CN112047895A - Triazole compound and preparation method and application thereof - Google Patents

Triazole compound and preparation method and application thereof Download PDF

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Publication number
CN112047895A
CN112047895A CN201910493139.7A CN201910493139A CN112047895A CN 112047895 A CN112047895 A CN 112047895A CN 201910493139 A CN201910493139 A CN 201910493139A CN 112047895 A CN112047895 A CN 112047895A
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Prior art keywords
alkyl
radical
compound
cycloalkyl
hydrogen
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Inventor
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

Abstract

The invention provides a triazole compound and a preparation method and application thereof; specifically, the invention relates to a triazole compound shown in formula (I) or a stereoisomer, a nitrogen oxide and a salt thereof of the triazole compound shown in formula (I), a preparation method thereof, application thereof as a bactericide, a form of a bactericidal composition thereof, and a method for preventing and treating plant diseases in agriculture or gardens by using the compounds or the composition; wherein R is1、R2、R3、R4、R5、R6、R7、Ra、Rb、Rc、Rd、ReX and n have the meanings given in the description.

Description

Triazole compound and preparation method and application thereof
Technical Field
The invention relates to the field of agriculture, in particular to triazole bactericide, a preparation method thereof and application thereof as a pathogenic fungus control agent in agriculture.
Background
Triazole fungicides are known plant disease control agents, and with the development of the times, green, broad-spectrum, low-toxicity and high-efficiency become important indexes for evaluating pesticides, so that new control agents with excellent controllability for various plant diseases need to be continuously developed.
Disclosure of Invention
The invention provides a novel triazole bactericide which has an excellent control effect on diseases caused by plant pathogenic fungi.
Specifically, the method comprises the following steps:
in one aspect, the invention provides a compound that is a compound having formula (I) or a stereoisomer, a nitroxide, or a salt thereof of the compound of formula (I):
Figure BDA0002087672170000011
wherein the content of the first and second substances,
R1and R2Each independently is hydrogen or C1-6An alkyl group;
R3is OR33；R33Is hydrogen, C1-6Alkyl radical, C2-6Alkenyl radical, C2-6Alkynyl, C3-8Cycloalkyl radical, C3-8cycloalkyl-C1-6Alkyl, phenyl or phenyl-C1-6An alkyl group;
R5is OR55；R55Is hydrogen, C1-6Alkyl radical, C2-6Alkenyl radical, C2-6Alkynyl, C3-8Cycloalkyl radical, C3-8cycloalkyl-C1-6Alkyl, phenyl or phenyl-C1-6An alkyl group;
R4and R6Each independently is hydrogen or C1-6An alkyl group;
or R5、R6And the carbon atom to which it is attached form C ═ O;
or R5、R3And the carbon atoms to which they are attached form ethylene oxide;
or R3、R2And the carbon atom to which it is attached form a carbon-carbon double bond;
n is 0, 1,2 or 3;
R7is halogen, cyano, hydroxy, nitro, amino, C1-6Alkyl radical, C1-6Alkoxy, halo C1-6Alkyl or halo C1-6An alkoxy group;
x is-O-, -S-or-CH2O-；
Ra、Rb、Rc、RdAnd ReEach independently is hydrogen, halogen, cyano, hydroxyl, mercapto, nitro, carboxyl (-COOH), C1-6Alkyl radical, C1-6Alkoxy, halo C1-6Alkyl, halo C1-6Alkoxy radical, C2-6Alkenyl radical, C2-6Alkynyl, halo C2-6Alkenyl, halo C2-6Alkynyl, C2-6Alkenyloxy radical, C2-6Alkynyloxy, C3-8Cycloalkyl, halo C3-8Cycloalkyl radical, C3-8Cycloalkyl oxy, C3-8cycloalkyl-C1-6Alkyl, -S (═ O)x-C1-6Alkyl, -C (═ O) -C1-6Alkyl, -C (═ O) O-C1-6Alkyl, -NR8R9、-C(＝O)NR10R11Phenyl, benzyl or phenoxy;
R8、R9、R10and R11Each independently is hydrogen, C1-6Alkyl radical, C3-8Cycloalkyl radical, C3-8cycloalkyl-C1-6Alkyl, phenyl or phenyl-C1-6An alkyl group;
x is 0, 1 or 2;
or RaAnd Rb、RbAnd Rc、RcAnd RdOr RdAnd Reform-O- (CH)2)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 RaAnd Rb、RbAnd Rc、RcAnd RdOr RdAnd ReAre respectively connected withThe carbon atoms to which they are attached form a benzene ring; the benzene ring is optionally substituted by 1,2, 3 or 4 substituents selected from halogen, cyano, hydroxy, nitro, C1-6Alkyl radical, C1-6Alkoxy, halo C1-6Alkyl or halo C1-6Substituent of alkoxy.
Wherein R is5、R6And the carbon atom to which it is attached form C ═ O, the corresponding structural formula is:
Figure BDA0002087672170000021
wherein R is1、R2、R3、R4、R7、n、Ra、Rb、Rc、Rd、ReAnd X has the meaning according to the invention.
Wherein R is5、R3And the carbon atom to which it is attached to form ethylene oxide, the corresponding formula is:
Figure BDA0002087672170000022
wherein R is1、R2、R4、R6、R7、n、Ra、Rb、Rc、Rd、ReAnd X has the meaning according to the invention.
Wherein R is3、R2And the carbon atom connected with the compound forms a carbon-carbon double bond, the corresponding structural formula is as follows:
Figure BDA0002087672170000023
wherein R is1、R4、R5、R6、R7、n、Ra、Rb、Rc、Rd、ReAnd X has the meaning according to the invention.
In some embodiments, X is-O-or-CH2O-。
In other embodiments, X is-O-.
In some embodiments, R1And R2Each independently is hydrogen or C1-4An alkyl group.
In other embodiments, R1And R2Each independently is hydrogen, -CH3、-CH2CH3、-CH2CH2CH3、-CH(CH3)2、-CH2CH2CH2CH3、-CH(CH3)CH2CH3、-CH2CH(CH3)CH3or-C (CH)3)3。
In still other embodiments, R1And R2Each independently hydrogen.
In some embodiments, R3Is OR33；R33Is hydrogen, C1-4Alkyl radical, C2-4Alkenyl radical, C2-4Alkynyl, C3-6Cycloalkyl radical, C3-6cycloalkyl-C1-4Alkyl, phenyl or phenyl-C1-4An alkyl group.
In other embodiments, R3Is OR33；R33Is 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.ident.CH, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl or benzyl.
In still other embodiments, R3Is OR33；R33Is hydrogen, -CH3、-CH2CH3、-CH2CH2CH3、-CH(CH3)2、-CH2CH2CH2CH3、-CH(CH3)CH2CH3、-CH2CH(CH3)CH3or-C (CH)3)3。
In still other embodiments, R3Is OR33；R33Is hydrogen.
In some embodiments, R4Is hydrogen or C1-4An alkyl group.
In other embodiments, R4Is hydrogen, -CH3、-CH2CH3、-CH2CH2CH3、-CH(CH3)2、-CH2CH2CH2CH3、-CH(CH3)CH2CH3、-CH2CH(CH3)CH3or-C (CH)3)3。
In some embodiments, R5Is OR55；R55Is hydrogen, C1-4Alkyl radical, C2-4Alkenyl radical, C2-4Alkynyl, C3-6Cycloalkyl radical, C3-6cycloalkyl-C1-4Alkyl, phenyl or phenyl-C1-4An alkyl group.
In other embodiments, R5Is OR55；R55Is 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.ident.CH, cyclopropyl, C.ident.CH,Cyclobutyl, cyclopentyl, cyclohexyl, phenyl or benzyl.
In still other embodiments, R5Is OR55；R55Is hydrogen, -CH3、-CH2CH3、-CH2CH2CH3、-CH(CH3)2、-CH2CH2CH2CH3、-CH(CH3)CH2CH3、-CH2CH(CH3)CH3or-C (CH)3)3。
In still other embodiments, R5Is OR55；R55Is hydrogen.
In some embodiments, R6Is hydrogen or C1-4An alkyl group.
In other embodiments, R6Is hydrogen, -CH3、-CH2CH3、-CH2CH2CH3、-CH(CH3)2、-CH2CH2CH2CH3、-CH(CH3)CH2CH3、-CH2CH(CH3)CH3or-C (CH)3)3。
In still other embodiments, R6Is hydrogen.
In some embodiments, n is 0, 1,2, or 3;
R7is halogen, cyano, hydroxy, nitro, amino, C1-4Alkyl radical, C1-4Alkoxy, halo C1-4Alkyl halo C1-4An alkoxy group.
In other embodiments, n is 0, 1,2, or 3;
R7is fluorine, chlorine, bromine, iodine, cyano, hydroxyl, nitro, amino, -CH3、-CH2CH3、-CH2CH2CH3、-CH(CH3)2、-CH2CH2CH2CH3、-CH(CH3)CH2CH3、-CH2CH(CH3)CH3、-C(CH3)3、-OCH3、-OCH2CH3、-OCH2CH2CH3、-OCH(CH3)2、-CF3or-OCF3。
In some embodiments, Ra、Rb、Rc、RdAnd ReEach independently is hydrogen, halogen, cyano, hydroxy, mercapto, nitro, carboxyl, C1-4Alkyl radical, C1-4Alkoxy, halo C1-4Alkyl, halo C1-4Alkoxy radical, C2-4Alkenyl radical, C2-4Alkynyl, halo C2-4Alkenyl, halo C2-4Alkynyl, C2-4Alkenyloxy radical, C2-4Alkynyloxy, C3-6Cycloalkyl, halo C3-6Cycloalkyl radical, C3-6Cycloalkyl oxy, C3-6cycloalkyl-C1-4Alkyl, -S (═ O)x-C1-4Alkyl, -C (═ O) -C1-4Alkyl, -C (═ O) O-C1-4Alkyl, -NR8R9、-C(＝O)NR10R11Phenyl, benzyl or phenoxy;
R8、R9、R10and R11Each independently is hydrogen, C1-4Alkyl radical, C3-6Cycloalkyl radical, C3-6cycloalkyl-C1-4Alkyl, phenyl or phenyl-C1-4An alkyl group;
x is 0, 1 or 2.
In other embodiments, Ra、Rb、Rc、RdAnd ReEach independently is hydrogen, fluorine, chlorine, bromine, iodine, cyano, hydroxyl, sulfydryl, nitro, carboxyl (-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.ident.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)2Phenyl, benzyl or phenoxy.
In some embodiments, the present invention provides a compound that is a stereoisomer, a nitroxide, or a salt thereof, of a compound having or of formula (I-A):
Figure BDA0002087672170000041
wherein R is1、R2、R3、R4、R5、R6、Ra、Rb、Rc、Rd、ReAnd X has the meaning according to the invention.
In some embodiments, the present invention provides a compound that is a stereoisomer, a nitroxide, or a salt thereof, of a compound having or of formula (II):
Figure BDA0002087672170000042
wherein R is4、R6、Ra、Rb、Rc、Rd、ReAnd X has the meaning according to the invention.
In some embodiments, the present invention provides a compound that is a stereoisomer, a nitroxide, or a salt thereof, of a compound having or of formula (II):
Figure BDA0002087672170000043
wherein R is4Is hydrogen or C1-4An alkyl group;
R6is hydrogen or C1-4An alkyl group;
x is-O-or-CH2O-；
Ra、Rb、Rc、RdAnd ReEach independently is hydrogen, halogen, cyano, hydroxy, mercapto, nitro, amino, C1-4Alkyl radical, C1-4Alkoxy, halo C1-4Alkyl, halo C1-4Alkoxy or phenyl.
In still other embodiments, R4Is hydrogen or-CH3；
R6Is hydrogen;
x is-O-or-CH2O-；
Ra、Rb、Rc、RdAnd ReEach independently is hydrogen, fluorine, chlorine, bromine, iodine, cyano, hydroxyl, mercapto, nitro, amino, -CH3、-CH2CH3、-CH2CH2CH3、-CH(CH3)2、-CH2CH2CH2CH3、-CH(CH3)CH2CH3、-CH2CH(CH3)CH3、-C(CH3)3Phenyl, -CF3or-OCF3。
In still other embodiments, the present invention provides a compound which is a stereoisomer, a nitroxide or a salt thereof of a compound having formula (II-1) or a compound of formula (II-1):
Figure BDA0002087672170000044
wherein R isa、Rb、Rc、RdAnd ReHave the meaning as described in the present invention.
In still other embodiments, the present invention provides a compound which is a stereoisomer, a nitroxide or a salt thereof of a compound having formula (II-1) or a compound of formula (II-1):
Figure BDA0002087672170000051
wherein R isa、Rb、Rc、RdAnd ReEach independently is hydrogen, halogen, cyano, hydroxy, mercapto, nitro, amino, C1-4Alkyl radical, C1-4Alkoxy, halo C1-4Alkyl, halo C1-4Alkoxy or phenyl.
In still other embodiments, Ra、Rb、Rc、RdAnd ReEach independently is hydrogen, fluorine, chlorine, bromine, iodine, cyano, hydroxyl, mercapto, nitro, -CH3、-CH2CH3、-CH2CH2CH3、-CH(CH3)2、-CH2CH2CH2CH3、-CH(CH3)CH2CH3、-CH2CH(CH3)CH3、-C(CH3)3Phenyl, -CF3or-OCF3。
In still other embodiments, the present invention provides a compound which is a stereoisomer, a nitroxide or a salt thereof of a compound having formula (II-1) or a compound of formula (II-1):
Figure BDA0002087672170000052
wherein R isa、Rb、RdAnd ReEach independently is hydrogen;
Rcis hydrogen, halogen, cyano, hydroxy, mercapto, nitro, C1-4Alkyl radical, C1-4Alkoxy, halo C1-4Alkyl, halo C1-4Alkoxy or phenyl.
In still other embodiments, RcIs hydrogen, fluorine, chlorine, bromine, iodine, cyano, hydroxyl, mercapto, nitro, -CH3、-CH2CH3、-CH2CH2CH3、-CH(CH3)2、-CH2CH2CH2CH3、-CH(CH3)CH2CH3、-CH2CH(CH3)CH3、-C(CH3)3Or a phenyl group.
In still other embodiments, the present invention provides a compound which is a stereoisomer, a nitroxide or a salt thereof of a compound having formula (II-1) or a compound of formula (II-1):
Figure BDA0002087672170000053
wherein R isa、Rb、Rc、RdAnd ReAs shown in table 1:
TABLE 1
Figure BDA0002087672170000054
Figure BDA0002087672170000061
In still other embodiments, the present invention provides a compound which is a stereoisomer, a nitroxide or a salt thereof of a compound having formula (II-2) or a compound of formula (II-2):
Figure BDA0002087672170000062
wherein R isa、Rb、Rc、RdAnd ReAs 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 still other embodiments, the present invention provides a compound which is a stereoisomer, a nitroxide or a salt thereof of a compound having formula (II-3) or a compound of formula (II-3):
Figure BDA0002087672170000063
wherein R isa、Rb、Rc、RdAnd ReAs shown in 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, a nitroxide, or a salt thereof, of a compound having or of formula (III):
Figure BDA0002087672170000071
wherein R is4、Ra、Rb、Rc、Rd、ReAnd X has the meaning according to the invention.
In some embodiments, the present invention provides a compound that is a stereoisomer, a nitroxide, or a salt thereof, of a compound having or of formula (III):
Figure BDA0002087672170000072
wherein R is4Is hydrogen or C1-4An alkyl group;
x is-O-or-CH2O-；
Ra、Rb、Rc、RdAnd ReEach independently is hydrogen, halogen, cyano, hydroxy, mercapto, nitro, amino, C1-4Alkyl radical, C1-4Alkoxy, halo C1-4Alkyl, halo C1-4Alkoxy or phenyl.
In still other embodiments, R4Is hydrogen or-CH3；
X is-O-or-CH2O-；
Ra、Rb、Rc、RdAnd ReEach is independentThe radix is hydrogen, fluorine, chlorine, bromine, iodine, cyano, hydroxyl, sulfydryl, nitro, amino-CH3、-CH2CH3、-CH2CH2CH3、-CH(CH3)2、-CH2CH2CH2CH3、-CH(CH3)CH2CH3、-CH2CH(CH3)CH3、-C(CH3)3Phenyl, -CF3or-OCF3。
In still other embodiments, the present invention provides a compound which is a stereoisomer, a nitroxide or a salt thereof of a compound having formula (III-1) or a compound of formula (III-1):
Figure BDA0002087672170000073
wherein R isa、Rb、Rc、RdAnd ReEach independently is hydrogen, halogen, cyano, hydroxy, mercapto, nitro, amino, C1-4Alkyl radical, C1-4Alkoxy, halo C1-4Alkyl, halo C1-4Alkoxy or phenyl;
x is-O-or-CH2O-。
In still other embodiments, Ra、Rb、Rc、RdAnd ReEach independently is hydrogen, fluorine, chlorine, bromine, iodine, cyano, hydroxyl, mercapto, nitro, amino, -CH3、-CH2CH3、-CH2CH2CH3、-CH(CH3)2、-CH2CH2CH2CH3、-CH(CH3)CH2CH3、-CH2CH(CH3)CH3、-C(CH3)3、-OCH3、-CF3、-OCF3Or a phenyl group.
In still other embodiments, the present invention provides a compound which is a stereoisomer, a nitroxide or a salt thereof of a compound having formula (III-2) or a compound of formula (III-2):
Figure BDA0002087672170000074
wherein R isa、Rb、Rc、RdAnd ReAs shown in table 4:
TABLE 4
Figure BDA0002087672170000081
In still other embodiments, the present invention provides a compound which is a stereoisomer, a nitroxide or a salt thereof of a compound having formula (III-3) or a compound of formula (III-3):
Figure BDA0002087672170000082
wherein R isa、Rb、Rc、RdAnd ReAs shown in table 5:
TABLE 5
Figure BDA0002087672170000083
Figure BDA0002087672170000091
In still other embodiments, the present invention provides a compound which is a stereoisomer, a nitroxide or a salt thereof of a compound having formula (III-4) or a compound of formula (III-4):
Figure BDA0002087672170000092
wherein R isa、Rb、Rc、RdAnd ReAs 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, a nitroxide, or a salt thereof, of a compound having or of formula (IV):
Figure BDA0002087672170000093
wherein R is4、R6、Ra、Rb、Rc、Rd、ReAnd X has the meaning according to the invention.
In still other embodiments, the present invention provides a compound which is a stereoisomer, a nitrogen oxide or a salt thereof of a compound having formula (IV-1) or a compound having formula (IV-1):
Figure BDA0002087672170000094
wherein R is4Is hydrogen or C1-4An alkyl group;
R6is hydrogen or C1-4An alkyl group;
Ra、Rb、Rc、Rdand ReEach independently is hydrogen, halogen, cyano, hydroxy, mercapto, nitro, amino, C1-4Alkyl radical, C1-4Alkoxy, halo C1-4Alkyl, halo C1-4Alkoxy or phenyl.
In still other embodiments, R4Is hydrogen or-CH3；
R6Is hydrogen or-CH3；
Ra、Rb、Rc、RdAnd ReEach independently is hydrogen, fluorine, chlorine, bromine, iodine, cyano, hydroxyl, mercapto, nitro, amino, -CH3、-CH2CH3、-CH2CH2CH3、-CH(CH3)2、-CH2CH2CH2CH3、-CH(CH3)CH2CH3、-CH2CH(CH3)CH3、-C(CH3)3、-CF3、-OCF3Or a phenyl group.
In still other embodiments, the present invention provides a compound which is a stereoisomer, a nitrogen oxide or a salt thereof of a compound having formula (IV-2) or a compound having formula (IV-2):
Figure BDA0002087672170000101
wherein R isa、Rb、Rc、RdAnd ReAs 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 still other embodiments, the present invention provides a compound which is a stereoisomer, a nitrogen oxide or a salt thereof of a compound having formula (IV-3) or a compound having formula (IV-3):
Figure BDA0002087672170000102
wherein R isa、Rb、Rc、RdAnd ReAs 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 still other embodiments, the present invention provides a compound which is a stereoisomer, a nitrogen oxide or a salt thereof of a compound having formula (IV-4) or a compound having formula (IV-4):
Figure BDA0002087672170000111
wherein R isa、Rb、Rc、RdAnd ReAs 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, a nitroxide, or a salt thereof, of a compound having or of formula (V):
Figure BDA0002087672170000112
wherein R isa、Rb、Rc、Rd、ReAnd X has the meaning according to the invention.
In some embodiments, the present invention provides a compound that is a stereoisomer, a nitroxide, or a salt thereof, of a compound having or of formula (V):
Figure BDA0002087672170000113
wherein R is4Is hydrogen or C1-4An alkyl group;
R6is hydrogen or C1-4An alkyl group;
x is-O-or-CH2O-；
Ra、Rb、Rc、RdAnd ReEach independently is hydrogen, halogen, cyano, hydroxy, mercapto, nitro, amino, C1-4Alkyl radical, C1-4Alkoxy, halo C1-4Alkyl, halo C1-4Alkoxy or phenyl.
In still other embodiments, R4Is hydrogen or-CH3；
R6Is hydrogen or-CH3；
X is-O-or-CH2O-；
Ra、Rb、Rc、RdAnd ReEach independently of the others is hydrogen, fluorine, chlorine, bromineIodine, -CH3、-CH2CH3、-CH2CH2CH3、-CH(CH3)2、-CH2CH2CH2CH3、-CH(CH3)CH2CH3、-CH2CH(CH3)CH3or-C (CH)3)3。
In still other embodiments, the present invention provides a compound which is a stereoisomer, a nitroxide or a salt thereof of a compound having formula (V-1) or a compound of formula (V-1):
Figure BDA0002087672170000121
wherein R isa、Rb、Rc、RdAnd ReHave the meaning as described in the present invention.
In still other embodiments, the present invention provides a compound which is a stereoisomer, a nitroxide or a salt thereof of a compound having formula (V-1) or a compound of formula (V-1):
Figure BDA0002087672170000122
wherein R isa、Rb、Rc、RdAnd ReEach independently of the others is hydrogen, halogen, C1-4Alkyl radical, C1-4Alkoxy, halo C1-4Alkyl or halo C1-4An alkoxy group.
In still other embodiments, Ra、Rb、Rc、RdAnd ReEach independently hydrogen, fluorine, chlorine, bromine, iodine, -CH3、-CH2CH3、-CH2CH2CH3、-CH(CH3)2、-CH2CH2CH2CH3、-CH(CH3)CH2CH3、-CH2CH(CH3)CH3or-C (CH)3)3。
In still other embodiments, the present invention provides a compound which is a stereoisomer, a nitroxide or a salt thereof of a compound having formula (V-2) or a compound of formula (V-2):
Figure BDA0002087672170000123
wherein R isa、Rb、Rc、RdAnd ReHave the meaning as described in the present invention.
In still other embodiments, the present invention provides a compound which is a stereoisomer, a nitroxide or a salt thereof of a compound having formula (V-2) or a compound of formula (V-2):
Figure BDA0002087672170000124
wherein R isa、Rb、Rc、RdAnd ReEach independently hydrogen or halogen.
In still other embodiments, the present invention provides a compound which is a stereoisomer, a nitroxide or a salt thereof of a compound having formula (V-1) or a compound of formula (V-1):
Figure BDA0002087672170000125
wherein R isa、Rb、Rc、RdAnd ReAs shown in table 10:
watch 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 still other embodiments, the present invention provides a compound which is a stereoisomer, a nitroxide or a salt thereof of a compound having formula (V-2) or a compound of formula (V-2):
Figure BDA0002087672170000131
wherein，Ra、Rb、Rc、RdAnd ReAs 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, a nitroxide, or a salt thereof, of a compound having or of formula (VI):
Figure BDA0002087672170000132
wherein R isa、Rb、Rc、RdAnd ReAs 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 compound having one of the following structures or a stereoisomer, a nitroxide, or a salt thereof of a compound having one of the following structures:
Figure BDA0002087672170000141
Figure BDA0002087672170000151
Figure BDA0002087672170000161
in another aspect, the present invention provides a composition comprising at least one compound of the present invention.
Further, the composition of the present invention further comprises an agriculturally pharmaceutically acceptable surfactant and/or carrier.
In another aspect, the present invention provides the use of a compound according to the present invention or a composition according to the present invention for controlling plant diseases.
In another aspect, the present invention provides a method of using a compound of the present invention or a composition of the present invention for controlling plant diseases.
Detailed description of the invention
Definitions and general terms
Reference will now be made in detail to certain embodiments of the invention, examples of which are illustrated by the accompanying structural and chemical formulas. The invention is intended to cover alternatives, modifications and equivalents, which may be included within the scope of the invention as defined by the appended claims. One 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 invention. The present invention is in no way limited to the methods and materials described herein. In the event that one or more of the incorporated documents, patents, and similar materials differ or contradict this application (including but not limited to defined terminology, application of terminology, described techniques, and the like), this application controls.
It will be further 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 subcombination.
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, the chemical elements are in accordance with the CAS version of the periodic Table of the elements, and the handbook of chemistry and Physics, 75 th edition, 1994. In addition, general principles of Organic Chemistry can be referred to as described in "Organic Chemistry", Thomas Sorrell, University Science Books, Sausaltito: 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" as used herein are intended to include "at least one" or "one or more" unless otherwise indicated or clearly contradicted by context. Thus, as used herein, the articles refer to one or to more than one (i.e., to at least one) of the objects. For example, "a component" refers to one or more components, i.e., there may be more than one component contemplated for use or use in embodiments of the described embodiments.
The term "comprising" is open-ended, i.e. includes the elements indicated in the present invention, but does not exclude other elements.
"stereoisomers" refers to compounds having the same chemical structure but differing in the arrangement of atoms or groups in space. Stereoisomers include enantiomers, diastereomers, conformers (rotamers), geometric isomers (cis/trans), atropisomers, and the like.
"enantiomer" refers to two isomers of a compound that are not overlapping but are in mirror image relationship to each other.
"diastereomer" refers to a stereoisomer that has two or more chiral neutrals and whose molecules are not mirror images of each other. Diastereomers have different physical properties, such as melting points, boiling points, spectral properties, and reactivities. Mixtures of diastereomers 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 general definitions of 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 an 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 denote the absolute configuration of a molecule with respect to one or more of its chiral centers. The prefixes d and l or (+) and (-) are the symbols used to specify the rotation of plane polarized light by the compound, where (-) or l indicates that the compound is left-handed. Compounds prefixed with (+) or d are dextrorotatory. A 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 may occur when there is no stereoselectivity or stereospecificity in the chemical reaction or process.
Any asymmetric atom (e.g., carbon, etc.) of a compound disclosed herein can exist in racemic or enantiomerically enriched forms, such as 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 exist as one of the possible isomers or as mixtures thereof, for example as racemates and mixtures of non-corresponding isomers (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 substituents 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.
Any resulting mixture of stereoisomers may be separated into pure or substantially pure geometric isomers, enantiomers, diastereomers, depending on differences in the physicochemical properties of the components, for example, by chromatography and/or fractional crystallization.
The racemates of any of the resulting end products or intermediates can be resolved into the optical enantiomers by known methods using methods familiar to those skilled in the art, e.g., by separation of the diastereomeric salts obtained. The racemic product can also be separated by chiral chromatography, e.g., High Performance Liquid Chromatography (HPLC) using a chiral adsorbent. In particular, enantiomers can be prepared by asymmetric synthesis.
The compounds of the invention may be optionally substituted with one or more substituents, as described herein, in compounds of the general formula above, or as specifically exemplified, sub-classes, and classes of compounds encompassed by the invention. It is 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 particular substituent. Unless otherwise indicated, an optional substituent group may be substituted at each substitutable position of the group. When more than one position in a given formula can be substituted with one or more substituents selected from a particular group, the substituents may be substituted at each position, identically or differently. Specifically, examples of "one or more" refer to 1,2, 3, 4, 5, 6, 7, 8, 9, or 10. Wherein said substituent may be, but is 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, alkylaminoalkyl, alkylaminoalkylamino, 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, aryl, arylalkyl, arylamino, heteroaryl, heteroarylalkyl, heteroarylamino, amido, sulfonyl, aminosulfonyl, and the like.
In addition, unless otherwise explicitly indicated, the descriptions of the terms "… independently" and "… independently" and "… independently" used in the present invention are interchangeable and should be understood in a broad sense to mean that the specific items expressed between the same symbols do not affect each other in different groups or that the specific items expressed between the same symbols in the same groups do not affect each other.
In the various parts of this specification, substituents of the disclosed compounds are disclosed in terms of group type or range. It is specifically intended that the invention includes each and every independent subcombination of the various members of these groups and ranges. For example, the term "C1-C6Alkyl "or" C1-6Alkyl "means in particular independently disclosed methyl, ethyl, C3Alkyl radical, C4Alkyl radical, C5Alkyl and C6An alkyl group.
The term "alkyl" or "alkyl group" as used herein, denotes a saturated, straight or branched chain, monovalent hydrocarbon group containing from 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 1-20 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 group (Et, -CH)2CH3) N-propyl (n-Pr, -CH)2CH2CH3) Isopropyl group (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 so on.
The term "alkoxy" means an alkyl group attached to the rest 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 so on.
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 sp2A double bond, wherein the alkenyl group may be optionally substituted with one or more substituents 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 contains 2 to 6 carbon atoms; in yet another embodiment, the alkeneThe radical 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) Allyl (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 radical may be optionally substituted with one or more substituents as described herein. In one embodiment, alkynyl groups contain 2-10 carbon atoms; in one embodiment, alkynyl groups contain 2-8 carbon atoms; in another embodiment, alkynyl groups contain 2-6 carbon atoms; in yet another embodiment, alkynyl groups contain 2-4 carbon atoms. Examples of alkynyl groups include, but are not limited to, -C.ident.CH, -C.ident.CCH3、-CH2-C≡CH、-CH2-C≡CCH3、-CH2CH2-C≡CH、-CH2-C≡CCH2CH3、-CH2CH2-C≡CH2CH3And so on.
The term "alkenyloxy" means an alkenyl group attached to the rest of the molecule through an oxygen atom, wherein the alkenyl group has the meaning as described herein.
The term "alkynyloxy" denotes an alkynyl group attached to the rest 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 from 3 to 12 carbon atoms. In one embodiment, the cycloalkyl group contains 3 to 10 carbon atoms; in another embodiment, cycloalkyl contains 3 to 8 carbon atoms; in yet another embodiment, the cycloalkyl group contains 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" denotes an alkyl group substituted by one or more cycloalkyl groups, wherein alkyl and cycloalkyl groups have the meaning as described herein.
The term "cycloalkyloxy" denotes a cycloalkyl group attached to the rest of the molecule through an oxygen atom, wherein the cycloalkyl group has the meaning as described herein.
The term "phenyl-alkyl" denotes an alkyl group substituted by 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" denotes an alkyl group substituted with one or more halogen atoms, examples of which include, but are not limited to, -CF3，-CHF2，-CH2Cl，-CH2CF3，-CH2CHF2，-CH2CH2CF3And the like.
The term "haloalkoxy" denotes an alkoxy group substituted with one or more halogen atoms, examples of which include, but are not limited to, -OCF3，-OCHF2，-OCHCl2，-OCH2CHF2，-OCH2CHCl2，-OCH(CH3)CHF2And the like.
The term "haloalkenyl" denotes an alkenyl group substituted with one or more halogen atoms.
The term "haloalkynyl" denotes an alkynyl group substituted by one or more halogen atoms.
The term "halocycloalkyl" denotes a cycloalkyl group substituted with one or more halogen atoms.
Salts of the compounds of the present invention include those derived from alkali or alkaline earth metals as well as those derived from ammonia and amines. Preferred cations include sodium, potassium, magnesium and those of formula N+(RAARBBRCCRDD) Ammonium cation of (2), wherein R isAA、RBB、RCCAnd RDDIndependently selected from hydrogen, C1-C6Alkyl and C1-C6A hydroxyalkyl group. Salts of compounds having formula (I), formula (I-A), formula (II), formula (III), formula (IV) or formula (V) may be prepared by treating a compound having formula (I), formula (I-A), formula (II), formula (III), formula (IV) or formula (V) with a metal hydroxide, such as sodium hydroxide, or an amine, such as ammonia, trimethylamine, diethanolamine, 2-methylthiopropylamine, diallylamine, 2-butoxyethylamine, morpholine, cyclododecylamine or benzylamine.
When a compound of the invention comprises a base moiety, acceptable salts can be formed from organic and inorganic acids, such as acetic, propionic, lactic, citric, tartaric, succinic, fumaric, maleic, malonic, mandelic, malic, phthalic, hydrochloric, hydrobromic, phosphoric, nitric, sulfuric, methanesulfonic, napthalenesulfonic, 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, having at least one additional component, typically further comprising an agriculturally pharmaceutically 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, moisture and temperature.
The surfactant may be any of various surfactants known in the field of pesticide formulation, and one or more of an emulsifier, a dispersant and a wetting agent are preferred in the present invention.
The carrier other than the surfactant may be any of various carriers known in the field of pesticide formulation, including various silicates, carbonates, sulfates, oxides, phosphates, plant carriers, and synthetic carriers. Specifically, for example: white carbon black, kaolin, diatomite, 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 any emulsifier known in the field of pesticide formulation, and specifically, the emulsifier may be one or more of calcium dodecylbenzenesulfonate, trisethylphenol 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 field of pesticide formulation, and specifically, the dispersing agent is one or more of acrylic acid homopolymer sodium salt, maleic acid disodium salt, naphthalene sulfonic acid formaldehyde condensation product sodium salt, rosin block polyoxyethylene ether polyoxypropylene ether sulfonate, hydroxyl-terminated polyoxyethylene polyoxypropylene ether block copolymer, triphenyl polyoxyethylene phenol phosphate, fatty alcohol polyoxyethylene ether phosphate and p-hydroxyphenyl lignosulfonate sodium salt.
The wetting agent can be various wetting agents known in the field of pesticide formulation, and specifically, the wetting agent can be one or more of sodium dodecyl sulfate, secondary alkyl sodium sulfate, sodium dodecyl benzene sulfonate, fatty alcohol-polyoxyethylene ether, alkyl naphthalene sulfonate and alkylphenol resin polyoxyethylene ether sulfate.
According to the bactericide composition, various preparation auxiliaries commonly used in the field of pesticide formulation can be further contained, and specifically, the preparation auxiliaries can be one or more of a solvent, a cosolvent, a thickening agent, an antifreezing agent, a capsule wall material, a protective agent, an antifoaming agent, a disintegrating agent, a stabilizing agent, a preservative and a binder.
The solvent may be any of various solvents known in the field of pesticide formulation, and specifically, the solvent may be one or more of an organic solvent, a vegetable oil, a mineral oil, a solvent oil and water.
Wherein the organic solvent comprises one or more of N-methylpyrrolidone, tetrahydrofuran, dimethyl sulfoxide, N-dimethyldecanamide, N-dimethylformamide, trimethylbenzene, tetramethylbenzene, dimethylbenzene, methylbenzene, 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, rosin-based vegetable oil, turpentine oil, epoxidized soybean oil, peanut oil, rapeseed oil, castor oil, corn oil and pine seed oil.
The mineral oil comprises one or more of liquid wax, engine oil, kerosene and lubricating oil.
Meanwhile, the solvent can also be used as a cosolvent.
The antifreeze can be various antifreeze agents known in the field of pesticide formulation, and the invention is preferably one or more of ethylene glycol, propylene glycol, glycerol and urea.
The thickener can be various thickeners known in the field of pesticide formulation, and specifically can be one or more of xanthan gum, polyvinyl alcohol, polypropylene alcohol, polyethylene glycol, white carbon black, diatomite, kaolin, clay, sodium alginate, magnesium aluminum silicate, sodium aluminum silicate, carboxymethyl cellulose, sodium hydroxypropyl cellulose and organic bentonite.
The capsule material can be various capsule materials known in the field of pesticide formulation, 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 pesticide formulation, and polyvinyl alcohol and/or polyethylene glycol is preferred in the present invention.
The defoaming agent may be any of those known in the field of agricultural agent formulation, and in the present invention, one or more of organosiloxane, tributyl phosphate and silicone are preferable.
The stabilizer is one or more selected from triphenyl phosphite, epichlorohydrin and acetic anhydride.
The antiseptic is selected from one or more of benzoic acid, sodium benzoate, 1, 2-benzisothiazolin-3-one (BIT), Kathon and potassium sorbate.
The invention also provides a preparation prepared from the bactericide composition, and the preparation is in the form of missible oil, aqueous emulsion, microemulsion, soluble liquid, aqueous suspension, suspoemulsion, ultra-low volume spray, oil suspension, microcapsule suspension, water surface spreading oil, wettable powder, water dispersible granule, dry suspension, soluble powder, soluble granule, emulsifiable powder, emulsifiable granule, solid microcapsule preparation, effervescent tablet, effervescent granule, water floating dispersion granule or seed coating. The above formulations 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, so as to obtain the emulsifiable concentrate preparation.
The preparation method of the aqueous emulsion can comprise, for example, mixing the active ingredient, the emulsifier, the cosolvent and the solvent to form a uniform oil phase; mixing water, thickener, antifreeze, etc. to obtain uniform water 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, for example, by mixing and stirring the active ingredient, emulsifier, and solvent to form a uniform transparent oil phase. Under stirring, water is gradually added to form a uniform and transparent microemulsion.
The preparation method of the water/oil suspending agent comprises the following steps: for example, water or oil can be used as a medium, and an auxiliary agent such as an active component and a surfactant is added into a sanding kettle, and after grinding to a certain particle size, filtration is performed. And adding the weighed thickening agent into the ground mother liquor, and uniformly shearing and dispersing. 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 active ingredients, the dispersing agent, the wetting agent, the carrier and the like are uniformly mixed, then are pulverized into a certain particle size through air flow, are added with water for kneading, are finally added into a granulator for granulation, and are dried to obtain the water dispersible granules or the soluble granules.
The preparation method of the soluble powder and the wettable powder comprises the following steps: for example, the active ingredients, various adjuvants and fillers such as other carriers can be thoroughly mixed and pulverized by a micronizer.
The germicide composition of the present invention may be provided in the form of a finished formulation, i.e., the components of the composition have been mixed; or in separate formulations which are self-mixing in a tub or tank prior to use and optionally diluted by mixing with water depending on the concentration of active desired.
For additional information regarding The field of formulation, see "The formulations's Toolbox-Product Forms for model Agriculture" by T.S. woods, The Food-Environment Challenge, T.Brooks and T.R. Roberts eds, Proceedings of The 9th International conformation on Pesticide Chemistry, The Royal Society of Chemistry, Cambridge, 1999, p.120. 133. See also U.S.3,235,361, column 6, line 16 to column 7, line 19 and examples 10-41; U.S. Pat. No. 3,309,192, column 5, column 43 to column 7, column 62 and examples 8, 12, 15, 39, 41, 52, 53, 58, 132, 138, 162, 164, 166, 167 and 169, 182; U.S.2,891,855 at column 3, line 66 to column 5, line 17 and examples 1-4; wed Control as a Science by Klingman, John Wiley and Sons, Inc., New York, 1961, pages 81-96; weed Control Handbook, 8 th edition, Blackwell Scientific Publications, Oxford, 1989, by Hance et al; and Developments in simulation technology, PJB Publications, Richmond, UK, 2000.
Application of the inventive compounds and compositions
The compound of the present invention is useful as a plant disease control agent. The present invention therefore also comprises a method for controlling plant diseases caused by phytopathogenic fungi, which comprises applying to the plants to be protected or to parts thereof or to the seeds of the plants to be protected an effective amount of a compound according to the invention or of a fungicidal composition comprising said compound. The compounds and/or compositions of the present invention provide control of diseases caused by a broad spectrum of phytopathogenic fungi of the classes Basidiomycetes, Ascomycetes, Oomycetes and Deuteromycetes. They are effective in controlling a broad spectrum of plant diseases, particularly foliar pathogens of ornamental, turf, vegetable, field, cereal and fruit crops. These pathogens include: oomycetes, including Phytophthora (Phytophthora) diseases such as Phytophthora infestans, Phytophthora sojae (Phytophthora megasporum), Phytophthora citri (Phytophthora parasitica), Phytophthora citrullus (Phytophthora parasiti), Phytophthora cinnamomi (Phytophthora cinnamomi) and Phytophthora cucurbitae (Phytophthora capsici), Pythium graminum (Pythium) species diseases such as Pythium turtium (Pythium aphanidermatum) diseases, and Peronosporaceae (Peronospora) species diseases such as Plasmopara viticola (Plasmopara viticola), Peronospora (Peronospora spp.) (including P. nicotianae (Peronospora tabacina) and P. parasitica (Pseudoperonospora Pseudoperonospora), including P. nicotianae (Pseudoperonospora cinerea) and P. Pseudoperonospora (Pseudoperonospora Pseudoperonospora) diseases including P); ascomycetes (including Alternaria (Alternaria) such as Alternaria solani and Phytophthora brassicae (Alternaria solani), Mycoporia globosa (Guignardia) diseases such as Staphylococcus viticola (Guignardia bidwell), Venturia (Venturia) diseases such as Venturia mali (Venturia inaequalis), Sphaerotheca (Sepia) diseases such as Microphyllum nodosum (Septorium nodorum) and Phytophthora parasitica (Septorii), Powderzia (Powdery) diseases such as Erysiphe graminis (Erysiphe spp.) and Sphaerotheca (Septoria oryzae), Powder Erysiphe (Erysiphe) diseases such as Microphyllum graminis (Erysiphe sp.) and Pseudoperonospora cinerea (Ostericola), Staphylococcus viticola (Uncinula necator), Pseudoperonospora cucumerina (Sphaerothecoides) and Pseudoperonospora cinerea (Botrytis), Scleroti cinerea) diseases such as Microphyllum cinerea (Botrytium cinerea), Scleroti cinerea) diseases such as Microphyllum cinerea (Botrytum cinerea), Scleroti cinerea (Potentilla) diseases such as Microphyllum cinerea (Botrytum cinerea), Scleroti cinerea) diseases such as Microphyllum cinerea (Potentilla cinerea), Scleroti cinerea (Potentilla cinerea), Scleroti cinerea) diseases such, Pyricularia oryzae (Magnaporthe grisea), Rhizoctonia solani (Phomopsis viticola), Helminthosporium (Helminthosporium) diseases such as northern leaf blight (Helminthosporium tritici reptilis), Moss reticulata (Pyrenophora teres), anthrax bacteria such as Hedychium nigrum (Glomerella) or Anthrax (Colletochium spp.) diseases (such as Colletotrichum graminicum (Colestochium graminicum) and watermelon anthrax (Colletochium orbiculosum)), and wheat holothrix graminis (Gaeumannomyces graminis); basidiomycetes, including rust diseases caused by the genus Puccinia (Puccinia spp.), such as Puccinia recondita (Puccinia recondita), Puccinia striiformis (Puccinia striiformis), Puccinia purpurea (Puccinia hordei), Puccinia graminis (Puccinia graminis) and Puccinia arachidis (Puccinia arachidis), coffee rust (hemix) and soybean rust (Phakopsora pachyrhizi); other pathogens include Rhizoctonia species (Rhizoctonia spp.) (such as Rhizoctonia solani); fusarium species diseases such as Fusarium roseum (Fusarium roseum), Fusarium graminearum (Fusarium graminearum), and Fusarium oxysporum (Fusarium oxysporum); verticillium dahliae (Verticillium dahliae); sclerotium rolfsii (sclerotiotium rolfsii); physalospora piricola (Rynchosporium secalis); black acerola (Cercosporium personatum), Episra nigrella (Cercospora arachidicola), and Episra fuscospora (Cercospora betacola); and other classes and species closely related to these pathogens. In addition to their fungicidal activity, the compositions or combinations also have a resistant activity against bacteria such as Erwinia amylovora (Erwinia amylovora), Xanthomonas campestris (Xanthomonas campestris), Pseudomonas syringae (Pseudomonas syringae) and other species.
The bactericide composition of the invention is simple in use method, and can be applied to crops and places where the crops grow by a conventional method such as soil mixing, spraying, pouring and the like before or after the germination of plant diseases, wherein the application amount is determined according to climatic conditions or crop states, generally 10-5000g is applied per mu, and the diluted application amount is 10-400mg/L (preferably 100-300 mg/L). The diluent is preferably water.
The bactericidal effect of the bactericide composition of the present invention is generally related to external factors such as climate, but the influence of climate can be alleviated by using appropriate dosage forms.
The compositions of the present invention may also be used in admixture with other compounds having fungicidal, insecticidal or herbicidal properties, as well as with nematicides, acaricides, protectants, herbicidal safeners, growth regulators, plant nutrients or soil conditioners, and the like.
General synthetic procedure
The following scheme describes the preparation of the compounds of the present invention. Unless otherwise indicated, the compounds of the invention may be prepared by the methods described herein. The starting materials, reagents and the like used in the preparation of the compounds of the present invention are commercially available or can be prepared by methods conventional in the art. In this specification, a structure is dominant if there is any difference between the chemical name and the chemical structure. In the present invention, the room temperature is 0 to 40 ℃ unless otherwise specified.
The test conditions of the nuclear magnetic resonance hydrogen spectrum of the invention are as follows: brookfield (Bruker) nuclear magnetic instrument at 400MHz or 600MHz in CDC1 at room temperature3，d6-DMSO，CD3OD or d6Acetone as solvent (reported in ppm) with TMS (0ppm) or chloroform (7.26ppm) as reference standard. When multiple peaks occur, the following abbreviations will be used: s (singleton), d (doublet), t (triplet), q (quatet, quartet), m (multiplet ), br (broadpeded, broad), dd (doublet of doublets), dt (doublet of triplets). 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 were: agilent 6120 Quadrupole HPLC-MS (column model: Zorbax SB-C18,2.1X 30mm,3.5 μm,6min, flow rate of 0.6mL/min, mobile phase: 5% -95% (CH containing 0.1% formic acid)3CN) in (H containing 0.1% formic acid)2Proportion in O)), at 210/254nm with UV detection, using electrospray ionization mode (ESI).
Synthetic schemes
The following synthetic schemes describe the steps for preparing the compounds disclosed herein. Wherein R isa、Rb、Rc、RdAnd ReHave the meaning as described in the present invention.
Synthesis scheme I
Figure BDA0002087672170000231
The target compounds III-2 and III-4 can be prepared by the first synthesis scheme. Reacting the compound a with isopropyl magnesium chloride to obtain a Grignard reagent, and reacting 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 reacting the compound e-1 or the compound e-2 with 1,2, 4-triazole in an alkaline system to obtain a target compound III-2 or a target compound III-4.
Synthesis scheme two
Figure BDA0002087672170000232
The target compound II-1 and the target compound IV-2 can be prepared by the second synthesis scheme. Reducing the target compound III-2 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 scheme three
Figure BDA0002087672170000241
The target compound II-3 and the target compound IV-4 can be prepared by a third synthesis scheme. Reducing the target compound III-4 by a reducing agent to obtain a target compound II-3; and dehydrating the target compound II-3 to obtain a target compound IV-4.
Synthesis scheme four
Figure BDA0002087672170000242
The target compound V-1 can be prepared by the fourth synthesis scheme. Dehydrating the target compound III-2 at high temperature (100-150 ℃) to obtain a compound f; and reducing the compound f by a reducing agent to obtain a target compound V-1.
Synthesis scheme five
Figure BDA0002087672170000243
The target compound V-2 can be prepared by the fifth synthesis scheme. Dehydrating the target compound III-4 at high temperature (100-150 ℃) to obtain a compound g; and reducing the compound g by a reducing agent to obtain a target compound V-2.
Detailed Description
The following examples are intended to illustrate 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
Figure BDA0002087672170000244
Step 1: synthesis of 1- (4-fluoro-2- (trifluoromethyl) phenyl) -2-methylpropan-1-one
At room temperature, 2-bromo-5-fluorotrifluoromethylbenzene (50.0g,206mmol) was dissolved in methyl tert-butyl ether (100mL), 2.0M isopropyl magnesium chloride (260mmol,130mL) in tetrahydrofuran was added dropwise under nitrogen protection, and after completion of the addition for 30 minutes, reaction was carried out at room temperature for 1 hour to obtain 4-fluoro-2-trifluoromethylphenylmagnesium chloride. Under the protection of nitrogen at room temperature, 4-fluoro-2-trifluoromethylphenylmagnesium chloride reaction solution is dropwise added to methyl tert-butyl ether (50mL) of isobutyryl chloride (30.9g,290mmol), and after dropwise addition, the reaction solution is reacted at room temperature for 3 hours. After quenching the reaction with water (200mL), 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 in 97.6% yield.
1H NMR(400MHz,CDCl3)(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 (4.00g,17.09mmol) and p-chlorophenol (2.56g,20.00mmol) were dissolved in N, N-dimethylformamide (30mL) at room temperature, potassium carbonate (3.40g,25.00mmol) was added, and the reaction was stirred at 110 ℃ for 5 hours. The reaction was poured into water (100mL), extracted with ethyl acetate (100mL × 2), 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)(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。
And 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 (3.00g,8.77mmol) was dissolved in methyl t-butyl ether (30mL) at room temperature, and liquid bromine (1.59g,10.00mmol) was added dropwise, after which the reaction was stirred at room temperature for 8 hours. The reaction was washed with sodium sulfite solution (40mL × 2), 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 with a yield of 95.5%.
1H NMR(400MHz,CDCl3)(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。
And 4, 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
At room temperature, 1,2, 4-triazole (1.38g,20.00mmol) and sodium hydroxide (0.60g,15.00mmol) are dissolved in dimethyl sulfoxide (30mL), heated to 90 ℃ and stirred for 1 hour, then a dimethyl sulfoxide solution (10mL) of 2-bromo-1- (4- (4-chlorophenoxy) -2- (trifluoromethyl) phenyl) -2-methylpropan-1-one (4.21g,10.00mmol) is added dropwise, heated to 130 ℃ and stirred for reaction for 8 hours. The reaction solution was poured into water (100mL), extracted with ethyl acetate (100mL × 2), 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 with a yield of 28.3%.
1H NMR(400MHz,CDCl3)(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 objective compounds in Table 13 were obtained by following the preparation method of example 1 using the corresponding compounds as starting materials.
Watch 13
Figure BDA0002087672170000251
Figure BDA0002087672170000261
Figure BDA0002087672170000271
Figure BDA0002087672170000281
Figure BDA0002087672170000291
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
Figure BDA0002087672170000292
1- (4- (2-chlorophenoxy) -2- (trifluoromethyl) phenyl) -2-hydroxy-2-methyl-3- (1H-1,2, 4-triazol-1-yl) propan-1-one (1.21g,2.83mmol) was dissolved in ethanol (20mL), sodium borohydride (0.11g,2.91mmol) was added, and the reaction was stirred at room temperature for 4 hours. The reaction was quenched with saturated ammonium chloride solution (20mL), extracted with ethyl acetate (40mL x 2), the organic phases combined, concentrated under reduced pressure, and the residue subjected to column chromatography [ petroleum ether/ethyl acetate (v/v) ═ 2/3] to give 1.15g of a white solid with a yield of 94.2%.
LC-MS:(M+1)m/z＝428.1。
The target compounds in Table 14 can be obtained by reducing the compounds in Table 13 with a reducing agent (e.g., sodium borohydride), respectively.
TABLE 14
Figure BDA0002087672170000301
Figure BDA0002087672170000311
Example 32: synthesis of 1- ((3- (4- (2-chlorophenoxy) -2- (trifluoromethyl) phenyl) -2-methyloxiran-2-yl) methyl) -1H-1,2, 4-triazole
Figure BDA0002087672170000312
1- (4- (2-chlorophenoxy) -2- (trifluoromethyl) phenyl) -2-methyl-3- (1H-1,2, 4-triazol-1-yl) propan-1, 2-diol (1.15g,2.67mmol) was dissolved in tetrahydrofuran (20mL), and sodium hydride (0.13g,5.43mmol) was added with stirring at 0 ℃ after completion of the addition, p-toluenesulfonyl chloride (0.57g,3.00mmol) was added after 10 minutes of further stirring at 0 ℃, and the reaction was further stirred at 0 ℃ for 3 hours after completion of the addition. The reaction was quenched with water (20mL), extracted with dichloromethane (40mL x 2), the organic phases combined and concentrated under reduced pressure, and the residue was subjected to column chromatography [ petroleum ether/ethyl acetate (v/v) ═ 17/3] to give 0.81g of a white solid in 74.1% yield.
1H NMR(400MHz,CDCl3)(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)(ppm):-61.06；
LC-MS:(M+1)m/z＝410.1。
The compounds in table 14 were prepared by the preparation methods of example 32, respectively, to obtain the target compounds in table 15.
Watch 15
Figure BDA0002087672170000313
Figure BDA0002087672170000321
Figure BDA0002087672170000331
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
Figure BDA0002087672170000332
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 (1.21g,2.83mmol) dimethylsulfoxide (20mL) was added with sodium hydroxide (0.20g,5.00mmol), and the reaction was heated to 130 ℃ and stirred for 4 hours. The reaction was poured into water (50mL), extracted with ethyl acetate (50mL × 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)(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)(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 the protection of nitrogen, (E) -1- (4- (4-chlorophenoxy) -2- (trifluoromethyl) phenyl) -2-methyl-3- (1H-1,2, 4-triazol-1-yl) propan-2-en-1-one (0.41g,1.0mmol) is dissolved in anhydrous methanol (5mL), the temperature is reduced to 0 ℃, sodium borohydride (0.19g,5.0mmol) is added while stirring, the reaction is continued at 0 ℃, after the completion of the TLC monitoring reaction, saturated ammonium chloride solution is added dropwise to quench the reaction (10mL), ethyl acetate is extracted (10mL x 2), the organic phases are combined, the mixture is washed with saturated saline (10mL), dried over anhydrous sodium sulfate, concentrated under reduced pressure, the residue is subjected to column chromatography [ petroleum ether/ethyl acetate (v/v) ═ 4/1], 0.36g of a white solid was obtained in 38% yield.
LC-MS:(M+1)m/z＝410.0。
The compounds shown in Table 13 were prepared in a similar manner to that in example 39 to give the objective compounds shown in Table 16.
TABLE 16
Figure BDA0002087672170000333
Figure BDA0002087672170000341
Test example
1) Wheat powdery mildew (wheat powder)
1-leaf and 1-heart-period potted wheat seedlings with consistent growth are selected, and oil marker pens are used for writing label numbers for experiments. Dissolving the raw medicine with solvent DMSO, and adding water containing 0.1% Tween-80 to dilute to 200 mg/L. Spraying stems and leaves, and drying the test material in the shade in a ventilated place after treatment.
Inoculating after 24 hr, and inoculating mature wheat powdery mildew spore on wheat seedling. And (4) carrying out greenhouse low-humidity culture (15-26 ℃) on the inoculated wheat seedlings, carrying out grading investigation according to the disease conditions of blank controls after 8d, and calculating the control effect according to disease indexes.
The test results are shown in table 17.
TABLE 17 prevention of wheat powdery mildew at 200mg/L by the compounds of the invention
Figure BDA0002087672170000342
Figure BDA0002087672170000351
2) Corn rust (maize rust (Puccinia sorghi Schw.))
Selecting potted corn seedlings with two leaf periods of consistent vigor, writing numbers on the cup body by using an oil marker pen, and discharging the numbers in sequence for testing. Dissolving the raw medicine with solvent DMSO, and adding water containing 0.1% Tween-80 to dilute to 200 mg/L. Spraying stems and leaves, and drying the test material in the shade in a ventilated place after treatment.
Inoculation is carried out about 24 hours after treatment. Collecting mature leaf of corn with rust spore, adding into water containing surfactant, washing off spore with writing brush, filtering with double-layer gauze to obtain spore suspension (2 × 10)6～5×106seed/mL), and evenly spraying and inoculating the corn seedlings by using an inoculation sprayer (the pressure is 0.1 MPa). Placing the inoculated potted corn in a moisture-keeping box (room) or an artificial climate room (the temperature is 25 ℃, and the relative humidity is 100%) for culturing, placing in an incubator (room) with the illumination intensity of more than 2000lx or a greenhouse for high-humidity culturing after 24h, carrying out grading investigation according to the blank control disease occurrence condition after about 7d, and calculating the control effect according to disease indexes.
The test results are shown in table 18.
TABLE 18 prevention of corn rust by the inventive compounds at 200mg/L
Compound (I) Control 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) Gray mold of soybean (Botrytis cinerea)
Potted soybean seedlings with the same leaf stage length and vigor are selected, and oil marker pens are used for writing label numbers for testing. Dissolving the raw medicine with solvent DMSO, and adding water containing 0.1% Tween-80 to dilute to 200 mg/L. Spraying stems and leaves, and drying the test material in the shade in a ventilated place after treatment.
Typically, the inoculation is carried out about 24 hours after the treatment. Lightly stabbing the center of the surface of the soybean leaf with a small needle, and sticking the side with hyphae to cover the surface wound of the leaf with a toothpick after preparing the fungus cake with the diameter of 5 mm.
Transferring the inoculated test material to an artificial climate chamber with alternating light and dark for culture (22 ℃, the humidity is more than 90 percent)
The diameter of the disease spot is measured by a caliper, and the prevention and treatment effect is calculated.
The test results are shown in table 19.
TABLE 19 control of Botrytis cinerea at 200mg/L for compounds of the invention
Compound (I) Control effect (%)
Example 6 98
Example 8 98
4) Cucumber anthracnose (Colletotrichum orbicular)
Potted cucumber seedlings with long leaf period and consistent vigor are selected, and oil marker pens are used for writing label numbers for testing. Dissolving the raw medicine with a solvent DMSO, and adding 0.1% Tween 80 water to dilute to 200 mg/L. Spraying stems and leaves, and drying the test material in the shade in a ventilated place after treatment.
Typically, the inoculation is carried out about 24 hours after the treatment. Adding sterile water into a culture dish full of spores, scraping surface spores, filtering with 2-4 layers of gauze to obtain a culture dish with a concentration of 7 multiplied by 104～8×104CFU/mL spore suspension, then using the inoculation atomizer (pressure 0.1MPa) on the rice seedlings evenly spray. And (4) after inoculation, moving the inoculated seeds into a phytotron, wherein the relative humidity is more than 85%, the temperature is 25-28 ℃, the light intensity is more than 2000lx, and after 5-7 days, the disease condition 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 by the compounds of the invention at 200mg/L
Compound (I) Control effect (%)
Example 30 100
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.

Claims (13)

1. A compound which is a stereoisomer, a nitroxide or a salt thereof having or being of formula (I):
Figure FDA0002087672160000011
wherein the content of the first and second substances,
R1and R2Each independently is hydrogen or C1-6An alkyl group;
R3is OR33；R33Is hydrogen, C1-6Alkyl radical, C2-6Alkenyl radical, C2-6Alkynyl, C3-8Cycloalkyl radical, C3-8cycloalkyl-C1-6Alkyl, phenyl or phenyl-C1-6An alkyl group;
R5is OR55；R55Is hydrogen, C1-6Alkyl radical, C2-6Alkenyl radical, C2-6Alkynyl, C3-8Cycloalkyl radical, C3-8cycloalkyl-C1-6Alkyl, phenyl or phenyl-C1-6An alkyl group;
R4and R6Each independently is hydrogen or C1-6An alkyl group;
or R5、R6And the carbon atom to which it is attached form C ═ O;
or R5、R3And the carbon atoms to which they are attached form ethylene oxide;
or R3、R2And the carbon atom to which it is attached form a carbon-carbon double bond;
n is 0, 1,2 or 3;
R7is halogen, cyano, hydroxy, nitro, amino, C1-6Alkyl radical, C1-6Alkoxy, halo C1-6Alkyl or halo C1-6An alkoxy group;
x is-O-or-CH2O-；
Ra、Rb、Rc、RdAnd ReEach independently is hydrogen, halogen, cyano, hydroxy, mercapto, nitro, carboxyl, C1-6Alkyl radical, C1-6Alkoxy, halo C1-6Alkyl, halo C1-6Alkoxy radical, C2-6Alkenyl radical, C2-6Alkynyl, halo C2-6Alkenyl, halo C2-6Alkynyl, C2-6Alkenyloxy radical, C2-6Alkynyloxy, C3-8Cycloalkyl, halo C3-8Cycloalkyl radical, C3-8Cycloalkyl oxy, C3-8cycloalkyl-C1-6Alkyl, -S (═ O)x-C1-6Alkyl, -C (═ O) -C1-6Alkyl, -C (═ O) O-C1-6Alkyl, -NR8R9、-C(＝O)NR10R11Phenyl, benzyl or phenoxy;
R8、R9、R10and R11Each independently is hydrogen, C1-6Alkyl radical, C3-8Cycloalkyl radical, C3-8cycloalkyl-C1-6Alkyl, phenyl or phenyl-C1-6An alkyl group;
x is 0, 1 or 2;
or RaAnd Rb、RbAnd Rc、RcAnd RdOr RdAnd Reform-O- (CH)2)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 RaAnd Rb、RbAnd Rc、RcAnd RdOr RdAnd ReRespectively form benzene rings with the carbon atoms connected with the benzene ring; the benzene ring is optionally substituted by 1,2, 3 or 4 substituents selected from halogen, cyano, hydroxy, nitro, C1-6Alkyl radical, C1-6Alkoxy, halo C1-6Alkyl or halo C1-6Substituent of alkoxy.
2. The compound of claim 1, wherein,
R3is OR33；R33Is hydrogen, C1-4Alkyl radical, C2-4Alkenyl radical, C2-4Alkynyl, C3-6Cycloalkyl radical, C3-6cycloalkyl-C1-4Alkyl, phenyl or phenyl-C1-4An alkyl group;
R5is OR55；R55Is hydrogen, C1-4Alkyl radical, C2-4Alkenyl radical, C2-4Alkynyl, C3-6Cycloalkyl radical, C3-6cycloalkyl-C1-4Alkyl, phenyl or phenyl-C1-4An alkyl group;
R4and R6Each independently is hydrogen or C1-4An alkyl group.
3. The compound of claim 2, wherein,
R3is OR33；R33Is hydrogen, -CH3、-CH2CH3、-CH2CH2CH3、-CH(CH3)2、-CH2CH2CH2CH3、-CH(CH3)CH2CH3、-CH2CH(CH3)CH3or-C (CH)3)3；
R5Is OR55；R55Is hydrogen, -CH3、-CH2CH3、-CH2CH2CH3、-CH(CH3)2、-CH2CH2CH2CH3、-CH(CH3)CH2CH3、-CH2CH(CH3)CH3or-C (CH)3)3；
R4And R6Each independently is hydrogen, -CH3、-CH2CH3、-CH2CH2CH3、-CH(CH3)2、-CH2CH2CH2CH3、-CH(CH3)CH2CH3、-CH2CH(CH3)CH3or-C (CH)3)3。
4. The compound of claim 1, wherein,
n is 0, 1,2 or 3;
R7is halogen, cyano, hydroxy, nitro, amino, C1-4Alkyl radical, C1-4Alkoxy, halo C1-4Alkyl or halo C1-4An alkoxy group;
Ra、Rb、Rc、Rdand ReEach independently is hydrogen, halogen, cyano, hydroxy, mercapto, nitro, carboxyl, C1-4Alkyl radical, C1-4Alkoxy, halo C1-4Alkyl, halo C1-4Alkoxy radical, C2-4Alkenyl radical, C2-4Alkynyl, halo C2-4Alkenyl, halo C2-4Alkynyl, C2-4Alkenyloxy radical, C2-4Alkynyloxy, C3-6Cycloalkyl, halo C3-6Cycloalkyl radical, C3-6Cycloalkyl oxy, C3-6cycloalkyl-C1-4Alkyl, -S (═ O)x-C1-4Alkyl, -C (═ O) -C1-4Alkyl, -C (═ O) O-C1-4Alkyl, -NR8R9、-C(＝O)NR10R11Phenyl, benzyl or phenoxy;
R8、R9、R10and R11Each independently is hydrogen, C1-4Alkyl radical, C3-6Cycloalkyl radical, C3-6cycloalkyl-C1-4Alkyl, phenyl or phenyl-C1-4An alkyl group;
x is 0, 1 or 2.
5. The compound of claim 4, wherein,
n is 0, 1,2 or 3;
R7is fluorine, chlorine, bromine, iodine, cyano, hydroxyl, nitro, amino, -CH3、-CH2CH3、-CH2CH2CH3、-CH(CH3)2、-CH2CH2CH2CH3、-CH(CH3)CH2CH3、-CH2CH(CH3)CH3、-C(CH3)3、-OCH3、-OCH2CH3、-OCH2CH2CH3、-OCH(CH3)2、-CF3or-OCF3；
Ra、Rb、Rc、RdAnd ReEach independently is hydrogen, fluorine, chlorine, bromine, iodine, cyano, hydroxyl, mercapto, nitro, carboxyl, -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.ident.CH, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, -SCH3、-S(＝O)2CH3、-C(＝O)CH3、-C(＝O)OCH3、-NH2Phenyl, benzyl or phenoxy.
6. The compound according to any one of claims 1 to 5, which is a stereoisomer, a nitroxide or a salt thereof having or represented by formula (I-A):
Figure FDA0002087672160000021
7. the compound according to any one of claims 1 to 6, which is a stereoisomer, a nitroxide or a salt thereof having or represented by formula (II):
Figure FDA0002087672160000022
8. the compound according to any one of claims 1 to 6, which is a stereoisomer, a nitroxide or a salt thereof having or of the compound of formula (III):
Figure FDA0002087672160000031
9. the compound according to any one of claims 1 to 6, which is a stereoisomer, a nitroxide or a salt thereof having or of the compound of formula (IV):
Figure FDA0002087672160000032
10. the compound according to any one of claims 1 to 6, which is a stereoisomer, a nitroxide or a salt thereof having or represented by formula (V):
Figure FDA0002087672160000033
11. the compound according to any one of claims 1 to 10, which is a compound having one of the following structures or a stereoisomer, a nitroxide or a salt thereof of a compound having one of the following structures:
Figure FDA0002087672160000034
Figure FDA0002087672160000041
Figure FDA0002087672160000051
12. a composition comprising a compound of any one of claims 1-11.
13. Use of a compound according to any one of claims 1 to 11 or a composition according to claim 12 for controlling plant diseases.
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