CN108689951B

CN108689951B - Triazole compound and application thereof in agriculture

Info

Publication number: CN108689951B
Application number: CN201810296811.9A
Authority: CN
Inventors: 李义涛; 林健; 姚文强; 徐俊星; 伍阳; 刘新烁
Original assignee: Dongguan Hec Pesticides R&d Co ltd
Current assignee: Dongguan dongyangguang pesticide R & D Co., Ltd
Priority date: 2017-04-05
Filing date: 2018-04-04
Publication date: 2020-05-19
Anticipated expiration: 2038-04-04
Also published as: EP3606910A4; WO2018184579A1; CN108689951A; EP3606910A1

Abstract

The invention provides a triazole compound and application thereof in agriculture; specifically, the invention provides a compound shown as a formula (A) and a preparation method thereof; compositions and formulations containing these compounds and their use as fungicides; wherein R is¹、R²、R³、w、R⁴、R⁵、R⁶、R⁷、R⁸、R⁹、R^a、R^bAnd x has the meaning as given in the present invention.

Description

Triazole compound and application thereof in agriculture

Technical Field

The invention provides a novel triazole compound and a preparation method thereof; compositions containing these compounds and their use in agriculture.

Background

To achieve high crop yields, it is extremely important to control plant diseases caused by phytopathogenic fungi. Plant diseases that damage ornamental, vegetable, field, cereal and fruit crops can cause significant reductions in yield, leading to increased costs of consumption. For this purpose, there are many products commercially available, but there is a continuing need for new compounds that are more effective, more economical, less toxic, environmentally safer or have different sites of action.

The invention provides a novel triazole compound with bactericidal activity.

Disclosure of Invention

The invention aims to provide a novel bactericidal compound with remarkable control effect on plant diseases, a bactericidal composition containing the bactericidal compound, a preparation and application of the bactericidal composition.

In one aspect, the present invention provides a compound of formula (a) or stereoisomers, N-oxides, and salts thereof of a compound of formula (a):

wherein:

R¹and R²Each independently hydrogen, alkyl, alkoxyalkyl, alkenyl, alkynyl, cycloalkyl, heterocyclyl, aryl, heteroaryl, cycloalkylalkyl, heterocyclylalkyl, arylalkyl, halo-substituted arylalkyl, orA heteroarylalkyl group; or R¹、R²And the N atom to which they are attached, together form a heterocyclic or heteroaryl group;

wherein is represented by R¹、R²The heterocyclic or heteroaryl group formed with the N atom to which it is attached is optionally substituted with one or more groups selected from R¹²Substituted with the substituent(s);

R³is hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, amino, carboxyl, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl or haloaryl;

w is 0, 1 or 2;

R⁴is hydrogen, alkyl, -C (═ O) -alkyl, -alkylene-C (═ O) -alkyl, -C (═ O) -O-alkyl, -alkylene-C (═ O) -O-alkyl, alkoxy, alkenyl, alkynyl, cycloalkyl, heterocyclyl, aryl, arylalkyl, cycloalkylalkyl, or heterocyclylalkyl; r⁴Optionally substituted by one or more groups selected from R¹⁴Substituted with the substituent(s);

each R^aAnd R^bIndependently hydrogen, fluoro, chloro, bromo, iodo, hydroxy, cyano, nitro, amino, carboxy, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, or cycloalkyl;

or R^aAnd R^bTogether form oxo (═ O);

x is 0, 1,2,3, 4, 5 or 6;

R⁵、R⁶、R⁷、R⁸and R⁹Each independently is hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, amino, carboxyl, -C (═ O) -NR^cR^d、-NR^m-C(＝O)-Rⁿ、-NR^p(OR^q)、-C(＝O)-R^x、-C(＝O)-OR^yAlkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, hydroxy-substituted alkyl, amino-substituted alkyl, cyano-substituted alkyl, alkoxy, haloalkoxy, hydroxy-substituted alkoxy, amino-substituted alkoxy, cyano-substituted alkoxy, alkylamino, alkylthio or aryloxy;

wherein R is⁵、R⁶Optionally together with the carbon atoms to which they are attached form a phenyl or naphthyl ring, optionally substituted by 1,2,3, 4, 5, 6, 7, 8 or 9R¹⁵Substituted with the substituent(s);

wherein R is⁶、R⁷Optionally together with the carbon atoms to which they are attached form a phenyl or naphthyl ring, optionally substituted by 1,2,3, 4, 5, 6, 7, 8 or 9R¹⁶Substituted with the substituent(s);

wherein R is⁷、R⁸Optionally together with the carbon atoms to which they are attached form a phenyl or naphthyl ring, optionally substituted by 1,2,3, 4, 5, 6, 7, 8 or 9R¹⁷Substituted with the substituent(s);

wherein R is⁸、R⁹Optionally together with the carbon atoms to which they are attached form a phenyl or naphthyl ring, optionally substituted by 1,2,3, 4, 5, 6, 7, 8 or 9R¹⁸Substituted with the substituent(s);

wherein R is^pAnd R^qEach independently is hydrogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, cycloalkyl, heterocyclyl, aryl, heteroaryl OR-C (═ O) -OR^y1；

Wherein R is^c、R^d、R^m、Rⁿ、R^y1、R^xAnd R^yEach independently is hydrogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, cycloalkyl, heterocyclyl, aryl or heteroaryl;

wherein R is¹、R²、R³、R⁵、R⁶、R⁷、R⁸、R⁹、R^a、R^b、R^c、R^d、R^m、Rⁿ、R^xAnd R^yOptionally substituted by 1,2,3, 4, 5 or 6R¹⁰Substituted;

each R¹⁰、R¹²And R¹⁴Independently hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro,Amino, carboxyl, -C (═ O) -OR^z、C_1-6Alkyl radical, C_2-6Alkenyl radical, C_2-6Alkynyl, halo C_1-6Alkyl, halo C_2-6Alkenyl, halo C_2-6Alkynyl, hydroxy-substituted C_1-6Alkyl, amino substituted C_1-6Alkyl, cyano-substituted C_1-6Alkyl radical, C_1-6Alkoxy, halo C_1-6Alkoxy, hydroxy-substituted C_1-6Alkoxy, amino substituted C_1-6Alkoxy, cyano-substituted C_1-6Alkoxy radical, C_1-6Alkylamino radical, C_3-8Cycloalkyl radical, C_6-10Aryl or C_1-9A heteroaryl group;

wherein R is^zIs C_1-6Alkyl radical, C_2-6Alkenyl radical, C_2-6Alkynyl, halo C_1-6Alkyl, halo C_2-6Alkenyl, halo C_2-6Alkynyl, C_3-8Cycloalkyl, 3-12 membered heterocyclyl, C_6-10Aryl or C_1-9A heteroaryl group;

each R¹⁵、R¹⁶、R¹⁷And R¹⁸Independently hydrogen, halogen, cyano, nitro, alkyl, alkenyl, alkynyl, alkoxy, alkylamino, haloalkyl or haloalkoxy;

with the proviso that when R¹And R²Is methyl, R³Is hydrogen, w is 2, R⁴Is hydrogen, when x is 0, R⁷Is not unsubstituted or substituted phenoxy, unsubstituted or substituted pyridyloxy, or unsubstituted or substituted naphthyloxy.

In some of these embodiments, the present invention provides compounds of formula (I) or stereoisomers, N-oxides, and salts thereof of compounds of formula (I):

wherein:

R¹and R²Each independently is hydrogen, alkyl, alkoxyalkyl, alkenyl, alkynyl, cycloalkyl, heterocyclyl, aryl, heteroaryl, cycloalkylalkyl, heterocyclylalkyl, or a pharmaceutically acceptable salt thereof,Arylalkyl, halo-substituted arylalkyl or heteroarylalkyl; or R¹、R²And the N atom to which they are attached, together form a heterocyclic or heteroaryl group;

R⁴is hydrogen, alkyl, C (═ O) -alkyl, -alkylene-C (═ O) -alkyl, -C (═ O) -O-alkyl, -alkylene-C (═ O) -O-alkyl, alkoxy, alkenyl, alkynyl, cycloalkyl, heterocyclyl, aryl, arylalkyl, cycloalkylalkyl, or heterocyclylalkyl; r⁴Optionally substituted by one or more groups selected from R¹⁴Substituted with the substituent(s);

or R^aAnd R^bTogether form oxo (═ O);

x is 0, 1,2,3, 4, 5 or 6;

each R¹⁰、R¹²And R¹⁴Independently hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, amino,Carboxy, -C (═ O) -OR^z、C_1-6Alkyl radical, C_2-6Alkenyl radical, C_2-6Alkynyl, halo C_1-6Alkyl, halo C_2-6Alkenyl, halo C_2-6Alkynyl, hydroxy-substituted C_1-6Alkyl, amino substituted C_1-6Alkyl, cyano-substituted C_1-6Alkyl radical, C_1-6Alkoxy, halo C_1-6Alkoxy, hydroxy-substituted C_1-6Alkoxy, amino substituted C_1-6Alkoxy, cyano-substituted C_1-6Alkoxy radical, C_1-6Alkylamino radical, C_3-8Cycloalkyl radical, C_6-10Aryl or C_1-9A heteroaryl group;

In some of these embodiments, R¹And R²Each independently is hydrogen, C_1-6Alkyl radical, C_1-6Alkoxy radical C_1-6Alkyl radical, C_2-6Alkenyl radical, C_2-6Alkynyl, C_3-8Cycloalkyl radical, C_2-10Heterocyclic group, C_6-10Aryl radical, C_1-9Heteroaryl group, C_3-8Cycloalkyl radical C_1-6Alkyl radical, C_2-10Heterocyclyl radical C_1-6Alkyl radical, C_6-10Aryl radical C_1-6Alkyl, halogen substituted C_6-10Aryl radical C_1-6Alkyl or C_1-9Heteroaryl C_1-6An alkyl group; or R¹、R²Together with the N atom to which they are attached form a 3-8 membered heterocyclic group or C_1-9A heteroaryl group;

wherein is represented by R¹、R²Together with the N atom to which they are attached form a 3-8 membered heterocyclic group or C_1-9Heteroaryl is optionally substituted by one or more groups selected from R¹²Substituted with the substituent(s);

R³is hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, amino, carboxyl, C_1-6Alkyl radical, C_2-6Alkenyl radical, C_2-6Alkynyl, halo C_1-6Alkyl, halo C_2-6Alkenyl, halo C_2-6Alkynyl, C_6-10Aryl or halo C_6-10An aryl group;

R⁴is hydrogen, C_1-6Alkyl, -C (═ O) -C_1-6Alkyl, -C_1-6alkylene-C (═ O) -C_1-6Alkyl, -C (═ O) -O-C_1-6Alkyl, -C_1-6alkylene-C (═ O) -O-C_1-6Alkyl radical, C_1-6Alkoxy radical, C_2-6Alkenyl radical, C_2-6Alkynyl, C_3-8Cycloalkyl, 3-12 membered heterocyclyl, C_6-10Aryl radical, C_6-10Aryl radical C_1-6Alkyl radical, C_3-8Cycloalkyl radical C_1-6Alkyl or C_2-10Heterocyclyl radical C_1-6An alkyl group; r⁴Optionally substituted by one or more groups selected from R¹⁴Substituted with the substituent(s);

each R^aAnd R^bIndependently hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, amino, carboxyl, C_1-6Alkyl radical, C_2-6Alkenyl radical, C_2-6Alkynyl, halo C_1-6Alkyl, halo C_2-6Alkenyl, halo C_2-6Alkynyl or C_3-8A cycloalkyl group;

or R^aAnd R^bTogether form oxo (═ O);

x is 0, 1,2,3, 4, 5 or 6;

R⁵、R⁶、R⁷、R⁸and R⁹Each independently is hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, amino, carboxyl, -C (═ O) -NR^cR^d、-NR^m-C(＝O)-Rⁿ、-NR^p(OR^q)、-C(＝O)-R^x、-C(＝O)-OR^y、C_1-6Alkyl radical, C_2-6Alkenyl radical, C_2-6Alkynyl, halo C_1-6Alkyl, halo C_2-6Alkenyl, halo C_2-6Alkynyl, hydroxy-substituted C_1-6Alkyl, amino substituted C_1-6Alkyl, cyano-substituted C_1-6Alkyl radical, C_1-6Alkoxy, halo C_1-6Alkoxy, hydroxy-substituted C_1-6Alkoxy, amino substituted C_1-6Alkoxy, cyano-substituted C_1-6Alkoxy radical, C_1-6Alkylamino radical, C_1-6Alkylthio or C_6-10An aryloxy group;

wherein R is^pAnd R^qEach independently is hydrogen, C_1-6Alkyl radical, C_2-6Alkenyl radical, C_2-6Alkynyl, halo C_1-6Alkyl, halo C_2-6Alkenyl, halo C_2-6Alkynyl, C_3-6Cycloalkyl, 3-8 membered heterocyclyl, C_6-10Aryl radical, C_1-6Heteroaryl OR-C (═ O) -OR^y1；

Wherein R is^c、R^d、R^m、Rⁿ、R^y1、R^xAnd R^yEach independently is hydrogen, C_1-6Alkyl radical, C_2-6Alkenyl radical, C_2-6Alkynyl, halo C_1-6Alkyl, halo C_2-6Alkenyl, halo C_2-6Alkynyl, C_3-6Cycloalkyl, 3-8 membered heterocyclyl, C_6-10Aryl or C_1-5A heteroaryl group;

each R¹⁰、R¹²And R¹⁴Independently hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, amino, carboxyl, -C (═ O) -OR^z、C_1-4Alkyl radical, C_2-4Alkenyl radical, C_2-4Alkynyl, halo C_1-4Alkyl, halo C_2-4Alkenyl, halo C_2-4Alkynyl, hydroxy-substituted C_1-4Alkyl, amino substituted C_1-4Alkyl, cyano-substituted C_1-4Alkyl radical, C_1-4Alkoxy, halo C_1-4Alkoxy, hydroxy-substituted C_1-4Alkoxy, amino substituted C_1-4Alkoxy, cyano-substituted C_1-4Alkoxy radical, C_1-4Alkylamino radical, C_3-6Cycloalkyl radical, C_6-10Aryl or C_1-5A heteroaryl group;

wherein R is^zIs C_1-4Alkyl radical, C_2-4Alkenyl radical, C_2-4Alkynyl, halo C_1-4Alkyl, halo C_2-4Alkenyl, halo C_2-4Alkynyl, C_3-6Cycloalkyl, 3-8 membered heterocyclyl, C_6-10Aryl or C_1-5A heteroaryl group;

each R¹⁵、R¹⁶、R¹⁷And R¹⁸Independently hydrogen, halogen, cyano, nitro, C_1-6Alkyl radical, C_2-6Alkenyl radical, C_2-6Alkynyl, C_1-6Alkoxy radical, C_1-6Alkylamino, halogeno C_1-6Alkyl or halo C_1-6An alkoxy group;

In other embodiments, R¹And R²Each independently is hydrogen, C_1-4Alkyl radical, C_1-3Alkoxy radical C_1-3Alkyl radical, C_2-4Alkenyl radical, C_2-4Alkynyl, C_3-6Cycloalkyl radical, C_2-6Heterocyclic group, C_6-10Aryl radical, C_1-5Heteroaryl group, C_3-6Cycloalkyl radical C_1-4Alkyl radical, C_2-6Heterocyclyl radical C_1-4Alkyl radical, C_6-10Aryl radical C_1-4Alkyl, halogen substituted C_6-10Aryl radical C_1-4Alkyl or C_1-5Heteroaryl C_1-4An alkyl group; or R¹、R²And the N atom to which it is attached form the following subformula:

wherein p is₁And p₂Each independently is 0, 1 or 2;

q is 0, 1 or 2;

X¹are-O-, -S- (O) -, -S- (O)₂-or-NH-;

each X²、X³、X⁴And X⁵Independently is N or CH;

wherein sub-formulae (i), (ii), (iii) or (iv) are optionally substituted with one or more groups selected from R¹²Substituted with the substituent(s).

In other embodiments, R¹And R²Each independently is hydrogen, -CH₃、-CH₂CH₃、-CH₂CH₂CH₃、-CH(CH₃)₂、-CH₂CH＝CH₂、-CH₂CH₂CH＝CH₂、-CH₂CH＝CHCH₃、-CH₂-O-CH₃、-CH₂CH₂-O-CH₃、-CH₂-O-CH₂CH₃、-CH₂CH₂-O-CH₂CH₃Cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, benzyl, 4-fluorobenzyl or 4-cyanobenzyl;

or R¹、R²And the N atom to which it is attached form the following subformula:

in some of these embodiments, R³Is hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, amino, carboxyl, C_1-4Alkyl radical, C_2-4Alkenyl radical, C_2-4Alkynyl, halo C_1-4Alkyl, halo C_2-4Alkenyl, halo C_2-4Alkynyl, C_6-10Aryl or halo C_6-10And (4) an aryl group.

In other embodiments, R³Is hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, amino, carboxyl, -CH₃、-CHF₂、-CH₂F、-CH₂CH₃、-CH₂CH₂F、-CH₂CHF₂、-CH₂CH₂CH₃、-CH(CH₃)₂、-C(CH₃)₃Phenyl, 2-fluorophenyl, 3-fluorophenyl or 4-fluorophenyl.

In some of these embodiments, R⁴Is hydrogen, C_1-4Alkyl, -C (═ O) -C_1-4Alkyl, -C_1-4alkylene-C (═ O) -C_1-4Alkyl, -C (═ O) -O-C_1-4Alkyl, -C_1-4alkylene-C (═ O) -O-C_1-4Alkyl radical, C_1-4Alkoxy radical, C_2-4Alkenyl radical, C_2-4Alkynyl, C_3-6CycloalkanesA group, a 3-to 10-membered heterocyclic group, C_6-10Aryl radical, C_6-10Aryl radical C_1-3Alkyl radical, C_3-6Cycloalkyl radical C_1-3Alkyl or C_2-6Heterocyclyl radical C_1-3An alkyl group; wherein R is⁴Optionally substituted by 1,2,3, 4 or 5 substituents selected from R¹⁴Substituted with the substituent(s); each R¹⁴Independently hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, amino, carboxyl, -C (═ O) -O-C_1-3Alkyl radical, C_1-3Alkyl radical, C_1-3Alkoxy radical, C_3-6Cycloalkyl or phenyl.

In other embodiments, R⁴Is hydrogen, -CH₃、-CHF₂、-CH₂(CN)、-CH₂CH₃、-CH(CN)CH₃、-CH₂CHF₂、-CH₂CH₂CH₃、-CH(CH₃)₂、-CH₂CH₂CH₂CH₃、-C(CH₃)₃、-CH₂CH＝CH₂、-CH₂CH₂CH＝CH₂、-CH₂CH＝CHCH₃、-C(＝O)-CH₃、-C(＝O)-CH₂CH₃、-C(＝O)-OCH₃、-C(＝O)-OCH₂CH₃、-CH₂-C(＝O)-OCH₃、-CH₂-C(＝O)-OCH₂CH₃、-OCH₃、-OCH₂CH₃、-OCH₂CH₂CH₃、-OCH(CH₃)₂Cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl or benzyl; or R⁴Is of the sub-structure:

in some of these embodiments, R⁵、R⁶、R⁷、R⁸And R⁹Each independently of the others is hydrogen, fluorine, chlorine, bromine, iodine, hydroxylRadical, cyano, nitro, amino, carboxyl, -C (═ O) -NR^cR^d、-NR^m-C(＝O)-Rⁿ、-NR^p(OR^q)、-C(＝O)-R^x、-C(＝O)-OR^y、C_1-4Alkyl radical, C_2-4Alkenyl radical, C_2-4Alkynyl, halo C_1-4Alkyl, halo C_2-4Alkenyl, halo C_2-4Alkynyl, hydroxy-substituted C_1-4Alkyl, amino substituted C_1-4Alkyl, cyano-substituted C_1-4Alkyl radical, C_1-4Alkoxy, halo C_1-4Alkoxy, hydroxy-substituted C_1-4Alkoxy, amino substituted C_1-4Alkoxy, cyano-substituted C_1-4Alkoxy radical, C_1-4Alkylamino radical, C_1-4Alkylthio or C_6-10An aryloxy group;

wherein R is^pAnd R^qEach independently is hydrogen, C_1-3Alkyl radical, C_2-4Alkenyl radical, C_2-4Alkynyl, halo C_1-3Alkyl, halo C_2-4Alkenyl, halo C_2-4Alkynyl, C_3-6Cycloalkyl, 3-6 membered heterocyclyl, C_6-10Aryl radical, C_1-5Heteroaryl OR-C (═ O) -OR^y1；

Wherein R is^c、R^d、R^m、Rⁿ、R^y1、R^xAnd R^yEach independently is hydrogen, C_1-4Alkyl radical, C_2-4Alkenyl radical, C_2-4Alkynyl, halo C_1-4Alkyl, halo C_2-4Alkenyl, halo C_2-4Alkynyl, C_3-6Cycloalkyl, 3-6 membered heterocyclyl, C_6-10Aryl or C_1-5A heteroaryl group;

wherein R is⁵、R⁶、R⁷、R⁸、R⁹、R^c、R^d、R^m、Rⁿ、R^y1、R^xAnd R^yOptionally substituted by 1,2,3, 4, 5 or 6R¹⁰Substituted; wherein each R¹⁰Have the meaning as described herein;

each R¹⁵、R¹⁶、R¹⁷And R¹⁸Independently hydrogen, halogen, cyano, nitro, C_1-4Alkyl radical, C_2-4Alkenyl radical, C_2-4Alkynyl, C_1-4Alkoxy radical, C_1-4Alkylamino, halogeno C_1-4Alkyl or halo C_1-4An alkoxy group.

In other embodiments, R⁵、R⁶、R⁷、R⁸And R⁹Each independently is hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, amino, carboxyl, -CH₃、-CH₂CH₃、-CH₂CH₂CH₃、-CH(CH₃)₂、-CH₂F、-CHF₂、-CF₃、-CH₂CH₂F、-CH₂CHF₂、-CH₂CF₃、-CH＝CH₂、-CH₂-CH＝CH₂、-OCH₃、-OCH₂CH₃、-OCH₂CH₂CH₃、-OCH(CH₃)₂、-OCF₃、-OCH₂CF₃、-NH-C(＝O)-CH₃、-NH-C(＝O)-CH₂CH₃、-NH-OH、-N(OH)-C(＝O)-OCH₃、-N(OC(＝O)OCH₃)-C(＝O)-OCH₃、-C(＝O)-CH₃、-C(＝O)-CH₂CH₃、-C(＝O)-OCH₃、-C(＝O)-OCH₂CH₃、-SCH₃、-SCH₂CH₃、-SCH₂CH₂CH₃、-SCH(CH₃)₂Phenoxy, halophenoxy, C_1-4Alkyl-substituted phenoxy, C_1-4Alkoxy-substituted phenoxy, C_1-4Haloalkyl-substituted phenoxy or C_1-4Haloalkoxy-substituted phenoxy.

In some of the embodiments of the present invention,

is of the sub-structure:

wherein:

each R⁵、R⁷、R⁸、R⁹、R^15a、R^15b、R^15c、R^15d、R^16a、R^16b、R^16c、R^16d、R^16e、R^16f、R^18a、R^18b、R^18cAnd R^18dIndependently hydrogen, halogen, cyano, nitro, C_1-6Alkyl radical, C_2-6Alkenyl radical, C_2-6Alkynyl, C_1-6Alkoxy radical, C_1-6Alkylamino, halogeno C_1-6Alkyl or halo C_1-6An alkoxy group.

In other embodiments, each R is⁵、R⁷、R⁸、R⁹、R^15a、R^15b、R^15c、R^15d、R^16a、R^16b、R^16c、R^16d、R^16e、R^16f、R^18a、R^18b、R^18cAnd R^18dIndependently of one another hydrogen, halogen, cyanoNitro group, C_1-4Alkyl radical, C_2-4Alkenyl radical, C_2-4Alkynyl, C_1-4Alkoxy radical, C_1-4Alkylamino, halogeno C_1-4Alkyl or halo C_1-4An alkoxy group.

In other embodiments, each R is⁵、R⁷、R⁸、R⁹、R^15a、R^15b、R^15c、R^15d、R^16a、R^16b、R^16c、R^16d、R^16e、R^16f、R^18a、R^18b、R^18cAnd R^18dIndependently hydrogen, fluorine, chlorine, bromine, iodine, cyano, nitro, methyl, ethyl, n-propyl, isopropyl, tert-butyl, vinyl, propenyl, allyl, ethynyl, propynyl, propargyl, methoxy, ethoxy, isopropoxy, tert-butoxy, difluoromethyl, trifluoromethyl, difluoromethoxy, trifluoromethoxy, dimethylamino or diethylamino.

In some of these embodiments, each R is^aAnd R^bIndependently hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, amino, carboxyl, C_1-4Alkyl radical, C_2-4Alkenyl radical, C_2-4Alkynyl, halo C_1-4Alkyl, halo C_2-4Alkenyl, halo C_2-4Alkynyl or C_3-6A cycloalkyl group;

or R^aAnd R^bTogether form oxo (═ O).

In other embodiments, each R is^aAnd R^bIndependently hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, amino, carboxyl, -CH₃、-CH₂CH₃、-CH₂CH₂CH₃、-CH(CH₃)₂、-CH₂F、-CHF₂、-CF₃、-CH₂CH₂F、-CH₂CHF₂、-CH₂CF₃、-CH＝CH₂、-CH₂-CH＝CH₂Cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl;

or R^aAnd R^bTogether shapeOxo (═ O).

In another aspect, the present invention provides a process for preparing a compound of formula (I), comprising:

reacting a compound shown in a formula (e) with disubstituted amino sulfonyl chloride to obtain a compound shown in a formula (I):

wherein: r¹、R²、R³、R⁴、R⁵、R⁶、R⁷、R⁸、R⁹、R^a、R^bAnd x has the meaning as given in the present invention.

In another aspect, the present invention provides a compound that is a compound represented by formula (II) or a stereoisomer, a nitroxide, and a salt of a compound represented by formula (II):

wherein: r³、R⁵、R⁶、R⁷、R⁸、R⁹、R^a、R^bAnd x has the meaning as given in the present invention.

In another aspect, the invention provides a composition comprising a compound of the invention.

In some embodiments, the composition further comprises an agriculturally acceptable surfactant and a 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 the control of plant diseases.

In some of these embodiments, the plant disease is caused by a plant pathogenic fungus.

The compounds of formula (a) or (I) may exist in different stereoisomers or optical isomers or tautomeric forms. The invention encompasses all such isomers and tautomers and mixtures thereof in various ratios, as well as isotopic forms such as heavy hydrogen-containing compounds.

Isotopically enriched compounds have the structure depicted by the formulae given herein, except that one or more atoms are replaced by an atom having a selected atomic mass or mass number. Exemplary isotopes that can be incorporated into compounds of the invention include isotopes of hydrogen, carbon, nitrogen, oxygen, phosphorus, sulfur, fluorine and chlorine, such as²H，³H，¹¹C，¹³C，¹⁴C，¹⁵N，¹⁷O，¹⁸O，¹⁸F，³¹P，³²P，³⁵S，³⁶Cl and¹²⁵I。

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.

The foregoing has outlined only certain aspects of the present invention and is not intended to be limited in these or other respects to the details described herein.

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 found in the descriptions of "Organic Chemistry", Thomas Sorrell, University Science Books, Sausaltito: 1999, and "March's Advanced Organic Chemistry" by Michael B.Smith and JerryMarch, 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-Hilldictionary 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" C_1-6Alkyl "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 "alkylene" denotes a saturated divalent hydrocarbon radical resulting from the removal of two hydrogen atoms from a saturated straight or branched chain hydrocarbon. Unless otherwise specified, the alkylene group contains 1 to 12 carbon atoms. In one embodiment, the alkylene group contains 1 to 8 carbon atoms; in one embodiment, the alkylene group contains 1 to 6 carbon atoms; in another embodiment, the alkylene group contains 1 to 4 carbon atoms; in yet another embodiment, the alkylene group contains 1 to 3 carbon atoms; in yet another embodiment, the alkylene group contains 1 to 2 carbon atoms. Examples of this include methylene (-CH)₂-, ethylene (-CH)₂CH₂-, propylene (-CH)₂CH₂CH₂-)，-CH(CH₃)CH₂-，-C(CH₃)₂-，-CH₂CH₂CH(CH₃)-，-CH₂CH₂C(CH₃)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 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 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) 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.

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 "alkylthio" means an alkyl group attached to the rest of the molecule through a sulfur atom, wherein the alkyl group has the meaning as described herein. Examples of alkylthio groups include, but are not limited to, -SCH₃、-SCH₂CH₃、-SCH₂CH₂CH₃、-SCH(CH₃)₂And so on.

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 terms "heterocyclyl" and "heterocycle" are used interchangeably herein and refer to a saturated or partially unsaturated monocyclic, bicyclic, or tricyclic ring containing 3 to 15 ring atoms, wherein no aromatic ring is included in the monocyclic, bicyclic, or tricyclic ring, and at least one ring atom is selected from the group consisting of nitrogen, sulfur, and oxygen atoms. Unless otherwise specified, heterocyclyl may be carbon-or nitrogen-based, and-CH₂-the group may optionally be replaced by-C (═ O) -. The sulfur atom of the ring may optionally be oxidized to the S-oxide. The nitrogen atom of the ring may optionally be oxidized to an N-oxygen compound. Examples of heterocyclyl groups include, but are not limited to, oxiranyl, azetidinyl, oxetanyl, thietanyl, pyrrolidinyl (e.g., 2-pyrrolidinyl), 2-pyrrolinyl, 3-pyrrolinyl, pyrazolidinyl, imidazolinyl, imidazolidinyl, tetrahydrofuranyl, dihydrofuranyl, tetrahydrothienyl, dihydrothienyl, 1, 3-dioxocyclopentyl, dithiocyclopentyl, tetrahydropyranyl, dihydropyranyl, 2H-pyranyl, 4H-pyranyl, tetrahydrothiopyranyl, piperidinyl (2-piperidinyl, 3-piperidinyl, 4-piperidinyl), morpholinyl, thiomorpholinyl, (1-oxo) -thiomorpholinyl, (1, 1-dioxo) -thiomorpholinyl, piperazinyl, dioxanyl, dithianyl, thioxanyl, homopiperazinyl, homopiperidinyl, oxepanyl, thiepanyl, 2-oxa-5-azabicyclo [2.2.1]Hept-5-yl, tetrahydropyridinyl. In heterocyclic radicals of-CH₂Examples of-groups substituted by-C (═ O) -include, but are not limited to, 2-oxopyrrolidinyl, oxo-1, 3-thiazolidinyl, 2-piperidinonyl, 3, 5-dioxopiperidinyl. Examples of sulfur atoms in heterocyclic groups that are oxidized include, but are not limited to, sulfolane, 1, 1-dioxothiomorpholinyl. Said heterocyclyl group being optionally substituted by one or more of the substituents described hereinSubstituted by a radical.

The terms "3-12 membered heterocyclyl", "3-10 membered heterocyclyl", "3-8 membered heterocyclyl" or "3-6 membered heterocyclyl", wherein "3-12 membered", "3-10 membered", "3-8 membered" or "3-6 membered" typically describe the number of ring-forming atoms in the molecule. For example, piperidinyl is 6-membered heterocyclyl.

The term "unsaturated" as used herein means that the group contains one or more unsaturations.

The term "heteroatom" refers to O, S, N, P and Si, including N, S and any oxidation state form of P; primary, secondary, tertiary amines and quaternary ammonium salt forms; or a form in which a hydrogen on a nitrogen atom in the heterocycle is substituted, for example, N (like N in 3, 4-dihydro-2H-pyrrolyl), NH (like NH in pyrrolidinyl) or NR (like NR in N-substituted pyrrolidinyl).

The term "halogen" refers to fluorine (F), chlorine (Cl), bromine (Br) or iodine (I).

The term "aryl" denotes monocyclic, bicyclic and tricyclic carbon ring systems containing 6 to 14 ring atoms, or 6 to 12 ring atoms, or 6 to 10 ring atoms, wherein at least one ring system is aromatic, wherein each ring system comprises a ring of 3 to 7 atoms with one or more attachment points to the rest of the molecule. The term "aryl" may be used interchangeably with the term "aromatic ring". Examples of the aryl group may include phenyl, indenyl, naphthyl and anthryl. The aryl group is optionally substituted with one or more substituents described herein.

The term "heteroaryl" denotes monocyclic, bicyclic and tricyclic ring systems containing 5 to 12 ring atoms, or 5 to 10 ring atoms, or 5 to 6 ring atoms, wherein at least one ring system is aromatic and at least one ring system contains one or more heteroatoms, wherein each ring system contains a ring of 5 to 7 atoms with one or more attachment points to the rest of the molecule. The term "heteroaryl" may be used interchangeably with the terms "heteroaromatic ring" or "heteroaromatic compound". The heteroaryl group is optionally substituted with one or more substituents described herein. In one embodiment, a heteroaryl group of 5-10 atoms contains 1,2,3, or 4 heteroatoms independently selected from O, S, and N.

Examples of heteroaryl groups include, but are not limited to, 2-furyl, 3-furyl, N-imidazolyl, 2-imidazolyl, 4-imidazolyl, 5-imidazolyl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, N-pyrrolyl, 2-pyrrolyl, 3-pyrrolyl, 2-pyridyl, 3-pyridyl, 4-pyridyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, pyridazinyl (e.g., 3-pyridazinyl), 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, tetrazolyl (e.g., 5-tetrazolyl), triazolyl (e.g., 2-triazolyl and 5-triazolyl), 2-thienyl, 3-thienyl, pyrazolyl, isothiazolyl, 1,2, 3-oxadiazolyl, 1,2, 5-oxadiazolyl, 1,2, 4-oxadiazolyl, 1,2, 3-triazolyl, 1,2, 3-thiadiazolyl, 1,3, 4-thiadiazolyl, 1,2, 5-thiadiazolyl, pyrazinyl, 1,3, 5-triazinyl, pyrimidinonyl, pyridonyl; the following bicyclic rings are also included, but are in no way limited to these: benzimidazolyl, benzofuranyl, benzotetrahydrofuranyl, benzothienyl, indolyl (e.g., 2-indolyl), benzopiperidinyl, and the like.

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⁺(R¹⁹R²⁰R²¹R²²) Ammonium cation of (2), wherein R is¹⁹、R²⁰、R²¹And R²²Independently selected from hydrogen, C₁-C₆Alkyl and C₁-C₆A hydroxyalkyl group. Salts of compounds of formula (I) may be prepared by treating a compound of formula (I) with a metal hydroxide (e.g., sodium hydroxide) or an amine (e.g., 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.

Detailed description of the Compounds of the invention

In one aspect, the invention provides compounds of formula (a) or stereoisomers, nitroxides and salts of compounds of formula (a):

wherein:

R¹and R²Each independently is hydrogen, alkyl, alkoxyalkyl, alkenyl, alkynyl, cycloalkyl, heterocyclyl, aryl, heteroaryl, cycloalkylalkyl, heterocyclylalkyl, arylalkyl, halo-substituted arylalkyl, or heteroarylalkyl; or R¹、R²And the N atom to which they are attached, together form a heterocyclic or heteroaryl group;

w is 0, 1 or 2;

or R^aAnd R^bTogether form oxo (═ O);

x is 0, 1,2,3, 4, 5 or 6;

wherein R is⁸、R⁹Optionally together with the carbon atoms to which they are attached form a benzene or naphthalene ring, optionally substituted by 1,2,3, 4, 5, 6, 7, 8 or 9From R¹⁸Substituted with the substituent(s);

wherein R is¹、R²、R³、R⁵、R⁶、R⁷、R⁸、R⁹、R^a、R^b、R^c、R^d、R^m-、Rⁿ、R^xAnd R^yOptionally substituted by 1,2,3, 4, 5 or 6R¹⁰Substituted;

each R¹⁰、R¹²And R¹⁴Independently hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, amino, carboxyl, -C (═ O) -OR^z、C_1-6Alkyl radical, C_2-6Alkenyl radical, C_2-6Alkynyl, halo C_1-6Alkyl, halo C_2-6Alkenyl, halo C_2-6Alkynyl, hydroxy-substituted C_1-6Alkyl, amino substituted C_1-6Alkyl, cyano-substituted C_1-6Alkyl radical, C_1-6Alkoxy, halo C_1-6Alkoxy, hydroxy-substituted C_1-6Alkoxy, amino substituted C_1-6Alkoxy, cyano-substituted C_1-6Alkoxy radical, C_1-6Alkylamino radical, C_3-8Cycloalkyl radical, C_6-10Aryl or C_1-9A heteroaryl group;

In some of these embodiments, the present invention provides compounds of formula (I), stereoisomers, N-oxides, and salts thereof:

wherein:

or R^aAnd R^bTogether form oxo (═ O);

x is 0, 1,2,3, 4, 5 or 6;

wherein R is⁸、R⁹Optionally together with the carbon atoms to which they are attached form a benzene or naphthalene ring, optionally substituted by 1,2,3, 4, 5, 6, 7, 8 or 9 substituents selected fromR¹⁸Substituted with the substituent(s);

wherein R is¹²Have the meaning as described in the present invention.

In some of these embodiments, R³Is hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, amino, carboxyl, C_1-6Alkyl radical, C_2-6Alkenyl radical, C_2-6Alkynyl, halo C_1-6Alkyl, halo C_2-6Alkenyl, halo C_2-6Alkynyl, C_6-10Aryl or halo C_6-10And (4) an aryl group.

In some of these embodiments, R⁴Is hydrogen, C_1-6Alkyl, -C (═ O) -C_1-6Alkyl, -C_1-6alkylene-C (═ O) -C_1-6Alkyl, -C (═ O) -O-C_1-6Alkyl, -C_1-6alkylene-C (═ O) -O-C_1-6Alkyl radical, C_1-6Alkoxy radical, C_2-6Alkenyl radical, C_2-6Alkynyl, C_3-8Cycloalkyl, 3-12 membered heterocyclyl, C_6-10Aryl radical, C_6-10Aryl radical C_1-6Alkyl radical, C_3-8Cycloalkyl radical C_1-6Alkyl or C_2-10Heterocyclyl radical C_1-6An alkyl group; r⁴Optionally substituted by one or more groups selected from R¹⁴Substituted with the substituent(s);

wherein R is¹⁴Have the meaning as described in the present invention.

In some of these embodiments, each R is^aAnd R^bIndependently hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, amino, carboxyl, C_1-6Alkyl radical, C_2-6Alkenyl radical, C_2-6Alkynyl, halo C_1-6Alkyl, halo C_2-6Alkenyl, halo C_2-6Alkynyl or C_3-8A cycloalkyl group;

or R^aAnd R^bTogether form oxo (═ O).

In some of these embodiments, x is 0, 1,2,3, 4, 5, or 6.

In some of these embodiments, R⁵、R⁶、R⁷、R⁸And R⁹Each independently is hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, amino, carboxyl, -C (═ O) -NR^cR^d、-NR^m-C(＝O)-Rⁿ、-NR^p(OR^q)、-C(＝O)-R^x、-C(＝O)-OR^y、C_1-6Alkyl radical, C_2-6Alkenyl radical, C_2-6Alkynyl, halo C_1-6Alkyl, halo C_2-6Alkenyl, halo C_2-6Alkynyl, hydroxy-substituted C_1-6Alkyl, amino substituted C_1-6Alkyl, cyano-substituted C_1-6Alkyl radical, C_1-6Alkoxy, halo C_1-6Alkoxy, hydroxy-substituted C_1-6Alkoxy, amino substituted C_1-6Alkoxy, cyano-substituted C_1-6Alkoxy radical,C_1-6Alkylamino radical, C_1-6Alkylthio or C_6-10An aryloxy group;

wherein R is^c、R^d、R^m、Rⁿ、R^p、R^q、R¹⁵、R¹⁶、R¹⁷、R¹⁸、R^xAnd R^yHave the meaning as described in the present invention.

In some of these embodiments, R^pAnd R^qEach independently is hydrogen, C_1-6Alkyl radical, C_2-6Alkenyl radical, C_2-6Alkynyl, halo C_1-6Alkyl, halo C_2-6Alkenyl, halo C_2-6Alkynyl, C_3-6Cycloalkyl, 3-8 membered heterocyclyl, C_6-10Aryl radical, C_1-6Heteroaryl OR-C (═ O) -OR^y1；

Wherein R is^y1Have the meaning as described in the present invention.

In some of these embodiments, R^c、R^d、R^m、Rⁿ、R^y1、R^xAnd R^yEach independently is hydrogen, C_1-6Alkyl radical, C_2-6Alkenyl radical, C_2-6Alkynyl, halo C_1-6Alkyl, halo C_2-6Alkenyl, halo C_2-6Alkynyl, C_3-6Cycloalkyl, 3-8 membered heterocyclyl, C_6-10Aryl or C_1-5A heteroaryl group.

In some of these embodiments, R is¹、R²、R³、R⁵、R⁶、R⁷、R⁸、R⁹、R^a、R^b、R^c、R^d、R^m、Rⁿ、R^xAnd R^yOptionally substituted by 1,2,3, 4, 5 or 6R¹⁰Substituted;

wherein each R¹⁰Have the meaning as described in the present invention.

In some of these embodiments, each R is¹⁰、R¹²And R¹⁴Independently hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, amino, carboxyl, -C (═ O) -OR^z、C_1-4Alkyl radical, C_2-4Alkenyl radical, C_2-4Alkynyl, halo C_1-4Alkyl, halo C_2-4Alkenyl, halo C_2-4Alkynyl, hydroxy-substituted C_1-4Alkyl, amino substituted C_1-4Alkyl, cyano-substituted C_1-4Alkyl radical, C_1-4Alkoxy, halo C_1-4Alkoxy, hydroxy-substituted C_1-4Alkoxy, amino substituted C_1-4Alkoxy, cyano-substituted C_1-4Alkoxy radical, C_1-4Alkylamino radical, C_3-6Cycloalkyl radical, C_6-10Aryl or C_1-5A heteroaryl group;

wherein each R^zHave the meaning as described in the present invention.

In some of these embodiments, R^zIs C_1-4Alkyl radical, C_2-4Alkenyl radical, C_2-4Alkynyl, halo C_1-4Alkyl, halo C_2-4Alkenyl, halo C_2-4Alkynyl, C_3-6Cycloalkyl, 3-8 membered heterocyclyl, C_6-10Aryl or C_1-5A heteroaryl group.

WhereinIn some embodiments, each R is¹⁵、R¹⁶、R¹⁷And R¹⁸Independently hydrogen, halogen, cyano, nitro, C_1-6Alkyl radical, C_2-6Alkenyl radical, C_2-6Alkynyl, C_1-6Alkoxy radical, C_1-6Alkylamino, halogeno C_1-6Alkyl or halo C_1-6An alkoxy group.

In some of these embodiments, R¹And R²Each independently is hydrogen, C_1-4Alkyl radical, C_1-3Alkoxy radical C_1-3Alkyl radical, C_2-4Alkenyl radical, C_2-4Alkynyl, C_3-6Cycloalkyl radical, C_2-6Heterocyclic group, C_6-10Aryl radical, C_1-5Heteroaryl group, C_3-6Cycloalkyl radical C_1-4Alkyl radical, C_2-6Heterocyclyl radical C_1-4Alkyl radical, C_6-10Aryl radical C_1-4Alkyl, halogen substituted C_6-10Aryl radical C_1-4Alkyl or C_1-5Heteroaryl C_1-4An alkyl group; or R¹、R²And the N atom to which it is attached form the following subformula:

wherein p is₁And p₂Each independently is 0, 1 or 2;

q is 0, 1 or 2;

X¹are-O-, -S- (O) -, -S- (O)₂-or-NH-;

each X²、X³、X⁴And X⁵Independently is N or CH;

wherein sub-formulae (i), (ii), (iii) or (iv) are optionally substituted with one or more groups selected from R¹²Substituted with the substituent(s);

wherein each R¹²Have the meaning as described in the present invention.

In some of these embodiments, R⁴Is hydrogen, C_1-4Alkyl, -C (═ O) -C_1-4Alkyl, -C_1-4alkylene-C (═ O) -C_1-4Alkyl, -C (═ O) -O-C_1-4Alkyl, -C_1-4alkylene-C (═ O) -O-C_1-4Alkyl radical, C_1-4Alkoxy radical, C_2-4Alkenyl radical, C_2-4Alkynyl, C_3-6Cycloalkyl, 3-10 membered heterocyclyl, C_6-10Aryl radical, C_6-10Aryl radical C_1-3Alkyl radical、C_3-6Cycloalkyl radical C_1-3Alkyl or C_2-6Heterocyclyl radical C_1-3An alkyl group; r⁴Optionally substituted by 1,2,3, 4 or 5 substituents selected from R¹⁴Substituted with the substituent(s);

wherein each R¹⁴Have the meaning as described in the present invention.

In some of these embodiments, each R is¹⁴Independently hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, amino, carboxyl, -C (═ O) -O-C_1-3Alkyl radical, C_1-3Alkyl radical, C_1-3Alkoxy radical, C_3-6Cycloalkyl or phenyl.

In some of these embodiments, R⁴Is hydrogen, -CH₃、-CHF₂、-CH₂(CN)、-CH₂CH₃、-CH(CN)CH₃、-CH₂CHF₂、-CH₂CH₂CH₃、-CH(CH₃)₂、-CH₂CH₂CH₂CH₃、-C(CH₃)₃、-CH₂CH＝CH₂、-CH₂CH₂CH＝CH₂、-CH₂CH＝CHCH₃、-C(＝O)-CH₃、-C(＝O)-CH₂CH₃、-C(＝O)-OCH₃、-C(＝O)-OCH₂CH₃、-CH₂-C(＝O)-OCH₃、-CH₂-C(＝O)-OCH₂CH₃、-OCH₃、-OCH₂CH₃、-OCH₂CH₂CH₃、-OCH(CH₃)₂Cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl or benzyl; or R⁴Is of the sub-structure:

in some of these embodiments, each R is^aAnd R^bIndependently hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, amino, carboxyl, C_1-4Alkyl radical, C_2-4Alkenyl radical, C_2-4Alkynyl, halo C_1-4Alkyl, halo C_2-4Alkenyl, halo C_2-4Alkynyl or C_3-6A cycloalkyl group.

In some of these embodiments, each R is^aAnd R^bIndependently hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, amino, carboxyl, -CH₃、-CH₂CH₃、-CH₂CH₂CH₃、-CH(CH₃)₂、-CH＝CH₂、-CH₂-CH＝CH₂、-CH₂F、-CHF₂or-CF₃。

In some of these embodiments, R⁵、R⁶、R⁷、R⁸And R⁹Each independently is hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, amino, carboxyl, -C (═ O) -NR^cR^d、-NR^m-C(＝O)-Rⁿ、-NR^p(OR^q)、-C(＝O)-R^x、-C(＝O)-OR^y、C_1-4Alkyl radical, C_2-4Alkenyl radical, C_2-4Alkynyl, halo C_1-4Alkyl, halo C_2-4Alkenyl, halo C_2-4Alkynyl, hydroxy-substituted C_1-4Alkyl, amino substituted C_1-4Alkyl, cyano-substituted C_1-4Alkyl radical, C_1-4Alkoxy, halo C_1-4Alkoxy, hydroxy-substituted C_1-4Alkoxy, amino substituted C_1-4Alkoxy, cyano-substituted C_1-4Alkoxy radical, C_1-4Alkylamino radical, C_1-4Alkylthio or C_6-10An aryloxy group;

wherein R is^c、R^d、R^m、Rⁿ、R^p、R^q、R^xAnd R^yHave the meaning as described in the present invention.

In some of these embodiments, R^pAnd R^qEach independently is hydrogen, C_1-3Alkyl radical, C_2-4Alkenyl radical, C_2-4Alkynyl, halo C_1-3Alkyl, halo C_2-4Alkenyl, halo C_2-4Alkynyl, C_3-6Cycloalkyl, 3-6 membered heterocyclyl, C_6-10Aryl radical, C_1-5Heteroaryl or-C (═ O) -OR^y1；

Wherein R is^y1Have the meaning as described in the present invention.

In some of these embodiments, R^c、R^d、R^m、Rⁿ、R^y1、R^xAnd R^yEach independently is hydrogen, C_1-4Alkyl radical, C_2-4Alkenyl radical, C_2-4Alkynyl, halo C_1-4Alkyl, halo C_2-4Alkenyl, halo C_2-4Alkynyl, C_3-6Cycloalkyl, 3-6 membered heterocyclyl, C_6-10Aryl or C_1-5A heteroaryl group.

In some of these embodiments, R⁵、R⁶Optionally together with the carbon atoms to which they are attached form a phenyl or naphthyl ring, optionally substituted by 1,2,3, 4, 5, 6, 7, 8 or 9R¹⁵Substituted with the substituent(s);

wherein R is¹⁵Have the meaning as described in the present invention.

In some of these embodiments, R⁶、R⁷Optionally together with the carbon atoms to which they are attached form a phenyl or naphthyl ring, optionally substituted by 1,2,3, 4, 5, 6, 7, 8 or 9R¹⁶Substituted with the substituent(s);

wherein R is¹⁶Have the meaning as described in the present invention.

In some of these embodiments, R⁷、R⁸Optionally together with the carbon atoms to which they are attached form a phenyl or naphthyl ring, optionally substituted by 1,2,3, 4, 5, 6, 7, 8 or 9R¹⁷Substituted with the substituent(s);

wherein R is¹⁷Have the meaning as described in the present invention.

In some of these embodiments, R⁸、R⁹Optionally together with the carbon atoms to which they are attached form a phenyl or naphthyl ring, optionally substituted by 1,2,3, 4, 5, 6, 7, 8 or 9R¹⁸Substituted with the substituent(s);

wherein R is¹⁸Having a structure as described in the inventionMeaning.

In some of these embodiments, R is⁵、R⁶、R⁷、R⁸、R⁹、R^c、R^d、R^m、Rⁿ、R^y1、R^xAnd R^yOptionally substituted by 1,2,3, 4, 5 or 6R¹⁰Substituted;

wherein R is¹⁰Have the meaning as described in the present invention.

In some of these embodiments, each R is¹⁵、R¹⁶、R¹⁷And R¹⁸Independently hydrogen, halogen, cyano, nitro, C_1-4Alkyl radical, C_2-4Alkenyl radical, C_2-4Alkynyl, C_1-4Alkoxy radical, C_1-4Alkylamino, halogeno C_1-4Alkyl or halo C_1-4An alkoxy group.

In other embodiments, R⁵、R⁶、R⁷、R⁸And R⁹Each independently is hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, amino, carboxyl, -CH₃、-CH₂CH₃、-CH₂CH₂CH₃、-CH(CH₃)₂、-CH₂F、-CHF₂、-CF₃、-CH₂CH₂F、-CH₂CHF₂、-CH₂CF₃、-CH＝CH₂、-CH₂-CH＝CH₂、-OCH₃、-OCH₂CH₃、-OCH₂CH₂CH₃、-OCH(CH₃)₂、-OCF₃、-OCH₂CF₃、-NH-C(＝O)-CH₃、-NH-C(＝O)-CH₂CH₃、-NH-OH、-N(OH)-C(＝O)-OCH₃、-N(OC(＝O)OCH₃)-C(＝O)-OCH₃、-C(＝O)-CH₃、-C(＝O)-CH₂CH₃、-C(＝O)-OCH₃、-C(＝O)-OCH₂CH₃、-SCH₃、-SCH₂CH₃、-SCH₂CH₂CH₃、-SCH(CH₃)₂Phenoxy, halophenoxy, C_1-4Alkyl radicalSubstituted phenoxy, C_1-4Alkoxy-substituted phenoxy, C_1-4Haloalkyl-substituted phenoxy or C_1-4Haloalkoxy-substituted phenoxy.

In some of the embodiments of the present invention,

is of the sub-structure:

wherein:

In other embodiments, each R is⁵、R⁷、R⁸、R⁹、R^15a、R^15b、R^15c、R^15d、R^16a、R^16b、R^16c、R^16d、R^16e、R^16f、R^18a、R^18b、R^18cAnd R^18dIndependently hydrogen, halogen, cyano, nitro, C_1-4Alkyl radical, C_2-4Alkenyl radical, C_2-4Alkynyl, C_1-4Alkoxy radical, C_1-4Alkylamino, halogeno C_1-4Alkyl or halo C_1-4An alkoxy group.

or R^aAnd R^bTogether form oxo (═ O).

In other embodiments, each R is^aAnd R^bIndependently hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, amino, carboxyl, -CH₃、-CH₂CH₃、-CH₂CH₂CH₃、-CH(CH₃)₂、-CH₂F、-CHF₂、-CF₃、-CH₂CH₂F、-CH₂CHF₂、-CH₂CF₃、-CH＝CH₂、-CH₂-CH＝CH₂、-OCH₃、-OCH₂CH₃、-OCH₂CH₂CH₃、-OCH(CH₃)₂、-OCF₃、-OCH₂CF₃Cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl;

or R^aAnd R^bTogether form oxo (═ O).

In some of these embodiments, the present invention provides compounds of formula (Ia), stereoisomers, N-oxides, and salts thereof, of compounds of formula (Ia):

wherein:

R⁵、R⁶、R⁷、R⁸and R⁹Each independently is hydrogen, fluoro, chloro, bromo, iodo, hydroxy, cyano, nitro, amino, carboxy, alkyl, haloalkyl, alkenyl, alkoxy, or haloalkoxy;

wherein R is⁵、R⁶Optionally together with the carbon atoms to which they are attached to form a phenyl ring, which is optionally substituted with 1,2,3 or 4 substituents selected from fluoro, chloro, bromo, iodo, cyano, nitro, alkyl, alkenyl, alkynyl, alkoxy, alkylamino, haloalkyl or haloalkoxy.

In still other embodiments, the present invention provides compounds of formula (Ia), stereoisomers, N-oxides, and salts thereof, wherein R is⁵、R⁶、R⁷、R⁸And R⁹Each independently is hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, amino, carboxyl, C_1-6Alkyl, halo C_1-6Alkyl radical, C_2-6Alkenyl radical, C_1-6Alkoxy or halo C_1-6An alkoxy group;

wherein R is⁵、R⁶Optionally together with the carbon atoms to which they are attached form a phenyl ring, optionally substituted by 1,2,3 or 4 substituents selected from fluoro, chloro, bromo, iodo, cyano, nitro, C_1-6Alkyl radical, C_1-6Alkoxy radical, C_1-6Alkylamino, halogeno C_1-6Alkyl or halo C_1-6Substituted by a substituent of alkoxy.

In still other embodiments, the present invention provides compounds of formula (Ia), stereoisomers, N-oxides, and salts thereof, wherein R is⁵、R⁶、R⁷、R⁸And R⁹Each independently is hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, amino, carboxyl, C_1-4Alkyl, halo C_1-4Alkyl radical, C_2-4Alkenyl radical, C_1-4Alkoxy or halo C_1-4An alkoxy group;

wherein R is⁵、R⁶Optionally together with the carbon atoms to which they are attached form a phenyl ring, optionally substituted by 1,2,3 or 4 substituents selected from fluoro, chloro, bromo, iodo, cyano, nitro, C_1-4Alkyl radical, C_1-4Alkoxy radical, C_1-4Alkylamino, halogeno C_1-4Alkyl or halo C_1-4Substituted by a substituent of alkoxy.

In still other embodiments, the present invention provides compounds of formula (Ia), stereoisomers, N-oxides, and salts thereof, wherein R is⁵、R⁶、R⁷、R⁸And R⁹Each independently is hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, amino, carboxyl, -CH₃、-CH₂CH₃、-CH₂CH₂CH₃、-CH(CH₃)₂、-CH₂F、-CHF₂、-CF₃、-CH₂CH₂F、-CH₂CHF₂、-CH₂CF₃、-CH＝CH₂、-OCH₃、-OCH₂CH₃、-OCH₂CH₂CH₃、-OCH(CH₃)₂、-OCF₃or-OCH₂CF₃；

Wherein R is⁵、R⁶Optionally together with the carbon atoms to which they are attached form a phenyl ring, optionally substituted by 1,2,3 or 4 substituents selected from fluoro, chloro, bromo, iodo, cyano, nitro, -CH₃、-CF₃、-OCH₃or-OCF₃Substituted with the substituent(s).

In some of these embodiments, the present invention provides a compound that is a compound having one of the following structures or stereoisomers, nitroxides, and salts of compounds having one of the following structures:

in another aspect, the present invention provides a process for preparing a compound of formula (I), comprising: reacting a compound shown in a formula (e) with disubstituted amino sulfonyl chloride to obtain a compound shown in a formula (I):

wherein:R¹、R²、R³、R⁴、R⁵、R⁶、R⁷、R⁸、R⁹、R^a、R^band x has the meaning as given in the present invention.

In another aspect, the invention provides a composition comprising a compound of the invention. Unless otherwise indicated, all tautomers, racemates, hydrates, solvates, metabolites, metabolic precursors and prodrugs of the compounds of formula (a), formula (I) or formula (Ia) of the present invention are also within the scope of the present invention.

In some embodiments, the composition according to the present invention further comprises an agriculturally pharmaceutically acceptable surfactant and a carrier.

In another aspect, the invention provides the use of a compound of the invention or a composition of the invention for the control of plant diseases, particularly as a fungicide. In some of these embodiments, the plant disease is caused by a plant pathogenic fungus.

Compositions and formulations of the compounds of the invention

The compounds of the invention are generally useful as fungicide active ingredients in compositions, i.e., formulations, typically also comprising an agriculturally acceptable surfactant and carrier.

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.

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 (Guignardia) diseases such as Staphylococcus viticola (Guignardiabidwell), Venturia (Venturia) diseases such as Venturia mali (Venturia inaequalis), Sphaerotheca (Sepia) diseases such as Microchaeta oryzae (Septoria nodorum) and Phytophthora parasitica (Septorii), Powderzia (Powderi) diseases such as Erysiphe graminis (Erysiphe spp.) and Sphaerotheca (Septoria), Powderiana (Potentilla graminis) diseases such as Microchaeta canis (Erysiphe sp.) and Pseudoperonospora cinerea (Pseudoperonospora cinerea), Microchaeta (Ucinula graminis), Pseudoperonospora cucumerina and Pseudoperonospora cinerea (Botrytis) diseases such as Microchaetobacter sphaera), Potentilla graminis (Potentilla), Potentilla (Potentilla graminis (Potentilla) diseases such as Microchaetotrichia cinerea), Sclerotiella (Sclerotiella) and Pseudoperonospora cinerea), Scleroticola (Potentilla fragi (Potentilla) diseases such as Microchaetotrichia cinerea), Scleroticola (Potentilla fragi (Potentilla) diseases, 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 (Verticilliumdahliae); 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 plant diseases germinate, wherein the application amount of the bactericide composition is determined according to climatic conditions or crop states, generally 10-5000g is applied per mu, and the bactericide composition is diluted to 10-400mg/L (preferably 100-300mg/L) for application. 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.

Synthesis scheme I

The compounds of formula (I) can be prepared by the first synthetic scheme, wherein R¹、R²、R³、R⁴、R⁵、R⁶、R⁷、R⁸、R⁹、R^a、R^bAnd x has the meaning as described in the present invention; y is chlorine, bromine or iodine. The compound of the formula (a) and chlorine gas are subjected to oxidation reaction at a certain temperature (such as-10 ℃ to 10 ℃) under an acidic condition (such as hydrochloric acid, dilute sulfuric acid, acetic acid and the like) to obtain a compound of a formula (b); a compound of formula (c) and R⁴-NH₂Nucleophilic substitution reaction is carried out at a certain temperature (such as-10 ℃ to 30 ℃) under an alkaline condition (such as sodium hydroxide, sodium hydride, potassium carbonate and the like) to obtain a compound shown in a formula (d); carrying out condensation reaction on the compound of the formula (b) and the compound of the formula (d) at a certain temperature (such as-10-40 ℃) under an alkaline condition (such as pyridine, triethylamine, potassium carbonate and the like) to obtain a compound of a formula (e); a compound of formula (e) and R¹R²N-SO₂The compound of formula (I) is obtained by condensation reaction of Cl under a certain temperature (such as-10 ℃ to 40 ℃) and under an alkaline condition (such as pyridine, triethylamine, potassium carbonate and the like).

Synthesis scheme two

The compounds of formula (I) may be prepared by synthesis scheme twoTo obtain wherein R¹、R²、R³、R⁴、R⁵、R⁶、R⁷、R⁸、R⁹、R^a、R^bAnd x has the meaning as described in the present invention; y is chlorine, bromine or iodine. The compound of the formula (a) and acyl chloride (such as benzene sulfonyl chloride and p-toluene sulfonyl chloride) are subjected to oxidation coupling reaction at a certain temperature (such as-10-40 ℃) under an alkaline condition (such as pyridine, triethylamine, potassium carbonate and the like) to obtain a compound of a formula (f); a compound of formula (f) and R¹R²N-SO₂Cl is subjected to condensation reaction at a certain temperature (such as-10-40 ℃) under an alkaline condition (such as pyridine, triethylamine, potassium carbonate and the like) to obtain a compound shown in a formula (g); the compound of the formula (g) and chlorine gas are subjected to oxidation reaction at a certain temperature (such as-10 ℃ to 10 ℃) under an acidic condition (such as hydrochloric acid, dilute sulfuric acid, acetic acid and the like) to obtain a compound of a formula (h); a compound of formula (h) with NH₂-R⁴Carrying out condensation reaction at a certain temperature (such as-10-40 ℃) under an alkaline condition (such as pyridine, triethylamine, potassium carbonate and the like) to obtain a compound shown in a formula (i); nucleophilic substitution reaction is carried out between the compound of the formula (I) and the compound of the formula (c) at a certain temperature (such as-10 ℃ to 40 ℃) under alkaline conditions (such as sodium hydroxide, sodium hydride, potassium carbonate and the like) to obtain the compound of the formula (I).

Synthesis scheme three

The compounds of formula (I) can be prepared by synthesis scheme III, wherein R¹、R²、R³、R⁴、R⁵、R⁶、R⁷、R⁸、R⁹、R^a、R^bAnd x has the meaning as described in the present invention. The compound of formula (h) and the compound of formula (d) undergo condensation reaction at a certain temperature (such as-10 ℃ to 40 ℃) under alkaline conditions (such as pyridine, triethylamine, potassium carbonate and the like) to obtain the compound of formula (I).

The following acronyms are used throughout the invention:

g, g; mg; mol; mmol millimole; h hours; min; l liter; mL, mL; m mol/L;

PE petroleum ether; EtOAc ethyl acetate; DMF N, N-dimethylformamide; THF tetrahydrofuran

Examples

EXAMPLE A Synthesis of intermediate 3-mercapto-1, 2, 4-triazole

Formic acid (24.2g,0.52mol), water (25mL) and thiosemicarbazide (20g,0.22mol) were added to a 100mL reaction flask and heated to 105 ℃ for half an hour; then slowly cooling to room temperature, and then slowly crystallizing at minus 10 ℃; finally, the solid was filtered and dried to give aldiminothiourea (22.3 g of white solid, 85% yield).

Aldehyde thiosemicarbazide (12g,0.1mol) was added to a 250mL single-neck flask, water (130mL) and sodium carbonate (21.2g,0.25mol) were added, and the temperature was raised to 100 ℃ for 4 hours; then slowly cooling to room temperature, adjusting the pH value to 4-5 by using dilute hydrochloric acid, slowly stirring at-10 ℃, and slowly crystallizing; the solid was filtered off and dried to give 5.6g of a white solid in 55% yield.

¹H-NMR(400MHz,DMSO-d₆):δ(ppm)8.24(s,1H),13.2(s,1H),13.5(s,1H)；

¹³C NMR(100MHz,DMSO-d₆):δ(ppm)140.7,166.1.

Example B Synthesis of intermediate 1H-1,2, 4-triazole-3-sulfonyl chloride

Dissolving 3-mercapto-1, 2, 4-triazole (3g,0.03mol) in a hydrochloric acid solution (2mol/L,50 mL); then, the temperature is reduced to 0 ℃, and after the mixture is stirred uniformly, chlorine gas (30 g) is slowly introduced, and the introduction is completed within 1 hour, so that white solid is gradually separated out; after stopping introducing chlorine, excess chlorine was purged with nitrogen at 0 ℃, filtered and dried to obtain 3.2g of white solid with a yield of 75%.

¹H-NMR(400MHz,DMSO-d₆):δ(ppm)9.31(s,1H),13.9(s,1H)；

¹³C NMR(100MHz,DMSO-d₆):δ(ppm)143.6,157.1.

EXAMPLE C Synthesis of intermediate 5-difluoromethyl-3-mercapto-1, 2, 4-triazole

Suspending thiosemicarbazide (4.45g,0.049mol) in xylene (200mL), heating to 40 ℃ and stirring, then slowly dropping difluoroacetic acid (5.76g,0.06mol), and after dropping, reacting at 40 ℃ for 30 minutes; heating to 160 ℃, adding a water separator device, and refluxing and separating water for 4 hours; finally, the mixture was slowly cooled to room temperature, allowed to stand for 10 hours, and precipitated, and the precipitate was filtered, dissolved in ethyl acetate (200mL), washed with dilute hydrochloric acid (1M,50mL) and water (50 mL. times.3), dried over magnesium sulfate, and concentrated to obtain 5.42g of a yellow solid with a yield of 73.3%.

¹H-NMR(400MHz,DMSO-d₆):δ(ppm)14.3(s,1H),13.9(s,1H),7.1(t,1H)；

¹⁹F NMR(DMSO-d₆):δ(ppm)-118.6.

EXAMPLE D Synthesis of intermediate 5- (difluoromethyl) -1H-1,2, 4-triazole-3-sulfonyl chloride

Dissolving 5-difluoromethyl-3-mercapto-1, 2, 4-triazole (8.9g,0.059mol) in a hydrochloric acid solution (2mol/L,125 mL); then, the temperature is reduced to 0 ℃, and chlorine gas (60g, the chlorine gas is introduced within 1 hour) is slowly introduced after the mixture is stirred uniformly; after stopping the introduction of chlorine, excess chlorine was purged with nitrogen at 0 deg.C, extracted with dichloromethane (100 mL. times.3), the organic phases were combined, dried over magnesium sulfate and concentrated to give 5.89g of a yellow oil in 46% yield.

¹H-NMR(400MHz,CDCl₃):δ(ppm)6.9(t,1H)；

¹³C NMR(100MHz,CDCl₃):δ(ppm)162.9,151.6,109.1；

¹⁹F NMR(CDCl₃):δ(ppm)-118.0.

EXAMPLE E Synthesis of intermediate 5-p-fluorophenyl-3-mercapto-1, 2, 4-triazole

Dissolving p-fluorobenzoyl chloride (3.16g,0.02mol) in THF (60mL), cooling to 5 ℃, stirring, adding thiosemicarbazide in batches (adding in six times, 3.64g,0.04mol), slowly heating to room temperature after the addition is finished, and reacting for 4 hours; after completion of the reaction, the reaction was quenched with a saturated sodium bicarbonate solution (20mL), extracted with ethyl acetate (100 mL. times.3), and the organic phases were combined, washed with a saturated sodium bicarbonate solution (50mL) and a sodium chloride solution (100mL), dried over magnesium sulfate, and concentrated to give 4.0g of a white solid in 94% yield.

Dissolving the solid (4.26 g of p-fluorobenzamide thiourea) obtained in the above into a water (60mL) solution of sodium hydroxide (4g,0.1mol), heating to 85 ℃, and stirring for reaction for 4 hours; then slowly cooling to room temperature, adjusting the pH value to 5, separating out solids, filtering out the solids, and drying to obtain 3.1 white solids with the yield of 85%.

¹H-NMR(400MHz,DMSO-d₆):δ(ppm)13.7(s,1H),7.9(t,2H),7.4(t,2H)；

¹³C NMR(100MHz,DMSO-d₆):δ(ppm)167.5,164.5,162.8,149.9,128.6,122.5,116.8,116.5.

EXAMPLE F Synthesis of intermediate 5- (4-fluorophenyl) -1H-1,2, 4-triazole-3-sulfonyl chloride

Dissolving 5-p-fluorophenyl-3-mercapto-1, 2, 4-triazole (3.9g,0.02mol) in a solution of hydrochloric acid (2mol/L,80 mL)/methanol (10 mL); then, the temperature is reduced to 0 ℃, and chlorine gas (30g, the chlorine gas is introduced within 1 hour) is slowly introduced after the mixture is stirred uniformly; after the chlorine feed was stopped, excess chlorine was purged with nitrogen at 0 deg.C, extracted with dichloromethane (100 mL. times.3), the organic phases combined, dried over magnesium sulfate and concentrated to a tan oil 2.25g, 43.1% yield.

EXAMPLE G Synthesis of intermediate N-benzylcyclopropylamine

Cyclopropane (3.3g,0.058mol), potassium carbonate (20g,0.15mol) and DMF (80mL) were added to a 250mL reaction flask and stirred well at room temperature; then, a solution of benzyl chloride (5.11g,0.04mol) in DMF (20mL) was slowly dropped into the reaction (dropping was completed within 1 hour), and after the dropping was completed, the reaction was carried out at room temperature for 48 hours; then, water (80mL) was added, and extraction was performed with ether (100mL × 3), and the organic phase was washed with saturated aqueous sodium chloride solution (100mL × 2), dried over magnesium sulfate, concentrated, and purified by column chromatography (EtOAc/PE (v/v) ═ 1/4) to obtain 3.06g of a yellow liquid, with a yield of 52%.

¹H-NMR(400MHz,DMSO-d₆):δ(ppm)7.3～7.2(m,5H),3.7(s,2H),2.0(m,1H),0.3～0.4(m,4H)；

¹³C NMR(100MHz,DMSO-d₆):δ(ppm)141.6,128.4,126.8,53.4,30.1,6.6.

By a similar synthetic procedure to that of example G, substituting the corresponding starting material for benzyl chloride, the intermediate compounds of table 1 can be obtained.

TABLE 1

EXAMPLE H intermediate N- (4- (trifluoromethoxy) phenyl) -1H-1,2, 4-triazole-3-sulphonamide

P-trifluoromethoxyaniline (3.18g,0.018mol), triethylamine (2.22g,0.022mol) and tetrahydrofuran (30mL) were added to a 100mL single-necked flask; stirring uniformly at room temperature, then slowly dropping a THF (15mL) solution of 1H-1,2, 4-triazole-3-sulfonyl chloride (3.32g,0.02mol) (dropping is completed within 1 hour), reacting for 12 hours, adding water (20mL), and adjusting the pH value to 5 with hydrochloric acid; finally, extraction is carried out with diethyl ether (100 mL. times.3), the organic phases are combined, dried over magnesium sulfate, concentrated and washed with n-hexane to give 2.5g of an off-white solid, yield: 46 percent.

¹H-NMR(400MHz,DMSO-d₆):δ(ppm)14.8(s,1H),10.9(s,1H),8.7(s,1H),7.3～7.1(m,3H)；

¹³C NMR(100MHz,DMSO-d₆):δ(ppm)161.4,146.3,144.7,137.0,122.4,121.7,114.6.

By a similar synthetic procedure to that of example H, using the corresponding starting materials and conditions, the intermediate compounds of table 2 can be obtained.

TABLE 2

EXAMPLE I Synthesis of intermediate N- (4-fluorobenzyl) -N-cyclopropylsulfonyl chloride

Sulfonyl chloride (13.4g,0.1mol) was dissolved in dichloromethane (20mL) at room temperature and stirred well; triethylamine (2.02g,0.02mol) and N- (4-fluorobenzyl) cyclopropylamine (1.65g,0.01mol) were then dissolved in dichloromethane (10 mL); slowly dripping the mixture into dichloromethane of sulfonyl chloride at room temperature, and after dripping is finished, heating to 70 ℃ for reflux reaction for 3 hours; then, unreacted sulfonyl chloride and the solvent were distilled off under reduced pressure to give a yellow oil.

EXAMPLE J Synthesis of intermediate 1, 2-bis (1H-1,2, 4-triazol-3-yl) disulfane

3-mercapto-1, 2, 4-triazole (50.50g,0.50mol) was dissolved in dichloromethane (300mL), and pyridine (39.50g,0.50mol) was added. Benzenesulfonyl chloride (44.20g,0.25mol) was slowly added dropwise with stirring at 0 ℃ over 2 h. After the addition was complete, the mixture was stirred at room temperature for 16 h. The dichloromethane was evaporated under reduced pressure using a rotary evaporator, and the residue was stirred for 1h with water (300mL) under mechanical stirring. Filtration was carried out, and the residue was washed with water (500mL) and ethyl acetate (200mL), respectively, and air-dried to give 46.54g of a yellow powder in 93.1% yield.

LC-MS:(M+1)m/z＝201.3.

EXAMPLE K Synthesis of intermediate 3, 3' -disulfanediylbis (N, N-dimethyl-1H-1, 2, 4-triazole-1-sulfonamide)

Under nitrogen protection, 1, 2-bis (1H-1,2, 4-triazol-3-yl) disulfane (40.00g,0.20mol) was dissolved in N, N-dimethylformamide (200mL), and potassium carbonate (41.40g,0.30mol) was added thereto, followed by stirring and mixing at 0 ℃. N, N-dimethylamino sulfonyl chloride (64.34g,0.45mol) is slowly dripped, and the reaction is continued for 6h after the dripping is finished for 2 h. After the reaction was completed, the reaction solution was slowly poured into water and stirred for 1 hour. Filtration and air drying of the solid gave 73.94g of a white powder with a yield of 89.3%.

LC-MS:(M+1)m/z＝415.2.

EXAMPLE L Synthesis of intermediate 1- (N, N-dimethylaminosulfonyl) -1H-1,2, 4-triazole-3-sulfonyl chloride

3, 3' -disulfanediylbis (N, N-dimethyl-1H-1, 2, 4-triazole-1-sulfonamide) (41.40g,0.10mol) was dissolved in 1, 2-dichloroethane (300mL), water (300mL) was added, cooling to 0 deg.C, acetic acid (100mL) was added, the temperature was controlled at 10 deg.C to 25 deg.C, chlorine (35.50g,0.50mol) was introduced for 2 hours, and the reaction was continued for half an hour. After completion of the reaction, the solution was transferred to a separatory funnel, allowed to stand for separation, the organic phase was washed three times with water (30mL), and the solvent was evaporated under reduced pressure using a rotary evaporator to obtain 47.23g of a white powder with a yield of 86.2%.

EXAMPLE M intermediate N³-cyclopropyl-N¹,N¹Synthesis of (dimethyl) -1H-1,2, 4-triazole-1, 3-disulfonamide

Under the protection of nitrogen, cyclopropylamine (1.14g,0.02mol), triethylamine (2.22g,0.022mol) and tetrahydrofuran (30mL) were added to a 100mL three-necked flask, stirred at 0 ℃ and a solution of 1- (N, N-dimethylaminosulfonyl) -1H-1,2, 4-triazole-3-sulfonyl chloride (6.04g,0.02mol) in tetrahydrofuran (20mL) was added dropwise over 10min, with white smoke appearing and a white solid gradually precipitated. After the addition was complete, the reaction was carried out at room temperature for 2 hours, the solid was removed by filtration, and the filtrate was freed from the solvent under reduced pressure using a rotary evaporator to give a pale yellow solid, which was recrystallized (EtOAc/PE (v/v) ═ 5/1) to give 4.42g of a white solid, yield: 75.1 percent.

¹H NMR(400MHz,DMSO-d₆):δ(ppm)9.30(s,1H),7.49(s,1H),2.96(s,6H),2.48(m,1H),0.63～0.56(m,2H),0.50～0.43(m,2H).

LC-MS:(M+1)m/z＝296.3.

By a similar synthetic procedure to that of example M, using the corresponding starting materials, the intermediate compounds of table 3 can be obtained.

TABLE 3

EXAMPLE N Synthesis of intermediate N-benzylprop-2-en-1-amine

Benzylamine (1.07g,10.0mmol), potassium carbonate (2.8g,20.00mmol) and DMF (30mL) are added into a 100mL three-necked flask, and 3-bromoprop-1-ene (1.2g,10.0mmol) is slowly added into the reaction system to react for 8 hours at room temperature of 25 ℃; quenching with water (30mL), extraction with ethyl acetate (20mL × 3), washing of the organic phase with saturated brine, drying over anhydrous magnesium sulfate, filtration, removal of the solvent from the filtrate under reduced pressure with a rotary evaporator, and purification by column chromatography (EtOAc/PE (v/v) ═ 1/5) gave 1.10g of a colorless liquid, yield: 75 percent.

LC-MS:(M+1)m/z＝148.1.

EXAMPLE O Synthesis of intermediate N-benzyloxetan-3-amine

Oxetan-3-amine (2.19g,30.0mmol), benzaldehyde (1.06g,10.0mmol), anhydrous MgSO₄(3.60g,30.0mmol) and methylene chloride (30mL) were added to a 100mL three-necked flask and reacted at room temperature at 25 ℃ for 12 hours. Filtering, and removing the solvent from the filtrate under reduced pressure by using a rotary evaporator to obtain the imine intermediate. The imine intermediate was dissolved in methanol (20mL) and NaBH was slowly added₄(0.38g,10.0mmol) was added to the reaction system, reacted at room temperature 25 ℃ for 5 hours, spin-dried, and purified by column chromatography (EtOAc/PE (v/v) ═ 1/5) to give 1.45g of a colorless liquid, yield: 89 percent.

LC-MS:(M+1)m/z＝164.1.

By a similar synthetic procedure to that of example O, using the corresponding starting materials and conditions, the intermediate compounds of table 4 can be obtained.

TABLE 4

EXAMPLE P Synthesis of intermediate 4-methylpiperazine-1-sulfonyl chloride

1-methylpiperazine (2.00g,0.02mol) and triethylamine (4.04g,0.04mol) were added to a 100mL reaction flask at 0 ℃, a solution of thionyl chloride (5.40g,0.04mol) in methylene chloride (30mL) was added dropwise to the reaction system, and after completion of the dropwise addition, the reaction was carried out at 0 ℃ for 2 hours; the reaction was then quenched with water, the organic phase separated, dried over anhydrous magnesium sulfate, and concentrated to give 3.30g of a pale yellow oil in 83% yield.

LC-MS:(M+1)m/z＝199.0.

By a similar synthetic procedure to that of example P, using the corresponding starting materials and conditions, the intermediate compounds of table 5 can be obtained.

TABLE 5

EXAMPLE Q Synthesis of intermediate N- (1-phenylethyl) cyclopropylamine

Cyclopropylamine (1.71g,30.0mmol), acetophenone (1.20g,10.0mmol) and toluene (30mL) were added to a 100mL three-necked flask and heated to 110 ℃ for reflux reaction for 12 hours. After cooling, toluene was removed under reduced pressure using a rotary evaporator to obtain an imine intermediate. The imine intermediate was dissolved in methanol (20mL) and NaBH was slowly added₄(0.38g,10.0mmol) was added to the reaction system, reacted at room temperature 25 ℃ for 5 hours, spin-dried, and purified by column chromatography (EtOAc/PE (v/v) ═ 1/5) to give 0.85g of a colorless liquid, yield: 53 percent.

LC-MS:(M+1)m/z＝162.1.

By a similar synthetic procedure to that of example Q, using the corresponding starting materials and conditions, the intermediate compounds of table 6 can be obtained.

TABLE 6

EXAMPLE R intermediate N³- (2, 2-difluoroethyl) -N¹,N¹Synthesis of (dimethyl) -1H-1,2, 4-triazole-1, 3-disulfonamide

2, 2-difluoroethylamine (0.41g,5.0mmol), triethylamine (1.01g,10.0mol) and tetrahydrofuran (20mL) were added to a 100mL single-neck bottle; after stirring uniformly at room temperature, 1- (N, N-dimethylaminosulfonyl) -1H-1,2, 4-triazole-3-sulfonyl chloride (1.37g,5.0mmol) was slowly added to the reaction system, and after reaction at room temperature of 25 ℃ for 12 hours, water (30mL) was added to quench, extraction was performed with ethyl acetate (20mL × 3), anhydrous magnesium sulfate was dried, filtration was performed, the filtrate was subjected to reduced pressure using a rotary evaporator to remove the solvent, and column chromatography purification (EtOAc/PE (v/v) ═ 1/3) was performed to obtain 1.10g of a white solid, yield: and 69 percent.

LC-MS:(M+1)m/z＝320.0.

EXAMPLE 1 Compound N³-benzyl-N³-cyclopropyl-N¹,N¹Synthesis of (dimethyl) -1H-1,2, 4-triazole-1, 3-disulfonamide

Under the protection of nitrogen, dissolving N-benzyl-N-cyclopropyl-1H-1, 2, 4-triazole-3-sulfonamide (0.28g,1mmol) in dry tetrahydrofuran (8mL), stirring at 0 ℃, and then adding sodium hydride (with the content of 60%, 60mg,1.5 mmol) in three times; after the addition, the reaction is continued to be stirred for 30 minutes at the temperature of 0 ℃, then the reaction is heated to the room temperature, N-dimethylaminosulfonyl chloride (0.286g,2mmol) is slowly dropped into the reaction kettle, and the reaction is carried out for 8 hours at the room temperature; water (5mL) was added, extracted with ethyl acetate (10mL × 3), dried over magnesium sulfate, concentrated, and purified by column chromatography (PE/EtOAc (v/v) ═ 5/1) to give 0.27g of a white powder in 70.2% yield.

¹H-NMR(400MHz,CDCl₃):δ(ppm)8.6(s,1H),7.4～7.3(m,5H),4.6(s,2H),3.0(m,6H),2.6～2.5(m,1H),0.8～0.6(m,4H)；

¹³C NMR(100MHz,CDCl₃):δ(ppm)163.0,145.8,135.9,128.6,128.4,128.3,127.8,54.7,38.8,30.8,7.3；

LC-MS:(M+1)m/z＝386.4.

EXAMPLE 2 Compound N³-cyclopropyl-N³- (4-fluorobenzyl) -N¹,N¹Synthesis of (dimethyl) -1H-1,2, 4-triazole-1, 3-disulfonamide

Adding N-cyclopropyl-N- (4-fluorobenzyl) -1H-1,2, 4-triazole-3-sulfonamide (0.296g,1.0mmol), potassium carbonate (0.28g,2.0mmol) and DMF (10mL) into a 100mL three-necked bottle, slowly adding N, N-dimethylamino sulfonyl chloride (0.215g,1.5mmol) into the reaction system, and reacting at room temperature of 25 ℃ for 8 hours; quenching with water (20mL), extraction with ethyl acetate (15mL × 3), washing of the organic phase with saturated brine, drying over anhydrous magnesium sulfate, filtration, removal of the solvent from the filtrate under reduced pressure with a rotary evaporator, and purification by column chromatography (EtOAc/PE (v/v) ═ 1/3) gave 0.250g of a white solid in yield: 62 percent.

¹H NMR(400MHz,CDCl₃):δ(ppm)8.6(s,1H),7.4(dd,2H),7.0(t,2H),4.5(s,2H),3.0(m,6H),2.5(m,1H),0.8～0.7(m,4H)；

¹³C NMR(100MHz,CDCl₃):δ(ppm)163.4,146.0,130.3,115.5,115.3,53.9,39.0,30.5,7.3；

LC-MS:(M+1)m/z＝404.4.

EXAMPLE 3 Compound N³-cyclopropyl-5- (difluoromethyl) -N³- (4-fluorobenzyl) -N¹,N¹Synthesis of (dimethyl) -1H-1,2, 4-triazole-1, 3-disulfonamide

Adding N-cyclopropyl-5- (difluoromethyl) -N- (4-fluorobenzyl) -1H-1,2, 4-triazole-3-sulfonamide (0.346g,1.0mmol), potassium carbonate (0.28g,2.0mmol) and DMF (10mL) into a 100mL three-necked bottle, slowly adding N, N-dimethylaminosulfonyl chloride (0.215g,1.5mmol) into the reaction system, and reacting at room temperature of 25 ℃ for 8 hours; quenching with water (20mL), extraction with ethyl acetate (15mL × 3), washing of the organic phase with saturated brine, drying over anhydrous magnesium sulfate, filtration, removal of the solvent from the filtrate under reduced pressure with a rotary evaporator, and purification by column chromatography (EtOAc/PE (v/v) ═ 1/3) gave 0.222g of a white solid in yield: 51 percent.

¹H-NMR(400MHz,DMSO-d₆):δ(ppm)7.4～7.3(m,2H),7.3～7.1(m,3H),4.4(s,2H),2.9(m,6H),2.1(m,1H),0.6～0.7(m,4H)；

LC-MS:(M+1)m/z＝454.5.

EXAMPLE 4 Compound N¹,N¹-dimethyl-N³Synthesis of- (3- (trifluoromethyl) phenyl) -1H-1,2, 4-triazole-1, 3-disulfonamide

3- (trifluoromethyl) aniline (0.81g,5.0mmol), pyridine (0.79g,10.0mol), and tetrahydrofuran (20mL) were added to a 100mL single-neck bottle; after stirring uniformly at room temperature, 1- (N, N-dimethylaminosulfonyl) -1H-1,2, 4-triazole-3-sulfonyl chloride (1.37g,5.0mmol) was slowly added to the reaction system, and after reaction at room temperature of 25 ℃ for 12 hours, water (30mL) was added to quench, extraction was performed with ethyl acetate (20mL × 3), anhydrous magnesium sulfate was dried, filtration was performed, the filtrate was subjected to reduced pressure using a rotary evaporator to remove the solvent, and column chromatography purification (EtOAc/PE (v/v) ═ 1/3) was performed to obtain 1.40g of a white solid, yield: 70 percent.

LC-MS:(M+1)m/z＝400.0.

EXAMPLE 5 Compound N³-cyclopropyl-N³- (4-fluorobenzyl) -5- (4-fluorophenyl) -N¹,N¹Synthesis of (dimethyl) -1H-1,2, 4-triazole-1, 3-disulfonamide

Adding N-cyclopropyl-N- (4-fluorobenzyl) -5- (4-fluorophenyl) -1H-1,2, 4-triazole-3-sulfonamide (0.390g,1.0mmol), potassium carbonate (0.28g,2.0mmol) and DMF (10mL) into a 100mL three-necked bottle, slowly adding N, N-dimethylaminosulfonyl chloride (0.215g,1.5mmol) into the reaction system, and reacting at room temperature of 25 ℃ for 8 hours; quenching with water (20mL), extraction with ethyl acetate (15mL × 3), washing of the organic phase with saturated brine, drying over anhydrous magnesium sulfate, filtration, removal of the solvent from the filtrate under reduced pressure with a rotary evaporator, and purification by column chromatography (EtOAc/PE (v/v) ═ 1/3) gave 0.303g of a white solid in yield: 61 percent.

¹H-NMR(400MHz,DMSO-d₆):δ(ppm)7.8～7.7(m,2H),7.3～7.2(m,7H),4.2(s,1H),3.0(m,6H),2.2(m,1H),0.7～0.6(m,4H)；

LC-MS:(M+1)m/z＝498.5.

EXAMPLE 6 Compound N³- (2-chloro-4-fluorophenyl) -5- (difluoromethyl) -N¹,N¹Synthesis of (dimethyl) -1H-1,2, 4-triazole-1, 3-disulfonamide

Under the protection of nitrogen, dissolving N- (2-chloro-4-fluorophenyl) -5- (difluoromethyl) -1H-1,2, 4-triazole-3-sulfonamide (0.360g,1mmol) in dry pyridine (10mL), and stirring at room temperature for 2 hours; then, N-dimethylaminosulfonyl chloride (0.286g,2mmol) is slowly dropped by an injector, and after the dropping is finished, the reaction is carried out for 24 hours at room temperature; water (10mL) was added, extracted with ethyl acetate (20mL × 3), washed with saturated aqueous sodium bicarbonate (10mL × 2), dried over magnesium sulfate, concentrated, and purified by column chromatography (PE/EtOAc (v/v) ═ 5/1); this gave 0.168g of a pale yellow powder in 39.0% yield.

¹H-NMR(400MHz,DMSO-d₆):δ(ppm)7.5～7.4(m,1H),7.3(t,1H),7.2(m,2H),3.0(m,6H)；

LC-MS:(M+1)m/z＝433.9.

EXAMPLE 7 Compound N¹,N³-dicyclopropyl-5- (difluoromethyl) -N¹,N³Synthesis of (4-fluorobenzyl) -1H-1,2, 4-triazole-1, 3-disulfonamide

Under the protection of nitrogen, dissolving N-cyclopropyl-5- (difluoromethyl) -N- (4-fluorobenzyl) -1H-1,2, 4-triazole-3-sulfonamide (0.350g,1mmol) in dry tetrahydrofuran (8mL), stirring at 0 ℃, and then adding sodium hydride (with the content of 60%, 60mg,1.5 mmol) in three times; after the addition, the reaction is continued to be stirred at 0 ℃ for 30 minutes, then the temperature is raised to the room temperature, N- (4-fluorobenzyl) -N-cyclopropyl sulfonyl chloride (0.526g,2mmol) is slowly dropped, and the reaction is carried out for 8 hours at the room temperature; water (5mL) was added, extracted with ethyl acetate (10mL × 3), dried over magnesium sulfate, concentrated, and purified by column chromatography (PE/EtOAc (v/v) ═ 5/1). This gave 0.217g of a pale yellow powder in 38.1% yield.

¹H-NMR(400MHz,DMSO-d₆):δ(ppm)7.4～7.1(m,8H),6.9(t,1H),4.3(s,4H),2.2(m,2H),0.6～0.4(m,8H)；

LC-MS:(M+1)m/z＝574.2.

EXAMPLE 8 Compound N³-cyclopropyl-N¹,N¹-dimethyl-N³Synthesis of (naphthalene-2-ylmethyl) -1H-1,2, 4-triazole-1, 3-disulfonamide

Will N³-cyclopropyl-N¹,N¹-dimethyl-1H-1, 2, 4-triazole-1, 3-disulfonamide (0.400g,1.36mmol), potassium carbonate (0.276g,2.0mmol), 2-chloromethylnaphthalene (0.320g,2.0mmol) and DMF (30mL) were added to a 100mL three-necked flask and reacted at room temperature overnight. The next day water (50mL) was added, extraction was performed with ethyl acetate (50mL × 3), the organic phase was washed with saturated brine, dried over magnesium sulfate, filtered, the filtrate was subjected to removal of the solvent under reduced pressure with a rotary evaporator, and column chromatography purification (EtOAc/PE (v/v) ═ 5/1) was performed to obtain 0.370g of a white solid, yield: 63.0 percent.

¹H NMR(600MHz,DMSO-d₆):δ(ppm)9.47(s,1H),7.93(dd,4H),7.58-7.51(m,3H),4.72(s,2H),2.99(s,6H),2.63(m,1H),0.78-0.69(m,4H).

LC-MS:(M+1)m/z＝436.5.

EXAMPLE 9 Compound N³-cyclopropyl-N¹,N¹-dimethyl-N³- (Naphthalen-1-ylmethyl) -1H-1,2, 4-triazole-Synthesis of 1, 3-disulfonamides

Will N³-cyclopropyl-N¹,N¹-dimethyl-1H-1, 2, 4-triazole-1, 3-disulfonamide (0.400g,1.36mmol), potassium carbonate (0.276g,2.0mmol), 1-chloromethylnaphthalene (0.320g,2.0mmol) and DMF (30mL) were added to a 100mL three-necked flask and reacted at room temperature overnight. The next day water (50mL) was added, extraction was performed with ethyl acetate (50mL × 3), the organic phase was washed with saturated brine, dried over magnesium sulfate, filtered, and the solvent was removed from the filtrate under reduced pressure using a rotary evaporator to obtain 0.516g of yellow liquid, yield: 87.2 percent.

¹H NMR(600MHz,DMSO-d₆):δ(ppm)9.54(s,1H),8.22(d,1H),7.98(dd,2H),7.65-7.53(m,4H),5.04(s,2H),3.04(s,6H),2.58(m,1H),0.63-0.53(m,4H).

LC-MS:(M+1)m/z＝436.3.

The target compounds of table 7 can be obtained by referring to the synthesis schemes of the present invention or the synthesis of specific examples, using the corresponding raw materials and conditions.

TABLE 7

Biological examples of the present invention

Test targets: rhizoctonia solani, botrytis cinerea, peronospora cubensis and erysiphe necator.

And (3) test treatment: the compound was dissolved in DMF to 1% EC for use. The bactericidal activity of the compounds of the invention at doses of 200ppm, 100ppm, 50ppm, 25ppm, 12.5ppm and 6.25ppm against 4 test targets was evaluated using the in vivo potting method.

The test method comprises the following steps:

(1) pseudoperonospora cubensis (Pseudoperonospora cubensis)

Selecting 1 potted cucumber seedling with consistent growth vigor in true leaf period (removing growing point), spraying, air drying, inoculating after 24 hr, taking fresh cucumber downy mildew diseased leaf, washing off sporocyst on back of diseased leaf with distilled water by using writing brush, and making into sporangium suspension (2-3X 10)⁵Pieces/ml). Uniformly spraying and inoculating on cucumber seedlings by using an inoculation sprayer (the pressure is 0.1MPa), and transferring the inoculated test material to artificial gasAnd (3) waiting for room, keeping the relative humidity of 100 percent and the temperature of about 21 ℃, keeping the temperature of about 21 ℃ after 24 hours, keeping the relative humidity of about 95 percent for moisture induction, performing grading investigation on the disease condition according to blank control after 5 days, and calculating the control effect according to disease indexes.

(2) Cucumber powdery mildew (Sphaerotheca fuliginea)

Selecting a cucumber seedling with a true leaf period and consistent growth vigor, and drying in the shade for 24 hours after spray treatment. Washing fresh powdery mildew spores on cucumber leaves, filtering the fresh powdery mildew spores by using double-layer gauze to prepare suspension with the spore concentration of about 10 ten thousand/ml, and spraying for inoculation. The inoculated test material is moved into a climatic environment, the relative humidity is kept between 60 and 70 percent, the temperature is kept between 21 and 23 ℃, the classification investigation is carried out according to the blank control morbidity situation after about 10 days, and the control effect is calculated according to the disease index.

(3) Cucumber gray mold (Botrytis cinerea)

The method adopts a leaf inoculation method. Two potted cucumber seedlings with the same growth vigor of the true leaf period are selected, and after the agent is sprayed and dried, a fungus cake is inoculated on the leaves. And after 24-26 ℃ dark light moisture preservation is carried out for 24h, natural light is recovered for moisture preservation culture for about 3 d. After the contrast is fully developed, the diameter of the lesion spot of each inoculation point is measured by a caliper, and the control effect is calculated.

(4) Rhizoctonia solani (Rhizoctonia solani)

Selecting potted corn seedlings with two leaves and one heart and consistent growth vigor, naturally drying after spraying treatment, inoculating for about 24 hours, and inoculating a fungus cake on leaves after the agent is sprayed and dried. And (4) after the dark light moisture preservation is carried out for 24 hours at the temperature of 25-26 ℃, the natural light moisture preservation culture is recovered for about 3 days. After the disease is sufficiently distributed in contrast, the length of the lesion spot of each inoculation point is measured by a caliper, and the control effect is calculated.

The test results are shown in tables A-E.

TABLE A control of cucumber downy mildew at 200ppm of the compounds according to the invention

TABLE B controlling effect of the compounds of the invention on cucumber downy mildew at 100ppm

Table C control of cucumber downy mildew by the compounds of the invention at different concentrations in comparison with cyazofamid and the compounds of patent WO2017118193

Table D control of cucumber downy mildew by the compounds of the invention at different concentrations in comparison with amisulbrom

TABLE E control of cucumber downy mildew by the compounds according to the invention at various concentrations in comparison with the compounds of patent WO 9401419

The results in the tables A and B show that the compound has obvious control effect on cucumber downy mildew under different concentrations; particularly, the control effect of the compounds of the present invention, for example, example 9, example 12, example 13, example 14, example 17, example 31 and example 132 against cucumber downy mildew can reach more than 40% at 6.25 ppm. The results in tables C to E show that the compounds of the present invention have better control effect on cucumber downy mildew at low concentrations than the prior art. In addition, the compound of the invention has obvious control effect on rhizoctonia solani, botrytis cinerea and erysiphe necator in 200ppm, and the control effect can reach more than 30%.

Inhibition Rate test of the present invention

The inhibition rate test process: adding a certain amount of liquid medicine to be tested into the first row of first holes in a sterile 96-hole culture plate, sequentially diluting to the 8 th hole according to the required dilution times, taking cucumber brown spot pathogen in logarithmic growth phase, measuring the pathogen density by a microscopic counting method, and diluting to 10% concentration by using culture solution⁷-10⁸CFU/mL, add the culture to a 96-well plate at 100. mu.L per well, and control at 9 th and 10 th. Repeating each gradient for 5-8 times, adding 10 μ L of tetrazolium bromide solution into each well after the culture plate is cultured at 37 deg.C for 2.5 hr, culturing for 1.5 hr, centrifuging at 3000r/min for 10min, and removing supernatant. Finally, 200. mu.L of SDS (Sodium dodecyl sulfate) solution is added into each well of a 96-well plate, the mixture is shaken for a plurality of minutes, and after the blue crystal is completely dissolved, the mixture is placed on an ELSIA instrument for reading.

The same method is used for testing the control effect on rice blast, potato late blight, wheat root rot, wheat scab, corn leaf curvularia leaf spot, soybean root rot, rape sclerotinia rot, cotton wilt, apple ring rot, apple alternaria leaf spot, citrus scab, grape anthracnose, peach brown rot, peanut net blotch, watermelon gummy stem blight and mango stem rot.

The formula for calculating the inhibition rate is as follows: inhibition (%) × (1 — sample empty OD value/control well OD value) × 100%. The results are shown in Table F.

TABLE F control of the different pathogenic bacteria by the compounds of the invention

The compound of the invention is subjected to spectrum expansion, and has outstanding control effect on potato late blight, wheat root rot and soybean root rot. In addition, the compound has certain control effect on cucumber brown spot, wheat scab, corn curvularia leaf spot, sclerotinia rot of colza, cotton wilt, apple ring spot, apple alternaria leaf spot, citrus scab, grape anthracnose, peach brown rot, peanut net blotch, watermelon gummy stem blight and mango base rot.

Meanwhile, the compound has high safety on crops and fruit trees such as rice, cucumber, wheat, potato, corn, soybean, rape, cotton, apple, orange, grape, peach tree, peanut, watermelon, mango and the like, and no obvious phytotoxicity is found in the concentration range of 1ppm to 200 ppm.

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

1. A compound which is a compound of formula (I) or a salt of a compound of formula (I):

wherein: r¹And R²Each independently is C_1-6An alkyl group; or R¹、R²Together with the N atom to which they are attached form a 3-8 membered heterocyclic group or C_1-9A heteroaryl group;

R³is hydrogen;

R⁴is C_3-8A cycloalkyl group; r⁴Optionally substituted by one or more groups selected from R¹⁴Substituted with the substituent(s);

each R^aAnd R^bIndependently hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, amino, carboxyl, C_1-6Alkyl or C_3-8A cycloalkyl group;

x is 1;

R⁵、R⁶、R⁷、R⁸and R⁹Each independently is hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, amino, carboxyl, -C (═ O) -NR^cR^d、-NR^m-C(＝O)-Rⁿ、-NR^p(OR^q)、-C(＝O)-R^x、-C(＝O)-OR^y、C_1-6Alkyl radical, C_2-6Alkenyl radical, C_2-6Alkynyl, halo C_1-6Alkyl radical, C_1-6Alkoxy, halo C_1-6Alkoxy radical, C_1-6Alkylamino radical, C_1-6Alkylthio or C_6-10An aryloxy group;

wherein R is⁵、R⁶Optionally together with the carbon atoms to which they are attached form a benzene or naphthalene ring, optionally substituted by 1 or 2 groups selected from R¹⁵Substituted with the substituent(s);

wherein R is⁶、R⁷Optionally together with the carbon atoms to which they are attached form a benzene or naphthalene ring, optionally substituted by 1 or 2 groups selected from R¹⁶Substituted with the substituent(s);

wherein R is⁷、R⁸Optionally together with the carbon atoms to which they are attached form a benzene or naphthalene ring, optionally substituted by 1 or 2 groups selected from R¹⁷Substituted with the substituent(s);

wherein R is⁸、R⁹Optionally together with the carbon atoms to which they are attached form a benzene or naphthalene ring, optionally substituted by 1 or 2 groups selected from R¹⁸Substituted with the substituent(s);

wherein R is^pAnd R^qEach independently is hydrogen, C_1-6Alkyl OR-C (═ O) -OR^y1；

Wherein R is^c、R^d、R^m、Rⁿ、R^y1、R^xAnd R^yEach independentlyIs hydrogen or C_1-6An alkyl group;

wherein R is⁵、R⁶、R⁷、R⁸And R⁹Optionally substituted by 1 or 2R¹⁰Substituted;

each R¹⁰、R¹²And R¹⁴Independently hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, amino, carboxyl, -C (═ O) -OR^z、C_1-4Alkyl radical, C_2-4Alkenyl radical, C_2-4Alkynyl, halo C_1-4Alkyl radical, C_1-4Alkoxy, halo C_1-4Alkoxy radical, C_1-4Alkylamino or C_3-6A cycloalkyl group;

wherein R is^zIs C_1-4An alkyl group;

each R¹⁵、R¹⁶、R¹⁷And R¹⁸Independently hydrogen, halogen, cyano, nitro, C_1-6Alkyl radical, C_1-6Alkoxy, halo C_1-6Alkyl or halo C_1-6An alkoxy group.

2. The compound of claim 1, wherein:

R¹and R²Each independently is C_1-4An alkyl group; or R¹、R²And the N atom to which it is attached form the following subformula:

wherein p is₁And p₂Each independently is 0, 1 or 2;

q is 0, 1 or 2;

X¹are-O-, -S- (O) -, -S- (O)₂-or-NH-;

each X²、X³、X⁴And X⁵Independently is N or CH;

3. The compound of claim 2, wherein:

R¹and R²Each independently is-CH₃、-CH₂CH₃、-CH₂CH₂CH₃or-CH (CH)₃)₂；

4. the compound of claim 1, wherein:

R⁴is C_3-6A cycloalkyl group; wherein R is⁴Optionally substituted by 1 or 2 substituents selected from R¹⁴Substituted with the substituent(s);

each R¹⁴Independently hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, amino, carboxyl, -C (═ O) -O-C_1-3Alkyl radical, C_1-3Alkyl radical, C_1-3Alkoxy or C_3-6A cycloalkyl group.

5. The compound of claim 4, wherein:

R⁴is cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl; or R⁴Is of the sub-structure:

6. the compound of claim 1, wherein:

R⁵、R⁶、R⁷、R⁸and R⁹Each independently is hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, amino, carboxyl, -C (═ O) -NR^cR^d、-NR^m-C(＝O)-Rⁿ、-NR^p(OR^q)、-C(＝O)-R^x、-C(＝O)-OR^y、C_1-4Alkyl radical, C_2-4Alkenyl radical, C_2-4Alkynyl, halo C_1-4Alkyl radical, C_1-4Alkoxy, halo C_1-4Alkoxy radical, C_1-4Alkylamino radical, C_1-4Alkylthio or C_6-10An aryloxy group;

wherein R is^pAnd R^qEach independently is hydrogen, C_1-3Alkyl OR-C (═ O) -OR^y1；

Wherein R is^c、R^d、R^m、Rⁿ、R^y1、R^xAnd R^yEach independently is hydrogen or C_1-4An alkyl group;

each R¹⁵、R¹⁶、R¹⁷And R¹⁸Independently hydrogen, halogen, cyano, nitro, C_1-4Alkyl radical, C_1-4Alkoxy, halo C_1-4Alkyl or halo C_1-4An alkoxy group.

7. The compound of claim 6, wherein:

R⁵、R⁶、R⁷、R⁸and R⁹Each independently is hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, amino, carboxyl, -CH₃、-CH₂CH₃、-CH₂CH₂CH₃、-CH(CH₃)₂、-CH₂F、-CHF₂、-CF₃、-CH₂CH₂F、-CH₂CHF₂、-CH₂CF₃、-CH＝CH₂、-CH₂-CH＝CH₂、-OCH₃、-OCH₂CH₃、-OCH₂CH₂CH₃、-OCH(CH₃)₂、-OCF₃、-OCH₂CF₃、-NH-C(＝O)-CH₃、-NH-C(＝O)-CH₂CH₃、-NH-OH、-N(OH)-C(＝O)-OCH₃、-N(OC(＝O)OCH₃)-C(＝O)-OCH₃、-C(＝O)-CH₃、-C(＝O)-CH₂CH₃、-C(＝O)-OCH₃、-C(＝O)-OCH₂CH₃、-SCH₃、-SCH₂CH₃、-SCH₂CH₂CH₃、-SCH(CH₃)₂Phenoxy, halophenoxy, C_1-4Alkyl-substituted phenoxy, C_1-4Alkoxy-substituted phenoxy, C_1-4Haloalkyl-substituted phenoxy or C_1-4Haloalkoxy-substituted phenoxy.

8. The compound of claim 1, wherein:

is of the sub-structure:

wherein:

each R⁵、R⁷、R⁸、R⁹、R^15a、R^15b、R^15c、R^15d、R^16a、R^16b、R^16c、R^16d、R^16e、R^16f、R^18a、R^18b、R^18cAnd R^18dIndependently hydrogen, halogen, cyano, nitro, C_1-6Alkyl radical, C_1-6Alkoxy, halo C_1-6Alkyl or halo C_1-6An alkoxy group.

9. The compound of claim 8, wherein:

each R⁵、R⁷、R⁸、R⁹、R^15a、R^15b、R^15c、R^15d、R^16a、R^16b、R^16c、R^16d、R^16e、R^16f、R^18a、R^18b、R^18cAnd R^18dIndependently hydrogen, halogen, cyano, nitro, C_1-4Alkyl radical, C_1-4Alkoxy, halo C_1-4Alkyl or halo C_1-4An alkoxy group.

10. The compound of claim 9, wherein:

each R⁵、R⁷、R⁸、R⁹、R^15a、R^15b、R^15c、R^15d、R^16a、R^16b、R^16c、R^16d、R^16e、R^16f、R^18a、R^18b、R^18cAnd R^18dIndependently hydrogen, fluorine, chlorine, bromine, iodine, cyano, nitro, methyl, ethyl, n-propyl, isopropyl, tert-butyl, methoxy, ethoxy, isopropoxy, tert-butoxy, difluoromethyl, trifluoromethyl, difluoromethoxy or trifluoromethoxy.

11. The compound of claim 1, wherein:

each R^aAnd R^bIndependently hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, amino, carboxyl, C_1-4Alkyl or C_3-6A cycloalkyl group.

12. The compound of claim 11, wherein:

each R^aAnd R^bIndependently hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, amino, carboxyl, -CH₃、-CH₂CH₃、-CH₂CH₂CH₃、-CH(CH₃)₂Cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.

13. The compound according to any one of claims 1 to 12, which is a compound having one of the following structures or a salt of a compound having one of the following structures:

14. a process for preparing a compound of formula (I) comprising:

wherein: r¹、R²、R³、R⁴、R⁵、R⁶、R⁷、R⁸、R⁹、R^a、R^bAnd x has the meaning given in any one of claims 1 to 12.

15. A compound which is a compound of formula (II) or a salt of a compound of formula (II):

wherein: r³、R⁵、R⁶、R⁷、R⁸、R⁹、R^a、R^bAnd x has the meaning given in any one of claims 1 or 6 to 12.

16. A composition comprising a compound of any one of claims 1-13.

17. The composition of claim 16, further comprising an agriculturally pharmaceutically acceptable surfactant and a carrier.

18. Use of a compound according to any one of claims 1 to 13 or a composition according to claim 16 or 17 for the control of plant diseases.