International Congress on Pesticide Chemistry,The Royal Society of Chemistry,Cambridge,1999, pages 120-133. See also U.S.3,235,361, column 6, line 16 to column 7, line 19 and examples 10-41; U.S.3,309,192, column 5, line 43 to column 7, line 62 and examples 8, 12, 15, 39, 41, 52, 53, 58, 132, 138-140, 162-164, 166, 167 and 169-182; U.S.2,891,855, column 3, line 66 to column 5, line 17 and examples 1-4; klingman's Weed Control AS A SCIENCE, john Wiley and Sons, inc., new York,1961, pages 81-96; weed Control Handbook, 8 th edition, blackwell Scientific Publications, oxford,1989; and Developments in formulation technology, PJB Publications, richmond, UK,2000.
Use of the compounds and compositions of the invention
The compounds of the present invention are useful as plant disease controlling agents. Thus, the present invention may also include a method for controlling plant diseases caused by phytopathogenic fungi, said method comprising applying to the plant to be protected or to a part thereof or to the seed of the plant to be protected an effective amount of a compound of the invention or a fungicidal composition comprising said compound. The compounds and/or compositions of the present invention provide control of diseases caused by broad-spectrum plant pathogenic fungi of basidiomycetes, ascomycetes, oomycetes and deuteromycetes. They are effective in controlling a broad spectrum of plant diseases, especially foliar pathogens in ornamental, lawn, vegetable, field, cereal and fruit crops. These pathogens include: oomycetes, including Phytophthora (Phytophthora) diseases such as Phytophthora infestans (Phytophthora infestans), phytophthora sojae (Phytophthora megasperma), citrus foot rot (Phytophthora parasitica), phytophthora camphorata (Phytophthora cinnamomi) and Phytophthora cucurbitae (Phytophthora capsici), pythium (Pythium) species diseases such as Pythium triclopyr (Pythium aphanidermatum), and downy (Peronosporaceae) species diseases such as downy mildew (Plasmopara viticola), downy (Peronospora spp.) (including downy mildew (Peronospora tabacina) and downy mildew (Peronospora parasitica)), pseudoperonospora spp.) (including downy mildew (Pseudoperonospora cubensis) and basidiomycetes (Bremia lactuca)); ascomycetes (including Alternaria (Alternaria) pathogens such as Alternaria solani (ALTERNARIA SOLANI) and Brassica oleracea (ALTERNARIA BRASSICAE), brevibacterium (Guignardia) pathogens such as Botrytis cinerea (Guignardia bidwell), cercospora (Venturia) pathogens such as Malus pumila (Venturia inaequalis), septoria (Septoria) pathogens such as Lesion glume (Septoria nodorum) and leaf blight (Septoria tritctii), leucopia (powdery mildew) pathogens such as Leuconostoc (Erysiphe spp.) (including Erysiphe graminea. And Sclerotinia glabra (ERYSIPHE GRAMINIS) and Sclerotinia glabra (Erysiphe polygoni)), vitis vinifera (Uncinula necatur), leuconostoc (Sphaerotheca fuligena) and Malus malis (Podosphaera leucotricha), wheat based pathogens (Pseudocercosporella herpotrichoides), botrytis (Botrytis) pathogens such as Botrytis cinerea (Botrytis), sclerotinia (Monilinia fructicola), sclerotinia (Sclerotinia sclerotiorum) and Sclerotinia (Sclerotinia sclerotiorum) pathogens such as Sclerotinia collecticola (69), sclerotinia (9763) and Sclerotinia collecticola (35) and Sclerotina (35) pathogens such as Rhizoctonia cerealis (35) and Sclerotina collectia (35) and Rhizoctonia cerealis (35) such as Leucor. Anthracis (35) and Rhizoctonia cerealis (35) and Leucor. Anthracis (35), including rust diseases caused by rust (Puccinia spp.) (e.g., puccinia recondita (Puccinia recondita), puccinia striolata (Puccinia striiformis), puccinia phyllanthus (Puccinia hordei), puccinia striolata (Puccinia graminis) and Puccinia striolata (Puccinia arachidis)), puccinia caffeensis (Hemileia vastatrix) and Puccinia sojae (Phakopsora pachyrhizi); other pathogens include Rhizoctonia species (Rhizoctonia spp.) (e.g., rhizoctonia solani (Rhizoctonia solani)); fusarium (Fusarium) species diseases such as Fusarium roseum, fusarium graminearum (Fusarium graminearum) and Fusarium oxysporum (Fusarium oxysporum); verticillium dahliae (Verticillium dahliae); southern blight (Sclerotium rolfsii); the fungus (Rynchosporium secalis); black spot bacteria (Cercosporidium personatum), black spot bacteria (Cercospora arachidicola) and brown spot bacteria (Cercospora beticola); and other classes and species closely related to these pathogens. In addition to their fungicidal activity, the compositions or combinations also have resistant activity against bacteria such as Pyricularia pyrifolia (Erwinia amylovora), xanthomonas campestris (Xanthomonas campestris), pseudomonas syringae (Pseudomonas syringae), and other species.
The bactericide composition provided by the invention is simple in use method, is applied to crops and the sites where the crops grow before or after germination of plant diseases according to a conventional method, such as soil mixing, spraying, pouring and the like, and the application amount of the bactericide composition is generally 10-5000g per mu according to climatic conditions or crop states, and is diluted to 10-400mg/L (preferably 100-300 mg/L). The diluent is preferably water.
The bactericidal composition of the present invention has a bactericidal effect generally related to external factors such as climate, but the influence of climate can be alleviated by using a proper dosage form.
The composition of the present invention may be used in combination with other compounds having bactericidal, insecticidal or herbicidal properties, or may be used in combination with nematicides, acaricides, protectants, herbicide safeners, growth regulators, plant nutrients or soil conditioners, etc.
General synthetic procedure
The following schemes describe the preparation of the compounds of the present invention. Unless otherwise indicated, the compounds of the present invention may be prepared by the methods described herein. The starting materials, reagents, and the like used in preparing the compounds of the invention are all commercially available or may be prepared by methods conventional in the art. In this specification, a structure is dominant if there is any difference between a chemical name and a chemical structure. In the present invention, the room temperature is 0 to 40℃unless otherwise specified.
The testing conditions of the nuclear magnetic resonance hydrogen spectrum of the invention are as follows: at room temperature, a Bruker (Bruker) 400MHz or 600MHz nuclear magnetic resonance apparatus was used with CDC1 3,d6-DMSO,CD3 OD or d 6 -acetone as solvent (reported in ppm) and TMS (0 ppm) or chloroform (7.26 ppm) as reference standard. When multiple peaks occur, the following abbreviations will be used: s (singlet ), d (doublet, doublet), t (triplet ), q (quartet, quartet), m (multiplet ), br (broadened, broad), dd (doublet of doublets, doublet), dt (doublet of triplets, doublet). Coupling constants are expressed in hertz (Hz).
The mass spectrum test conditions used in the invention are as follows: the conditions for low resolution Mass Spectrometry (MS) data determination are: agilent 6120 Quadrupole HPLC-MS (column model: zorbax SB-C18, 2.1X30 mm,3.5 μm,6min, flow rate 0.6mL/min, mobile phase: 5% -95% (ratio of CH 3 CN with 0.1% formic acid in H 2 O with 0.1%) was UV detected at 210/254nm, electrospray ionization mode (ESI).
Synthetic scheme
The following synthetic schemes describe the steps for preparing the disclosed compounds. Wherein R a、Rb、Rc、Rd and R e have the meaning described in the present invention.
Synthesis scheme one
The target compounds III-2 and III-4 can be prepared by a first synthesis scheme. The format reagent obtained after the compound a reacts with isopropyl magnesium chloride reacts with isobutyryl chloride to obtain a compound b; reacting the compound b with a compound c-1 or a compound c-2 in an alkaline system to obtain a compound d-1 or a compound d-2; reacting the compound d-1 or the compound d-2 with liquid bromine to obtain a compound e-1 or a compound e-2; and (3) reacting the compound e-1 or the compound e-2 with a 1,2, 4-triazole alkaline system to obtain a target compound III-2 or a target compound III-4.
Synthesis scheme II
The target compound II-1 and the target compound IV-2 can be prepared by a synthesis scheme II. The target compound III-2 is reduced by a reducing agent to obtain a target compound II-1; dehydrating the target compound II-1 to obtain a target compound IV-2.
Synthesis of a third embodiment
The target compounds II-3 and IV-4 can be prepared by the synthesis scheme III. The target compound III-4 is reduced by a reducing agent to obtain a target compound II-3; dehydrating the target compound II-3 to obtain a target compound IV-4.
Synthesis scheme IV
The target compound V-1 can be prepared by a synthesis scheme IV. Dehydrating the target compound III-2 at a high temperature (100-150 ℃) to obtain a compound f; the compound f is reduced by a reducing agent to obtain the target compound V-1.
Synthesis scheme five
The target compound V-2 can be prepared by a synthesis scheme five. Dehydrating the target compound III-4 at a high temperature (100-150 ℃) to obtain a compound g; the target compound V-2 is obtained after the compound g is reduced by a reducing agent.
Detailed Description
The following examples are illustrative of the invention but are not intended to limit the scope of the invention.
EXAMPLE 1 Synthesis of 1- (4- (4-chlorophenoxy) -2- (trifluoromethyl) phenyl) -2-hydroxy-2-methyl-3- (1H-1, 2, 4-triazol-1-yl) propan-1-one
Step 1: synthesis of 1- (4-fluoro-2- (trifluoromethyl) phenyl) -2-methylpropan-1-one
2-Bromo-5-fluorotrifluoromethylbenzene (50.0 g,206 mmol) was dissolved in methyl tert-butyl ether (100 mL), and a 2.0M solution of isopropyl magnesium chloride (260 mmol,130 mL) in tetrahydrofuran was added dropwise under nitrogen protection at room temperature for 30 minutes, followed by reaction at room temperature for 1 hour to give 4-fluoro-2-trifluoromethylphenyl magnesium chloride. The reaction mixture was added dropwise to methyl t-butyl ether (50 mL) of isobutyryl chloride (30.9 g,290 mmol) under nitrogen at room temperature, and after the completion of the addition, the mixture was reacted at room temperature for 3 hours. After quenching the reaction with water (200 mL), the organic phase was separated, washed with water (50 mL. Times.2) and concentrated under reduced pressure to give 47.0g of a yellow liquid with a yield of 97.6%.
1H NMR(400MHz,CDCl3)δ(ppm):7.74(dt,J＝7.8,1.2Hz,1H),7.45(td,J＝7.9,5.6Hz,1H),7.27(tdd,J＝8.2,2.6,0.9Hz,1H),3.50(sept,J＝6.8Hz,1H),1.22(d,J＝6.8Hz,6H);
LC-MS:(M+1)m/z＝235.0。
Step 2: synthesis of 1- (4- (4-chlorophenoxy) -2- (trifluoromethyl) phenyl) -2-methylpropan-1-one
1- (4-Fluoro-2- (trifluoromethyl) phenyl) -2-methylpropan-1-one (4.00 g,17.09 mmol) and parachlorophenol (2.56 g,20.00 mmol) were dissolved in N, N-dimethylformamide (30 mL), potassium carbonate (3.40 g,25.00 mmol) was added, and the reaction stirred at 110℃for 5 hours. The reaction solution was poured into water (100 mL), extracted with ethyl acetate (100 ml×2), and the organic phase was concentrated under reduced pressure, and the residue was subjected to column chromatography [ petroleum ether/ethyl acetate (v/v) =9/1 ], to give 4.33g of a yellow solid with a yield of 74.1%.
1H NMR(400MHz,CDCl3)δ(ppm):7.51(d,J＝8.6Hz,1H),7.42-7.38(m,2H),7.33(t,J＝3.2Hz,1H),7.08(dd,J＝8.6,2.3Hz,1H),7.03(m,2H),3.20(sept,J＝6.8Hz,1H),1.22(d,J＝6.8Hz,6H);
LC-MS:(M+1)m/z＝343.0。
Step 3: synthesis of 2-bromo-1- (4- (4-chlorophenoxy) -2- (trifluoromethyl) phenyl) -2-methylpropan-1-one
1- (4- (4-Chlorophenoxy) -2- (trifluoromethyl) phenyl) -2-methylpropan-1-one (3.00 g,8.77 mmol) was dissolved in methyl tert-butyl ether (30 mL) at room temperature, bromine (1.59 g,10.00 mmol) was added dropwise, and the mixture was stirred at room temperature after the completion of the dropwise addition for 8 hours. The reaction solution was washed with sodium sulfite solution (40 ml×2), and the organic phase was concentrated under reduced pressure, and the residue was subjected to column chromatography [ petroleum ether/ethyl acetate (v/v) =9/1 ], to give 3.57g of a white solid, yield 95.5%.
1H NMR(400MHz,CDCl3)δ(ppm):7.51(d,J＝8.6Hz,1H),7.42-7.38(m,2H),7.33(t,J＝3.2Hz,1H),7.08(dd,J＝8.6,2.3Hz,1H),7.03(m,2H),2.22(s,6H);
LC-MS:(M+1)m/z＝423.0。
Step 4: synthesis of 1- (4- (4-chlorophenoxy) -2- (trifluoromethyl) phenyl) -2-hydroxy-2-methyl-3- (1H-1, 2, 4-triazol-1-yl) propan-1-one
1,2, 4-Triazole (1.38 g,20.00 mmol), sodium hydroxide (0.60 g,15.00 mmol) were dissolved in dimethyl sulfoxide (30 mL), and after stirring at 90℃for 1 hour, a solution of 2-bromo-1- (4- (4-chlorophenoxy) -2- (trifluoromethyl) phenyl) -2-methylpropan-1-one (4.21 g,10.00 mmol) in dimethyl sulfoxide (10 mL) was added dropwise thereto, and the mixture was heated to 130℃and stirred for 8 hours. The reaction solution was poured into water (100 mL), extracted with ethyl acetate (100 ml×2), and the organic phases were combined, concentrated under reduced pressure, and the residue was subjected to column chromatography [ petroleum ether/ethyl acetate (v/v) =3/2 ], to give 1.21g of a colorless oily liquid in 28.3% yield.
1H NMR(400MHz,CDCl3)δ(ppm):8.19(s,1H),7.97(s,1H),7.51(d,J＝8.6Hz,1H),7.44-7.37(m,2H),7.30(t,J＝3.2Hz,1H),7.08(dd,J＝8.6,2.3Hz,1H),7.03(dd,J＝9.5,2.6Hz,2H),4.91-4.78(m,2H),4.36(d,J＝13.9Hz,1H),1.54(s,3H);
LC-MS:(M+1)m/z＝426.1。
The preparation of example 1 was followed using the corresponding compound as starting material to give the target compounds in Table 13.
TABLE 13
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Example 23: synthesis of 1- (4- (2-chlorophenoxy) -2- (trifluoromethyl) phenyl) -2-methyl-3- (1H-1, 2, 4-triazol-1-yl) propane-1, 2-diol
1- (4- (2-Chlorophenoxy) -2- (trifluoromethyl) phenyl) -2-hydroxy-2-methyl-3- (1H-1, 2, 4-triazol-1-yl) propan-1-one (1.21 g,2.83 mmol) was dissolved in ethanol (20 mL), sodium borohydride (0.11 g,2.91 mmol) was added and the reaction was stirred at room temperature for 4 hours. The reaction was quenched by addition of saturated ammonium chloride solution (20 mL), extracted with ethyl acetate (40 mL x 2), the organic phases were combined, concentrated under reduced pressure, and the residue was purified by column chromatography [ petroleum ether/ethyl acetate (v/v) =2/3 ], affording 1.15g of a white solid with a yield of 94.2%.
LC-MS:(M+1)m/z＝428.1。
The compounds of table 13 were reduced with a reducing agent (e.g., sodium borohydride) to give the target compounds of table 14.
TABLE 14
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Example 32: synthesis of 1- ((3- (4- (2-chlorophenoxy) -2- (trifluoromethyl) phenyl) -2-methyl oxiran-2-yl) methyl) -1H-1,2, 4-triazole
1- (4- (2-Chlorophenoxy) -2- (trifluoromethyl) phenyl) -2-methyl-3- (1H-1, 2, 4-triazol-1-yl) propane-1, 2-diol (1.15 g,2.67 mmol) was dissolved in tetrahydrofuran (20 mL), sodium hydride (0.13 g,5.43 mmol) was added at 0deg.C with stirring, stirring was continued at 0deg.C for 10 minutes after the addition, and p-toluenesulfonyl chloride (0.57 g,3.00 mmol) was added, and stirring was continued at 0deg.C after the addition for 3 hours. The reaction was quenched with water (20 mL), extracted with dichloromethane (40 mL x 2), the organic phases combined, concentrated under reduced pressure, and the residue was purified by column chromatography [ petroleum ether/ethyl acetate (v/v) =17/3 ] to give 0.81g of a white solid with a yield of 74.1%.
1H NMR(400MHz,CDCl3)δ(ppm):8.21(s,1H),7.98(s,1H),7.50(d,J＝7.9Hz,1H),7.41(d,J＝8.6Hz,1H),7.30(d,J＝6.9Hz,1H),7.26-7.24(m,1H),7.18(t,J＝7.3Hz,1H),7.10-6.99(m,2H),4.60(d,J＝14.8Hz,1H),4.33(d,J＝14.8Hz,1H),4.00(s,1H),1.00(s,3H);
19F NMR(376MHz,CDCl3)δ(ppm):-61.06；
LC-MS:(M+1)m/z＝410.1。
The compounds of table 14 were prepared by the preparation method of example 32, respectively, to give the objective compounds of table 15.
TABLE 15
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Example 39: (E) Synthesis of (E) -1- (4- (4-chlorophenoxy) -2- (trifluoromethyl) phenyl) -2-methyl-3- (1H-1, 2, 4-triazol-1-yl) prop-2-en-1-ol
Step 1: (E) Synthesis of (E) -1- (4- (4-chlorophenoxy) -2- (trifluoromethyl) phenyl) -2-methyl-3- (1H-1, 2, 4-triazol-1-yl) prop-2-en-1-one
1- (4- (4-Chlorophenoxy) -2- (trifluoromethyl) phenyl) -2-hydroxy-2-methyl-3- (1H-1, 2, 4-triazol-1-yl) propan-1-one (1.21 g,2.83 mmol) dimethyl sulfoxide (20 mL) was added sodium hydroxide (0.20 g,5.00 mmol), and the mixture was heated to 130℃and stirred for 4 hours. The reaction solution was poured into water (50 mL), extracted with ethyl acetate (50 mL x 2), the organic phases were combined, concentrated under reduced pressure, and the residue was subjected to column chromatography [ petroleum ether/ethyl acetate (v/v) =19/1 ], to give 0.51g of a white solid with a yield of 44.3%.
1H NMR(400MHz,CDCl3)δ(ppm):8.19(s,1H),8.00(s,1H),7.65(d,J＝8.6Hz,1H),7.51(d,J＝2.2Hz,1H),7.31-7.26(m,2H),7.11-7.06(m,1H),7.02(d,J＝8.7Hz,1H),5.68(s,1H),2.61(s,1H),1.78(s,3H);
19F NMR(376MHz,CDCl3)δ(ppm):-57.90；
LC-MS:(M+1)m/z＝408.0。
Step 2: (E) Synthesis of (E) -1- (4- (4-chlorophenoxy) -2- (trifluoromethyl) phenyl) -2-methyl-3- (1H-1, 2, 4-triazol-1-yl) prop-2-en-1-ol
Under nitrogen protection, (E) -1- (4- (4-chlorophenoxy) -2- (trifluoromethyl) phenyl) -2-methyl-3- (1H-1, 2, 4-triazol-1-yl) prop-2-en-1-one (0.41 g,1.0 mmol) was dissolved in anhydrous methanol (5 mL), sodium borohydride (0.19 g,5.0 mmol) was added with stirring, after the addition was completed, stirring was continued at 0 ℃, after the TLC monitoring the reaction was completed, saturated ammonium chloride solution was added dropwise to quench the reaction (10 mL), ethyl acetate was extracted (10 mL x 2), the organic phases were combined, washed with saturated brine (10 mL), dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the residue was purified by column chromatography [ petroleum ether/ethyl acetate (v/v) =4/1 ], to give 0.36g of white solid with a yield of 38%.
LC-MS:(M+1)m/z＝410.0。
The compounds of table 13 were prepared by a method similar to that of example 39 to give the target compounds of table 16.
Table 16
Test case
1) Wheat powdery mildew (wheat powdery mildew)
1 Leaf and 1 heart phase pot wheat seedlings with consistent growth vigor are selected, and a label number is written by an oily marker pen for test. Dissolving the crude drug solvent DMSO, and adding water containing 0.1% Tween-80 to dilute to 200mg/L. Spraying stems and leaves, and drying the test material in the shade at a ventilation position after treatment.
Inoculating for about 24 hours after treatment, and gently shaking out mature wheat powdery mildew spores and inoculating on wheat seedlings. Culturing wheat seedlings in a greenhouse at low humidity (15-26 ℃) after inoculation, and grading and investigating according to the disease condition of a blank control after 8 days, and calculating the control effect according to disease fingers.
The test results are shown in Table 17.
TABLE 17 control of wheat powdery mildew at 200mg/L of the inventive Compound
2) Corn rust (soybean rust (Puccinia sorghi schw.))
The potted corn seedlings with consistent growth vigor in the two leaf periods are selected, the oil marker is used for writing numbers on the cup body, and the numbers are discharged in sequence for test. Dissolving the crude drug solvent DMSO, and adding water containing 0.1% Tween-80 to dilute to 200mg/L. Spraying stems and leaves, and drying the test material in the shade at a ventilation position after treatment.
Inoculation was performed about 24 hours after treatment. Taking mature corn leaves of rust spores, adding the corn leaves into water containing a surfactant, washing spores with a writing brush, filtering the mixture by double-layer gauze to prepare spore suspension (2X 10 6～5×106/mL), and uniformly spraying and inoculating the spore suspension on corn seedlings by an inoculating sprayer (the pressure is 0.1 MPa). The inoculated potted corn is placed in a humidity preservation box (room) or an artificial climate room (the temperature is 25 ℃ and the relative humidity is 100%) for culture, and is placed in an incubator (room) or a greenhouse with the illumination intensity of more than 2000lx for high humidity culture after 24 hours, and the grading investigation is carried out about 7 days according to the disease condition of a blank control, and the control effect is calculated according to the disease index.
The test results are shown in Table 18.
TABLE 18 control of corn rust at 200mg/L of the compounds of the invention
Compounds of formula (I) Preventing effect (%)
Example 2 90
Example 4 100
Example 19 90
Example 21 100
Example 30 98
Example 32 100
Example 35 98
Example 37 90
Example 38 100
Example 40 100
Example 41 100
Example 42 100
Example 43 100
3) Botrytis cinerea (soybean gray mold)
And selecting potted soybean seedlings with consistent growth vigor in the two-leaf period, and writing a label number by using an oily marker pen for test. Dissolving the crude drug solvent DMSO, and adding water containing 0.1% Tween-80 to dilute to 200mg/L. Spraying stems and leaves, and drying the test material in the shade at a ventilation position after treatment.
Inoculation is generally carried out about 24 hours after treatment. The center of the soybean leaf epidermis is pricked lightly with a small needle, a prepared bacterial cake with the diameter of 5mm is attached to the surface wound of the leaf by a toothpick.
The inoculated test material is transferred to a light-dark alternate artificial climate chamber for culture (22 ℃ C., humidity > 90%)
And measuring the diameter of the disease spots by using a caliper, and calculating the control effect.
The test results are shown in Table 19.
TABLE 19 control of soybean gray mold with the inventive compound at 200mg/L
Compounds of formula (I) Preventing effect (%)
Example 6 98
Example 8 98
4) Cucumber anthracnose (cucumber anthracnose (Colletotrichum orbiculare))
And selecting potted cucumber seedlings with consistent growth vigor in two leaf periods, and writing a label number by using an oily marker pen for test. Dissolving the crude drug solvent DMSO, and then adding 0.1% Tween 80 water to dilute to 200mg/L. Spraying stems and leaves, and drying the test material in the shade at a ventilation position after treatment.
Inoculation is generally carried out about 24 hours after treatment. Adding sterile water into a culture dish full of spores, scraping surface spores, filtering with 2-4 layers of gauze to prepare a spore suspension with the concentration of 7X 10 4～8×104 CFU/mL, and uniformly spraying on rice seedlings by an inoculation sprayer (the pressure is 0.1 MPa). After inoculation, the mixture is transferred into a climatic chamber, the relative humidity is more than 85 percent, the temperature is 25-28 ℃, the light intensity is more than 2000lx, and after 5-7 days, the disease investigation is carried out, and the prevention effect is calculated according to the disease index.
The test results are shown in Table 20.
TABLE 20 control of cucumber anthracnose with the inventive Compound at 200mg/L
Compounds of formula (I) Preventing effect (%)
Example 30 100
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the scope of the technical concept of the present invention, and all the simple modifications belong to the protection scope of the present invention.

Claims (3)

1. A compound which is a compound having one of the following structures or a salt thereof:
2. A composition comprising the compound of claim 1.
3. Use of a compound according to claim 1 or a composition according to claim 2 for controlling powdery mildew and/or maize rust in wheat.
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