CN112624987A - Cyclopentyl-substituted disulfonamide compound and application thereof in agriculture - Google Patents

Cyclopentyl-substituted disulfonamide compound and application thereof in agriculture Download PDF

Info

Publication number
CN112624987A
CN112624987A CN201910903533.3A CN201910903533A CN112624987A CN 112624987 A CN112624987 A CN 112624987A CN 201910903533 A CN201910903533 A CN 201910903533A CN 112624987 A CN112624987 A CN 112624987A
Authority
CN
China
Prior art keywords
compound
alkyl
radical
cyclopentyl
disulfonamide
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201910903533.3A
Other languages
Chinese (zh)
Inventor
李义涛
林健
李法霖
高国良
肖曹
姚文强
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dongguan Hec Pesticides R&d Co ltd
Original Assignee
Dongguan Hec Pesticides R&d Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dongguan Hec Pesticides R&d Co ltd filed Critical Dongguan Hec Pesticides R&d Co ltd
Priority to CN201910903533.3A priority Critical patent/CN112624987A/en
Publication of CN112624987A publication Critical patent/CN112624987A/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • C07D249/10—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D249/12—Oxygen or sulfur atoms
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/647—Triazoles; Hydrogenated triazoles
    • A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles

Abstract

The invention belongs to the field of pesticides, and particularly relates to a cyclopentyl-substituted disulfonamide compound and application thereof in agriculture; the compound is shown as a general formula (I); in the formula (I), RaAnd RbIs hydrogen, C1‑6Alkyl, etc., RcAnd RdIs hydrogen, fluorine, chlorine, bromine or methyl, X is-CH2-etc. R1、R2、R3、R4And R5Is hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, amino, C1‑6Alkyl, etc.; the compound, the composition and/or the preparation containing the compound have good bactericidal activity, and are applied as bactericides in agriculture.

Description

Cyclopentyl-substituted disulfonamide compound and application thereof in agriculture
Technical Field
The present invention provides a novel cyclopentyl-substituted disulfonamide compound and a preparation method thereof; and the use of cyclopentyl-substituted disulfonamide compounds and compositions and/or formulations containing these compounds as plant disease control agents 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 present invention provides a novel cyclopentyl-substituted disulfonamide compound having bactericidal activity, which has excellent control effect against plant diseases, particularly cucumber downy mildew, at a low dose.
Disclosure of Invention
The object of the present invention is to provide a novel fungicidal compound having a remarkable controlling effect on plant diseases, a fungicidal composition and/or preparation containing the fungicidal compound, and use thereof as a fungicide.
In one aspect, the invention provides a compound that is a compound of formula (I) or a stereoisomer, a nitroxide, or a salt thereof of a compound of formula (I):
Figure BDA0002212583200000011
wherein:
Raand RbEach independently is hydrogen, C1-6Alkyl radical, C2-6Alkenyl radical, C2-6Alkynyl, C3-8Cycloalkyl radical, C3-8cycloalkyl-C1-3Alkyl-, phenyl optionally substituted with 1,2,3, 4 or 5 halogens or phenyl-C optionally substituted with 1,2,3, 4 or 5 halogens1-3Alkyl-; or Ra、RbAnd the N atom to which they are attached, form a 3-8 membered heterocyclyl or 5-10 membered heteroaryl;
Rcand RdEach independently is hydrogen, fluorine, chlorine, bromine or methyl;
x is- (CR)eRf)n-；
Each ReAnd RfIndependently hydrogen or methyl;
or Re、RfAnd the C atom to which it is attached form C ═ O;
n is 0 or 1;
R1、R2、R3、R4and R5Each independently is hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, amino, C1-6Alkyl radical, C2-6Alkenyl radical, C2-6Alkynyl, halo C2-6Alkenyl, halo C2-6Alkynyl, C2-6Alkenyloxy radical, C2-6Alkynyloxy, C1-6Alkoxy radical, C1-6Alkylthio, halo C1-6Alkyl, halo C1-6Alkoxy, halo C1-6Alkylthio radical, C1-6Alkyl NH-, (C)1-6Alkyl radical)2N-、C1-6alkyl-C (═ O) -, C1-6alkoxy-C (═ O) -or phenyl;
or R1、R2Together with the carbon atoms to which they are attached form a benzene ring;
or R2、R3Together with the carbon atoms to which they are attached form a benzene ring;
or R3、R4Together with the carbon atoms to which they are attached form a benzene ring;
or R4、R5Together with the carbon atoms to which they are attached form a benzene ring;
the conditions are as follows: the compounds of the formula (I) are not
a)N3-benzyl-N3-cyclopentyl-N1,N1-dimethyl-1H-1, 2, 4-triazole-1, 3-disulfonamide;
b)N3-cyclopentyl-N1,N1-dimethyl-N3- (4-methylbenzyl) -1H-1,2, 4-triazole-1, 3-disulfonamide;
c)N3-cyclopentyl-N3- (4-fluorobenzyl) -N1,N1-dimethyl-1H-1, 2, 4-triazole-1, 3-disulfonamide;
d)N3-cyclopentyl-N3- (4-methoxybenzyl) -N1,N1-dimethyl-1H-1, 2, 4-triazole-1, 3-disulfonamide;
e)N3-cyclopentyl-N3- (2, 6-dichlorobenzyl) -N1,N1-dimethyl-1H-1, 2, 4-triazole-1, 3-disulfonamide;
f)N3-cyclopentyl-N1,N1-dimethyl-N3- (2- (trifluoromethyl) benzyl) -1H-1,2, 4-triazole-1, 3-disulfonamide;
g)N3-cyclopentyl-N3- (3-fluorobenzyl) -N1,N1-dimethyl-1H-1, 2, 4-triazole-1, 3-disulfonamide;
h)N3-cyclopentyl-N3- (4-isopropylbenzyl) -N1,N1-dimethyl-1H-1, 2, 4-triazole-1, 3-disulfonamide;
i)N3-cyclopentyl-N3- (3, 4-dimethylbenzyl) -N1,N1-dimethyl-1H-1, 2, 4-triazole-1, 3-disulfonamide; and
j)N3-cyclopentyl-N1,N1-dimethyl-N3- (2-oxo-2-phenylethyl) -1H-1,2, 4-triazole-1, 3-disulfonamide.
Wherein, the structural formulas corresponding to the compound a) to the compound j) are shown in the following table:
Figure BDA0002212583200000021
Figure BDA0002212583200000031
in some embodiments, the invention provides a compound of formula (I) or a stereoisomer, a nitroxide, or a salt thereof,
Raand RbEach independently is hydrogen、C1-4Alkyl radical, C2-4Alkenyl radical, C2-4Alkynyl, C3-6Cycloalkyl radical, C3-6cycloalkyl-C1-3Alkyl-, phenyl optionally substituted by 1,2,3, 4 or 5 fluoro, chloro, bromo or iodo or phenyl-C optionally substituted by 1,2,3, 4 or 5 fluoro, chloro, bromo or iodo1-3An alkyl group-.
In other embodiments, the invention provides a compound of formula (I) or a stereoisomer, a nitroxide or a salt thereof,
Raand RbEach independently hydrogen, methyl, ethyl, n-propyl, isopropyl, vinyl, propenyl, allyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl or benzyl.
In still other embodiments, the present invention provides a compound of formula (I), or a stereoisomer, a nitroxide, or a salt thereof,
Raand RbEach independently is methyl.
In some embodiments, the invention provides a compound of formula (I) or a stereoisomer, a nitroxide, or a salt thereof,
R1、R2、R3、R4and R5Each independently is hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, amino, C1-4Alkyl radical, C2-4Alkenyl radical, C2-4Alkynyl, C1-4Alkoxy radical, C1-4Alkylthio, halo C1-4Alkyl, halo C1-4Alkoxy, halo C1-4Alkylthio radical, C1-4Alkyl NH-, (C)1-4Alkyl radical)2N-、C1-4alkyl-C (═ O) -, C1-4alkoxy-C (═ O) -or phenyl.
In other embodiments, the invention provides a compound of formula (I) or a stereoisomer, a nitroxide or a salt thereof,
R1、R2、R3、R4and R5Each independently is hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, amino, -CH3、-CH2CH3、-CH2CH2CH3、-CH(CH3)2、-C(CH3)3、-OCH3、-OCH2CH3、-OCH2CH2CH3、-OCH(CH3)2、-OC(CH3)3、-SCH3、-SCH2CH3、-CH2F、-CHF2、-CF3、-OCH2F、-OCHF2、-OCF3、-SCF3、CH3O-C (═ O) -or phenyl.
In some embodiments, the invention provides a compound of formula (I) or a stereoisomer, a nitroxide, or a salt thereof,
Figure BDA0002212583200000041
is of the sub-structure:
Figure BDA0002212583200000042
in another aspect, the present invention provides a compound which is a compound having one of the following structures or a stereoisomer, a nitroxide or a salt thereof of the compound having one of the following structures:
Figure BDA0002212583200000051
Figure BDA0002212583200000061
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 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/or carrier.
In another aspect, the present invention provides the use of a compound according to the present invention or a composition according to the present invention for the control of plant diseases.
Further, the present invention provides the use of a compound according to the present invention or a composition according to the present invention as a fungicide.
In some of these embodiments, the plant disease is caused by a plant pathogenic fungus.
In other embodiments, the plant disease is cucumber downy mildew.
In another aspect, the present invention provides a method of controlling plant disease comprising applying to a plant or locus of a plant an effective amount of a compound according to the invention or a composition according to the invention.
Isotopically enriched compounds have the structure given in the present invention, 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.
Salts of the compounds of the invention, including those derived from alkali or alkaline earth metals, as well as from ammonia and aminesThose of (a). 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 having formula (I) may be prepared by treating a compound having 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.
Definitions and general terms
Reference will now be made in detail to certain embodiments of the invention, examples of which are illustrated by the accompanying structural and chemical formulas. The invention is intended to cover alternatives, modifications and equivalents, which may be included within the scope of the invention as defined by the appended claims. One skilled in the art will recognize that many methods and materials similar or equivalent to those described herein can be used in the practice of the present invention. The present invention is in no way limited to the methods and materials described herein. In the event that one or more of the incorporated documents, patents, and similar materials differ or contradict this application (including but not limited to defined terminology, application of terminology, described techniques, and the like), this application controls.
It will be further appreciated that certain features of the invention, which are, for clarity, described in the context of separate embodiments, may also be provided in combination in a single embodiment. Conversely, various features of the invention which are, for brevity, described in the context of a single embodiment, may also be provided separately or in any suitable subcombination.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. All patents and publications referred to herein are incorporated by reference in their entirety.
The following definitions, as used herein, should be applied unless otherwise indicated. For the purposes of the present invention, the chemical elements are in accordance with the CAS version of the periodic Table of the elements, and the handbook of chemistry and Physics, 75 th edition, 1994. In addition, general principles of Organic Chemistry can be referred to as described in "Organic Chemistry", Thomas Sorrell, University Science Books, Sausaltito: 1999, and "March's Advanced Organic Chemistry" by Michael B.Smith and Jerry March, John Wiley & Sons, New York:2007, the entire contents of which are incorporated herein by reference.
The articles "a," "an," and "the" as used herein are intended to include "at least one" or "one or more" unless otherwise indicated or clearly contradicted by context. Thus, as used herein, the articles refer to one or to more than one (i.e., to at least one) of the objects. For example, "a component" refers to one or more components, i.e., there may be more than one component contemplated for use or use in embodiments of the described embodiments.
The term "comprising" is open-ended, i.e. includes the elements indicated in the present invention, but does not exclude other elements.
The term "stereoisomers" refers to compounds having the same chemical structure, but differing in the arrangement of atoms or groups in space. Stereoisomers include enantiomers, diastereomers, conformers (rotamers), geometric isomers (cis/trans), atropisomers, and the like.
"enantiomer" refers to two isomers of a compound that are not overlapping but are in mirror image relationship to each other.
"diastereomer" refers to a stereoisomer that has two or more chiral neutrals and whose molecules are not mirror images of each other. Diastereomers have different physical properties, such as melting points, boiling points, spectral properties, and reactivities. Mixtures of diastereomers may be separated by high resolution analytical procedures such as electrophoresis and chromatography, e.g., HPLC.
The stereochemical definitions and rules used in the present invention generally follow the general definitions of S.P. Parker, Ed., McGraw-Hill Dictionary of Chemical Terms (1984) McGraw-Hill Book Company, New York; and Eliel, E.and Wilen, S., "Stereochemistry of Organic Compounds", John Wiley & Sons, Inc., New York, 1994.
Many organic compounds exist in an optically active form, i.e., they have the ability to rotate the plane of plane polarized light. In describing optically active compounds, the prefixes D and L or R and S are used to denote the absolute configuration of a molecule with respect to one or more of its chiral centers. The prefixes d and l or (+) and (-) are the symbols used to specify the rotation of plane polarized light by the compound, where (-) or l indicates that the compound is left-handed. Compounds prefixed with (+) or d are dextrorotatory. A particular stereoisomer is an enantiomer and a mixture of such isomers is referred to as an enantiomeric mixture. A50: 50 mixture of enantiomers is referred to as a racemic mixture or racemate, which may occur when there is no stereoselectivity or stereospecificity in the chemical reaction or process.
Any asymmetric atom (e.g., carbon, etc.) of a compound disclosed herein can exist in racemic or enantiomerically enriched forms, such as the (R) -, (S) -or (R, S) -configuration. In certain embodiments, each asymmetric atom has at least 50% enantiomeric excess, at least 60% enantiomeric excess, at least 70% enantiomeric excess, at least 80% enantiomeric excess, at least 90% enantiomeric excess, at least 95% enantiomeric excess, or at least 99% enantiomeric excess in the (R) -or (S) -configuration.
Depending on the choice of starting materials and methods, the compounds of the invention may exist as one of the possible isomers or as mixtures thereof, for example as racemates and mixtures of non-corresponding isomers (depending on the number of asymmetric carbon atoms). Optically active (R) -or (S) -isomers can be prepared using chiral synthons or chiral reagents, or resolved using conventional techniques. If the compound contains a double bond, the substituents may be in the E or Z configuration; if the compound contains a disubstituted cycloalkyl group, the substituents of the cycloalkyl group may have cis or trans configuration.
Any resulting mixture of stereoisomers may be separated into pure or substantially pure geometric isomers, enantiomers, diastereomers, depending on differences in the physicochemical properties of the components, for example, by chromatography and/or fractional crystallization.
The racemates of any of the resulting end products or intermediates can be resolved into the optical enantiomers by known methods using methods familiar to those skilled in the art, e.g., by separation of the diastereomeric salts obtained. The racemic product can also be separated by chiral chromatography, e.g., High Performance Liquid Chromatography (HPLC) using a chiral adsorbent. In particular, enantiomers can be prepared by asymmetric synthesis.
In addition, unless otherwise explicitly indicated, the descriptions of the terms "… independently" and "… independently" and "… independently" used in the present invention are interchangeable and should be understood in a broad sense to mean that the specific items expressed between the same symbols do not affect each other in different groups or that the specific items expressed between the same symbols in the same groups do not affect each other.
In the various parts of this specification, substituents of the disclosed compounds are disclosed in terms of group type or range. It is specifically intended that the invention includes each and every independent subcombination of the various members of these groups and ranges. For example, the term "C1-C6Alkyl "or" C1-6Alkyl "means in particular independently disclosed methyl, ethyl, C3Alkyl radical, C4Alkyl radical, C5Alkyl and C6An alkyl group.
The term "alkyl" or "alkyl group" as used herein, denotes a saturated, straight or branched chain, monovalent hydrocarbon group containing from 1 to 20 carbon atoms. 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 "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 toNot 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) I-propoxy (i-PrO, i-propoxy, -OCH (CH)3)2) Isobutoxy (i-BuO, i-butoxy, CH (CH)3)2CH2O-), isopentyloxy (CH)3)2CH2CH2O-), and the like.
The term "alkenyloxy" means an alkenyl group attached to the rest of the molecule through an oxygen atom, wherein the alkenyl group has the meaning as described herein. Examples of alkenyloxy groups include, but are not limited to, CH2＝CH-O、CH2＝CHCH2-O and the like.
The term "alkynyloxy" denotes an alkynyl group attached to the rest of the molecule through an oxygen atom, wherein the alkynyl group has the meaning as described herein.
The term "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 term "cycloalkylalkyl" denotes an alkyl group substituted by one or more cycloalkyl groups, wherein the alkyl group and the cycloalkyl group have the meaning as described herein.
The term "haloalkyl" denotes an alkyl group substituted with one or more halogen atoms, wherein the alkyl group has the meaning as described herein. Examples of haloalkyl include, but are not limited to, -CH2F，-CHF2，-CH2Cl，-CH2Br，-CF3，-CH2CF3，-CH2CH2F，-CH2CH2Cl，-CH2CH2Br，-CH2CHF2，-CH2CH2CF3，-CH2CH2CH2F，-CH2CH2CH2Cl，-CH2CH2CH2Br，-CHFCH2CH3，-CHClCH2CH3And so on.
The term "haloalkoxy" denotes an alkoxy group substituted by one or more halogen atoms, wherein the alkoxy group has the meaning as described herein. Examples of haloalkoxy include, but are not limited to, -OCH2F，-OCHF2，-OCH2Cl，-OCH2Br，-OCF3，-OCH2CF3，-OCH2CH2F，-OCH2CH2Cl，-OCH2CH2Br，-OCH2CHF2，-OCH2CH2CF3，-OCH2CH2CH2F，-OCH2CH2CH2Cl，-OCH2CH2CH2Br，-OCHFCH2CH3，-OCHClCH2CH3And so on.
The term "haloalkylthio" denotes an alkylthio group substituted by one or more halogen atoms, wherein the alkylthio group has the meaning as described herein.
In the various parts of this specification, linking substituents are described. Where the structure clearly requires a linking group, the markush variables listed for that group are understood to be linking groups. For example, if the structure requires a linking group and the markush group definition for that variable recites "alkyl" or "aryl," it is understood that the "alkyl" or "aryl" represents an attached alkylene group or arylene group, respectively.
The term "alkylene" refers to a saturated divalent hydrocarbon radical resulting from the removal of two hydrogen atoms from a saturated hydrocarbon radical. Unless otherwise specified, the alkylene group contains 1 to 12 carbon atoms, in other embodiments 1 to 6 carbon atoms, in other embodiments 1 to 4 carbon atoms, and in other embodiments 1 to 2 carbon atoms. Examples of this include methylene (-CH)2-, ethylene (-CH)2CH2-, isopropylidene (-CH (CH)3)CH2-) 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, dihydrothienyl1, 3-dioxolanyl, 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, thiaxanyl, homopiperazinyl, homopiperidinyl, oxepanyl, thiacycloheptyl, 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. The heterocyclyl group is optionally substituted with one or more substituents described herein.
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 "phenylalkyl" denotes an alkyl group substituted with one or more phenyl groups, wherein the alkyl group has the meaning as described herein. Examples of phenylalkyl groups include benzyl, phenethyl, and the like.
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.
In another embodiment, the ring atoms of the heteroaryl group comprise 1 to 9 carbon atoms and 1 to 4 heteroatoms selected from N, O or S; in another embodiment, the ring atoms of the heteroaryl group comprise 1 to 5 carbon atoms and 1 to 4 heteroatoms selected from N, O or S.
In yet another embodiment, heteroaryl represents a 5-or 6-membered heteroaryl group containing 1-4N heteroatoms; in yet another embodiment, heteroaryl represents a 5 membered heteroaryl group containing 1-3 heteroatoms selected from N, O or S; in yet another embodiment, heteroaryl represents a 5 membered heteroaryl group containing 1-3 heteroatoms selected from N or O; in yet another embodiment, heteroaryl represents a 5 membered heteroaryl group containing 1-3 heteroatoms selected from N or S.
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.
The term "halogen" refers to fluorine (F), chlorine (Cl), bromine (Br) or iodine (I).
The term "haloalkenyl" denotes an alkenyl group substituted with one or more halogen atoms, wherein the alkenyl group has the meaning as described herein.
The term "haloalkynyl" denotes an alkynyl group substituted by one or more halogen atoms, wherein the alkynyl group has the meaning as described herein.
Compositions and formulations of the compounds of the invention
The compounds of the invention are generally useful as fungicide active ingredients in compositions or formulations, typically also comprising an agriculturally acceptable surfactant and/or 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 globosa (Guignardia) diseases such as Staphylococcus viticola (Guignardia bidwell), Venturia (Venturia) diseases such as Venturia mali (Venturia inaequalis), Sphaerotheca (Sepia) diseases such as Microchaeta (Septoria nodorum) and Phytophthora parasitica (Septorii), Powderzia (Powderi) diseases such as Erysiphe graminis (Erysiphe spp.) and Sphaerotheca (Septoria), Powderiana graminis (Erysiphe sp.) diseases such as Microchaeta oryzae (Erysiphe graminis) and Pseudoperonospora rosea (Botrytis), Staphylococcus viticola (Uncinula necator), Pseudomonas cucumerina (Sphaerothecoides) and Pseudoperonospora cinerea (Botrytis), Scleroticola (Botrytis cinerea) diseases such as Microchaetobacter sphaera, Scleroticola (Botrytis cinerea), Scleroti cinerea), Scleroticola (Potentilla) diseases such as Microchaetotrichia cinerea), Scleroti cinerea (Potentilla cinerea), Scleroti cinerea) diseases such as Microchaetotrichia cinerea (Scleroti cinerea), Sc, Pyricularia oryzae (Magnaporthe grisea), Rhizoctonia solani (Phomopsis viticola), Helminthosporium (Helminthosporium) diseases such as northern leaf blight (Helminthosporium tritici reptilis), Moss reticulata (Pyrenophora teres), anthrax bacteria such as Hedychium nigrum (Glomerella) or Anthrax (Colletochium spp.) diseases (such as Colletotrichum graminicum (Colestochium graminicum) and watermelon anthrax (Colletochium orbiculosum)), and wheat holothrix graminis (Gaeumannomyces graminis); basidiomycetes, including rust diseases caused by the genus Puccinia (Puccinia spp.), such as Puccinia recondita (Puccinia recondita), Puccinia striiformis (Puccinia striiformis), Puccinia purpurea (Puccinia hordei), Puccinia graminis (Puccinia graminis) and Puccinia arachidis (Puccinia arachidis), coffee rust (hemix) and soybean rust (Phakopsora pachyrhizi); other pathogens include Rhizoctonia species (Rhizoctonia spp.) (such as Rhizoctonia solani); fusarium species diseases such as Fusarium roseum (Fusarium roseum), Fusarium graminearum (Fusarium graminearum), and Fusarium oxysporum (Fusarium oxysporum); verticillium dahliae (Verticillium dahliae); sclerotium rolfsii (sclerotiotium rolfsii); physalospora piricola (Rynchosporium secalis); black acerola (Cercosporium personatum), Episra nigrella (Cercospora arachidicola), and Episra fuscospora (Cercospora betacola); and other classes and species closely related to these pathogens. In addition to their fungicidal activity, the compositions or combinations also have a resistant activity against bacteria such as Erwinia amylovora (Erwinia amylovora), Xanthomonas campestris (Xanthomonas campestris), Pseudomonas syringae (Pseudomonas syringae) and other species.
The bactericide composition of the invention is simple in use method, and can be applied to crops and places where the crops grow by a conventional method such as soil mixing, spraying, pouring and the like before or after the germination of plant diseases, wherein the application amount is determined according to climatic conditions or crop states, generally 10-5000g is applied per mu, and the diluted application amount is 10-400mg/L (preferably 100-300 mg/L). The diluent is preferably water.
The bactericidal effect of the bactericide composition of the present invention is generally related to external factors such as climate, but the influence of climate can be alleviated by using appropriate dosage forms.
The compositions of the present invention may also be used in admixture with other compounds having fungicidal, insecticidal or herbicidal properties, as well as with nematicides, acaricides, protectants, herbicidal safeners, growth regulators, plant nutrients or soil conditioners, and the like.
General synthetic procedure
The following schemes describe the preparation of the compounds of the present invention, which may be prepared by the methods described herein, unless further indicated. The raw materials, reagents and the like used for preparing the compound of the invention are all commercially available, and the suppliers are Annaiji chemical, Aladdin, carbofuran and the like; or the raw materials and reagents used for preparing the compound of the present invention 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.
The test conditions of the nuclear magnetic resonance hydrogen spectrum of the invention are as follows: brookfield (Bruker) nuclear magnetic instrument at 400MHz or 600MHz in CDC1 at room temperature3，d6-DMSO，CD3OD or d6Acetone as solvent (reported in ppm) with TMS (0ppm) or chloroform (7.26ppm) as reference standard. When multiple peaks occur, the following abbreviations will be used: s (singleton), d (doublt,doublet), t (triplet ), q (quatet, quartet), m (multiplet ), br (broadenered, broad), dd (dautlet of doublets, doublet), dt (dautlet of triplets, doublet). Coupling constants are expressed in hertz (Hz).
The conditions for the low resolution Mass Spectrometry (MS) data determination of the invention are: agilent 6120 Quadrupole HPLC-MS (column model: Zorbax SB-C18,2.1X30mm,3.5 μm,6min, flow rate 0.6mL/min, mobile phase 5% -95% (CH with 0.1% formic acid)3CN) in (H containing 0.1% formic acid)2Proportion in O)), at 210/254nm with UV detection, using electrospray ionization mode (ESI).
Synthesis scheme I
Figure BDA0002212583200000161
The target compound of formula (c) may be prepared by synthetic scheme one. Nucleophilic substitution reaction is carried out between the compound of the formula (a) and the compound of the formula (b) under alkaline conditions (such as sodium hydroxide, sodium hydride, potassium carbonate and the like) to obtain a target compound of the formula (c); wherein R isc、Rd、R1、R2、R3、R4And R5Have the meaning as described in the present invention; hal is chlorine, bromine or iodine.
Synthesis scheme two
Figure BDA0002212583200000162
The target compound of formula (c-1) may be prepared by synthesis scheme two. Nucleophilic substitution reaction is carried out on the compound of the formula (a) and the compound of the formula (b-1) under alkaline conditions (such as sodium hydroxide, sodium hydride, potassium carbonate and the like) to obtain a target compound of the formula (c-1); wherein R is1、R2、R3、R4And R5Have the meaning as described in the present invention; hal is chlorine, bromine or iodine.
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 1, 2-bis (1H-1,2, 4-triazol-3-yl) disulfane
Figure BDA0002212583200000163
3-mercapto-1, 2, 4-triazole (101.0g,1.00mol) was dissolved in dichloromethane (500mL), and pyridine (79.0g,1.00mol) was added. Benzenesulfonyl chloride (88.30g,0.50mol) was slowly added dropwise with stirring at 0 ℃ over 2 h. After the addition was complete, the mixture was stirred at 25 ℃ for 18 h. The dichloromethane was evaporated under reduced pressure using a rotary evaporator and the residue was stirred for 1h with water (500mL) added under mechanical stirring. Filtration was carried out, and the residue was washed with water (800mL) and ethyl acetate (300mL), respectively, and air-dried to give 95.2g of a yellow powder in 95.2% yield.
LC-MS:(M+1)m/z＝201.1.
EXAMPLE B Synthesis of intermediate 3, 3' -Dithio (N, N-dimethyl-1H-1, 2, 4-triazole-1-sulfonamide)
Figure BDA0002212583200000171
1, 2-bis (1H-1,2, 4-triazol-3-yl) disulfane (60.0g,0.30mol) was dissolved in N, N-dimethylformamide (300mL) under nitrogen, potassium carbonate (69.0g,0.50mol) was added, and the mixture was stirred and mixed at 0 ℃. N, N-dimethylaminosulfonyl chloride (93.34g,0.65mol) is slowly dropped into the mixture, and after the dropping is finished for 2 hours, the reaction is continued for 6 hours. 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 107.2g of a white powder with a yield of 86.3%.
LC-MS:(M+1)m/z＝415.0.
EXAMPLE C Synthesis of intermediate 1- (N, N-dimethylaminosulfonyl) -1H-1,2, 4-triazole-3-sulfonyl chloride
Figure BDA0002212583200000172
3, 3' -disulfanediylbis (N, N-dimethyl-1H-1, 2, 4-triazole-1-sulfonamide) (41.40g,0.10mol) was dissolved in 1, 2-dichloroethane (150mL), water (300mL) was added, cooling to 0 deg.C, acetic acid (150mL) 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 48.11g of a white powder with a yield of 87.8%.
LC-MS:(M+1)m/z＝274.8.
EXAMPLE D intermediate N3-cyclopentyl-N1,N1Synthesis of (dimethyl) -1H-1,2, 4-triazole-1, 3-disulfonamide
Figure BDA0002212583200000173
Under the protection of nitrogen, cyclopentylamine (1.70g,0.02mol), triethylamine (2.02g,0.02mol) and tetrahydrofuran (30mL) are added into a 100mL three-necked bottle, stirred at 0 ℃, and a solution of 1- (N, N-dimethylaminosulfonyl) -1H-1,2, 4-triazole-3-sulfonyl chloride (5.48g,0.02mol) in tetrahydrofuran (20mL) is dropwise added within 10min, so that white smoke appears and white solid is gradually separated out. After the addition was complete, the reaction was carried out at room temperature for 2h, 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 4.96g of a white solid, yield: 76.7 percent.
1H NMR(400MHz,DMSO-d6):δ(ppm)9.30(s,1H),7.66(s,1H),4.38(dt,1H),2.96(s,6H),1.70(d,2H),1.44(ddd,4H),1.29(s,2H).
LC-MS:(M+1)m/z＝324.1.
Example 1: n is a radical of3- (4-bromobenzyl) -N3-cyclopentyl-N1,N1Synthesis of (E) -dimethyl-1H-1, 2, 4-triazole-1, 3-disulfonamide
Figure BDA0002212583200000181
Will N3-cyclopentyl-N1,N1-dimethyl-1H-1, 2, 4-triazole-1, 3-disulfonamide (0.32g,1.0mmol), potassium carbonate (0.28g,2.0mmol) and DMF (10mL) are added into a 100mL three-necked bottle, and then 1-bromo-4- (bromomethyl) benzene (0.37g,1.5mmol) is slowly added into the reaction system to react for 8 hours at room temperature of 25 ℃; after quenching with water (20mL), extraction with ethyl acetate (15 mL. times.3), washing of the organic phase with saturated brine, drying over anhydrous magnesium sulfate, filtration, and removal of the solvent from the filtrate under reduced pressure using a rotary evaporator, 0.29g of a colorless oily liquid was obtained, yield: 60 percent.
1H NMR(400MHz,CDCl3):δ(ppm)8.68(s,1H),7.70(d,J＝7.6Hz,1H),7.54(d,J＝7.9Hz,1H),7.38(t,J＝7.5Hz,1H),7.16(t,J＝7.5Hz,1H),4.62(s,2H),4.53–4.40(m,1H),3.10(s,6H),1.71(s,2H),1.62–1.55(m,2H),1.51–1.42(m,2H),1.33–1.29(m,2H).
LC-MS:(M+1)m/z＝492.0.
Example D (intermediate N) was prepared analogously to example 13-cyclopentyl-N1,N1-dimethyl-1H-1, 2, 4-triazole-1, 3-disulfonamide) and corresponding raw materials to obtain the target compounds in the table 1.
TABLE 1
Figure BDA0002212583200000182
Figure BDA0002212583200000191
Figure BDA0002212583200000201
Figure BDA0002212583200000211
Figure BDA0002212583200000221
Figure BDA0002212583200000231
Figure BDA0002212583200000241
Biological examples of the present invention
Test targets: cucumber downy mildew
And (3) test treatment: the compound was dissolved in DMF to 1% EC for use. The bactericidal activity of the compounds on cucumber downy mildew is evaluated by using a living pot culture method under different dosages.
Selecting 1 potted cucumber seedling with consistent growth vigor in true leaf period (removing growing point), spraying, air drying, inoculating 24 hr later, taking fresh cucumber downy mildew diseased leaf, washing off sporocyst on back of diseased leaf with distilled water by writing brush, and making into sporangium suspension (2-3x 10)5one/mL). Uniformly spraying and inoculating on cucumber seedlings by using an inoculation sprayer (the pressure is 0.1MPa), transferring inoculated test materials to an artificial climate chamber, keeping the relative humidity at 100% and the temperature at about 21 ℃, keeping the temperature at about 21 ℃ after 24 hours, keeping the relative humidity at about 95% for moisture induction, carrying out grading investigation according to blank control disease occurrence conditions after 5 days, and calculating the control effect according to disease indexes.
The test results are shown in tables A-C.
TABLE A control of cucumber downy mildew at 200ppm of the compounds according to the invention
Practice ofExample (b) DefendMedicine for curing diabetesEffect of (1)Fruit (％)
Practice ofExample (b) 1 100
Practice ofExample (b) 2 100
Practice ofExample (b) 3 100
Practice ofExample (b) 4 100
Practice ofExample (b) 5 100
Practice ofExample (b) 6 100
Practice ofExample (b) 7 100
Practice ofExample (b) 8 100
Practice ofExample (b) 9 100
Practice ofExample (b) 10 100
Practice ofExample (b) 11 100
Practice ofExample (b) 12 100
Practice ofExample (b) 13 100
Practice ofExample (b) 14 100
Practice ofExample (b) 15 100
Practice ofExample (b) 16 100
Practice ofExample (b) 17 100
Practice ofExample (b) 18 100
Practice ofExample (b) 19 100
Practice ofExample (b) 20 100
Practice ofExample (b) 21 100
Practice ofExample (b) 22 100
Practice ofExample (b) 23 100
Practice ofExample (b) 24 100
Practice ofExample (b) 25 100
TABLE B controlling effect of the compounds of the invention on cucumber downy mildew at 100ppm
Figure BDA0002212583200000251
Figure BDA0002212583200000261
TABLE C control of cucumber downy mildew at 50ppm with the compounds according to the invention
Figure BDA0002212583200000262
Figure BDA0002212583200000271
Figure BDA0002212583200000281
Figure BDA0002212583200000291
The results in tables A to C show that the compound has obvious control effect on cucumber downy mildew under different concentrations and has good development prospect.
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 (10)

1. A compound which is a compound of formula (I) or a stereoisomer, a nitroxide or a salt thereof:
Figure FDA0002212583190000011
wherein:
Raand RbEach independently is hydrogen, C1-6Alkyl radical, C2-6Alkenyl radical, C2-6Alkynyl, C3-8Cycloalkyl radical, C3-8cycloalkyl-C1-3Alkyl-, phenyl optionally substituted with 1,2,3, 4 or 5 halogens or phenyl-C optionally substituted with 1,2,3, 4 or 5 halogens1-3Alkyl-; or Ra、RbAnd the N atom to which they are attached, form a 3-8 membered heterocyclyl or 5-10 membered heteroaryl;
Rcand RdEach independently is hydrogen, fluorine, chlorine, bromine or methyl;
x is- (CR)eRf)n-；
Each ReAnd RfIndependently hydrogen or methyl;
or Re、RfAnd the C atom to which it is attached form C ═ O;
n is 0 or 1;
R1、R2、R3、R4and R5Each independently is hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, amino, C1-6Alkyl radical, C2-6Alkenyl radical, C2-6Alkynyl, halo C2-6Alkenyl, halo C2-6Alkynyl, C2-6Alkenyloxy radical, C2-6Alkynyloxy, C1-6Alkoxy radical, C1-6Alkylthio, halo C1-6Alkyl, halo C1-6Alkoxy, halo C1-6Alkylthio radical, C1-6Alkyl NH-, (C)1-6Alkyl radical)2N-、C1-6alkyl-C (═ O) -, C1-6alkoxy-C (═ O) -or phenyl;
or R1、R2Together with the carbon atoms to which they are attached form a benzene ring;
or R2、R3Together with the carbon atoms to which they are attached form a benzene ring;
or R3、R4Together with the carbon atoms to which they are attached form a benzene ring;
or R4、R5Together with the carbon atoms to which they are attached form a benzene ring;
the conditions are as follows: the compounds of the formula (I) are not
a)N3-benzyl-N3-cyclopentyl-N1,N1-dimethyl-1H-1, 2, 4-triazole-1, 3-disulfonamide;
b)N3-cyclopentyl-N1,N1-dimethyl-N3- (4-methylbenzyl) -1H-1,2, 4-triazole-1, 3-disulfonamide;
c)N3-cyclopentyl-N3- (4-fluorobenzyl) -N1,N1-dimethyl-1H-1, 2, 4-triazole-1, 3-disulfonamide;
d)N3-cyclopentyl-N3- (4-methoxybenzyl) -N1,N1-dimethyl-1H-1, 2, 4-triazole-1, 3-disulfonamide;
e)N3-cyclopentyl-N3- (2, 6-dichlorobenzyl) -N1,N1-dimethyl-1H-1, 2, 4-triazole-1, 3-disulfonamide;
f)N3-cyclopentyl-N1,N1-dimethyl-N3- (2- (trifluoromethyl) benzyl) -1H-1,2, 4-triazole-1, 3-disulfonamide;
g)N3-cyclopentyl-N3- (3-fluorobenzyl) -N1,N1-dimethyl-1H-1, 2, 4-triazole-1, 3-disulfonamide;
h)N3-cyclopentyl-N3- (4-isopropylbenzyl) -N1,N1-dimethyl-1H-1, 2, 4-triazole-1, 3-disulfonamide;
i)N3-cyclopentyl-N3- (3, 4-dimethylbenzyl) -N1,N1-dimethyl-1H-1, 2, 4-triazole-1, 3-disulfonamide; and
j)N3-cyclopentyl-N1,N1-dimethyl-N3- (2-oxo-2-phenylethyl) -1H-1,2, 4-triazole-1, 3-disulfonamide.
2. The compound of claim 1, wherein:
Raand RbEach independently is hydrogen, C1-4Alkyl radical, C2-4Alkenyl radical, C2-4Alkynyl, C3-6Cycloalkyl radical, C3-6cycloalkyl-C1-3Alkyl-, phenyl optionally substituted by 1,2,3, 4 or 5 fluoro, chloro, bromo or iodo or phenyl-C optionally substituted by 1,2,3, 4 or 5 fluoro, chloro, bromo or iodo1-3An alkyl group-.
3. The compound of claim 2, wherein:
Raand RbEach independently hydrogen, methyl, ethyl, n-propyl, isopropyl, vinyl, propenyl, allyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl or benzyl.
4. The compound of claim 1, wherein:
R1、R2、R3、R4and R5Each independently is hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, amino, C1-4Alkyl radical, C2-4Alkenyl radical, C2-4Alkynyl, C1-4Alkoxy radical, C1-4Alkylthio, halo C1-4Alkyl, halo C1-4Alkoxy, halo C1-4Alkylthio radical, C1-4Alkyl NH-, (C)1-4Alkyl radical)2N-、C1-4alkyl-C (═ O) -, C1-4alkoxy-C (═ C)O) -or phenyl.
5. The compound of claim 4, wherein:
R1、R2、R3、R4and R5Each independently is hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, amino, -CH3、-CH2CH3、-CH2CH2CH3、-CH(CH3)2、-C(CH3)3、-OCH3、-OCH2CH3、-OCH2CH2CH3、-OCH(CH3)2、-OC(CH3)3、-SCH3、-SCH2CH3、-CH2F、-CHF2、-CF3、-OCH2F、-OCHF2、-OCF3、-SCF3、CH3O-C (═ O) -or phenyl.
6. A compound which is a compound having one of the following structures or a stereoisomer, a nitroxide or a salt thereof of a compound having one of the following structures:
Figure FDA0002212583190000021
Figure FDA0002212583190000031
Figure FDA0002212583190000041
7. a composition comprising a compound of any one of claims 1-6.
8. The composition of claim 7, further comprising an agriculturally pharmaceutically acceptable surfactant and/or carrier.
9. Use of the compound according to any one of claims 1 to 6 or the composition according to claim 7 or 8 for controlling plant diseases.
10. A method of controlling plant diseases which comprises applying to a plant or to the locus of a plant an effective amount of a compound according to any one of claims 1 to 6 or a composition according to claim 7 or 8.
CN201910903533.3A 2019-09-24 2019-09-24 Cyclopentyl-substituted disulfonamide compound and application thereof in agriculture Pending CN112624987A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910903533.3A CN112624987A (en) 2019-09-24 2019-09-24 Cyclopentyl-substituted disulfonamide compound and application thereof in agriculture

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910903533.3A CN112624987A (en) 2019-09-24 2019-09-24 Cyclopentyl-substituted disulfonamide compound and application thereof in agriculture

Publications (1)

Publication Number Publication Date
CN112624987A true CN112624987A (en) 2021-04-09

Family

ID=75283165

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910903533.3A Pending CN112624987A (en) 2019-09-24 2019-09-24 Cyclopentyl-substituted disulfonamide compound and application thereof in agriculture

Country Status (1)

Country Link
CN (1) CN112624987A (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115093374A (en) * 2021-06-28 2022-09-23 华中师范大学 Triazole sulfonamide derivative, preparation method and application thereof, bactericide and application thereof
CN115232081A (en) * 2021-04-25 2022-10-25 华中师范大学 Triazole sulfonamide derivative containing allyl fragment, preparation method and application thereof, bactericide and application thereof
CN115477619A (en) * 2021-06-16 2022-12-16 华中师范大学 Triazole sulfonamide derivative containing oxime ether fragment, preparation method and application thereof, bactericide and application thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1051729A (en) * 1989-11-15 1991-05-29 先灵农业化学品公司 Imidazole fungicides
WO2018184579A1 (en) * 2017-04-05 2018-10-11 Dongguan Hec Tech R&D Co., Ltd. Triazole compound and use thereof in agriculture

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1051729A (en) * 1989-11-15 1991-05-29 先灵农业化学品公司 Imidazole fungicides
WO2018184579A1 (en) * 2017-04-05 2018-10-11 Dongguan Hec Tech R&D Co., Ltd. Triazole compound and use thereof in agriculture
CN108689951A (en) * 2017-04-05 2018-10-23 东莞东阳光科研发有限公司 3-triazole compounds and its application in agricultural

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
陈永明 等: "黄瓜霜霉病的研究进展及登记防治农药的分析", 《农学学报》, vol. 8, no. 8, pages 9 - 15 *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115232081A (en) * 2021-04-25 2022-10-25 华中师范大学 Triazole sulfonamide derivative containing allyl fragment, preparation method and application thereof, bactericide and application thereof
WO2022228402A1 (en) * 2021-04-25 2022-11-03 华中师范大学 Triazole sulfonamide derivative containing alkenyl fragments, preparation method therefor and application thereof, and bactericide and application thereof
CN115477619A (en) * 2021-06-16 2022-12-16 华中师范大学 Triazole sulfonamide derivative containing oxime ether fragment, preparation method and application thereof, bactericide and application thereof
WO2022262814A1 (en) * 2021-06-16 2022-12-22 华中师范大学 Triazole sulfonamide derivative containing oxime ether fragments, preparation method therefor and application thereof, and bactericide and application thereof
CN115477619B (en) * 2021-06-16 2024-01-26 华中师范大学 Triazole sulfonamide derivative containing oxime ether fragment, preparation method and application thereof, bactericide and application thereof
CN115093374A (en) * 2021-06-28 2022-09-23 华中师范大学 Triazole sulfonamide derivative, preparation method and application thereof, bactericide and application thereof
CN115093374B (en) * 2021-06-28 2023-11-24 武汉智汇农耀科技有限公司 Triazole sulfonamide derivative, preparation method and application thereof, bactericide and application thereof

Similar Documents

Publication Publication Date Title
CN108689951B (en) Triazole compound and application thereof in agriculture
CN110950810B (en) Triazole compound and application thereof in agriculture
CN112624988B (en) New triazole compound and application thereof in agriculture
CN112624987A (en) Cyclopentyl-substituted disulfonamide compound and application thereof in agriculture
CN112638884B (en) Triazole sulfonamide derivative and preparation method and application thereof
CN110577498B (en) Triazole compound and application thereof in agriculture
CN109311853B (en) Triazole derivatives and their use in agriculture
CN115667229A (en) Triazole sulfonamide derivative and preparation method and application thereof
CN114105959A (en) Triazole sulfonamide derivative and application thereof
CN113429356B (en) Triazole sulfonamide derivative and application thereof in agriculture
CN112624965B (en) Novel oxime derivative and application thereof in agriculture
CN114516846A (en) Triazole sulfonamide derivative and preparation method and application thereof
CN113135863B (en) Novel triazole compound and application thereof in agriculture
CN110914261B (en) Oxadiazole oxime derivative and application thereof in agriculture
CN112979629B (en) Oxime derivatives and application thereof in agriculture
CN112979628B (en) Diphenyl ether substituted oxime derivative and its application in agriculture
CN112979633B (en) Novel oxime derivative, preparation method and application thereof
CN114516845A (en) Triazole sulfonamide derivative and preparation method and application thereof
CN113929665A (en) Aryl-substituted triazole sulfonamide derivative and preparation method and application thereof
CN112442018B (en) Triazole-1, 3-disulfonamide derivative and application thereof in agriculture
CN112110894B (en) Phenyl oxime derivative and preparation method and application thereof
CN112110911B (en) 1,3, 4-Oxadiazole oxime derivative and preparation method and application thereof
CN114685392A (en) Phenyl-tetrazole oxime derivative and preparation method and application thereof
CN114685393A (en) Novel oxime derivative, preparation method thereof and application thereof in agriculture
CN112979628A (en) Oxime derivative substituted by diphenyl ether and application thereof in agriculture

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination