CN109311853A - Triazole derivative and its application in agricultural - Google Patents

Triazole derivative and its application in agricultural Download PDF

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Publication number
CN109311853A
CN109311853A CN201880002367.3A CN201880002367A CN109311853A CN 109311853 A CN109311853 A CN 109311853A CN 201880002367 A CN201880002367 A CN 201880002367A CN 109311853 A CN109311853 A CN 109311853A
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alkyl
aryl
halogenated
heteroaryl
heterocycle
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CN109311853B (en
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李义涛
姚文强
徐俊星
伍阳
刘新烁
林健
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Dongguan dongyangguang pesticide R & D Co., Ltd
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Dongguan Dongyang Sunshine Medical Intelligent Device R&d Co ltd
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    • 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
    • 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
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/84—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms six-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,4
    • 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
    • A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/06—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
    • C07D471/04—Ortho-condensed systems

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)

Abstract

The present invention provides a kind of triazole derivative and its application in agricultural；Specifically, the present invention provides a kind of stereoisomer, nitrogen oxides and salt such as formula (I) compound represented or formula (I) compound represented, preparation method；Composition and preparation containing these compounds and its purposes as prevention and treatment plant pathogenic fungi；Wherein R1、R2、Y、L1、L2There is meaning as described in the present invention with ring A.

Description

Triazole derivative and its application in agricultural Technical field
The present invention provides a kind of new triazole derivative and preparation method thereof, the composition containing these compounds and its application in agricultural.
Background technique
Triazole derivative because of it to broad spectrum activity, the high efficiency of plant pathogenic fungi the features such as, be widely used in ornamental crops, vegetable crop, field crop, cereal crops and fruit tree crop.Agricultural largely using for a long time due to pesticide now, so that the disease on crop, so that the control efficiency of pesticide be made to be substantially reduced, causes consumer cost to rise to which create resistances.Therefore, it is necessary to continually develop the new compound for providing more preferable control efficiency to solve these problems.
Summary of the invention
The present invention provides a kind of novel triazole antifungal agents, and composition and preparation containing such compound, for controlling plant pathogenic fungi.Specifically:
On the one hand, the present invention relates to stereoisomer, nitrogen oxides and the salt of one kind such as formula (I) compound represented or formula (I) compound represented:
Wherein,
R 1And R 2It is each independently hydrogen, alkyl, alkenyl, alkynyl, naphthenic base, heterocycle, aryl, heteroaryl, cycloalkyl-alkyl, heterocyclylalkyl group, aryl alkyl or heteroaryl alkyl；
Or R 1、R 2Heterocycle or heteroaryl are formed together with connected nitrogen-atoms；
Wherein, by R 1、R 2The heterocycle or heteroaryl being formed together with connected nitrogen-atoms are optionally selected from R by one or more 5Substituent group replaced；
Y is hydrogen, halogen, hydroxyl, cyano, nitro, amino, carboxyl, alkyl, alkenyl, alkynyl, halogenated alkyl, halogenated alkenyl, halo alkynyl, aryl, aryl alkyl, halogenated aryl or haloarylalkyl；
L 1And L 2It is each independently-(CR 3R 4) n-、-(CR 11R 22) m-O-、-(CR 33R 44) o-NR nOr-(CR 55R 66) p-S(O) q-；
Wherein, R 3And R 4It is each independently the alkyl that alkyl, the cyano that alkyl, the hydroxyl that hydrogen, halogen, amino, hydroxyl, cyano, nitro, alkyl, alkenyl, alkynyl, halogenated alkyl, amino replace replace replace or the alkyl that nitro replaces；
Or R 3、R 4C=O can be formed with the carbon atom being connected；
R 11、R 22、R 33、R 44、R 55And R 66It is each independently hydrogen, alkyl or halogenated alkyl；
R nFor hydrogen or alkyl；
Wherein, 0,1,2,3,4 or 5 n；
M, o and p is each independently 0,1,2,3 or 4；
Q is 0,1 or 2；
Or i) n >=2 when, two R on adjacent carbons 3Naphthenic base, heterocycle, aryl or heteroaryl can be formed together with two adjacent carbon atoms；Or ii) m >=2 when, two R on adjacent carbons 11Naphthenic base, heterocycle, aryl or heteroaryl can be formed together with two adjacent carbon atoms；Or iii) o >=2 when, two R on adjacent carbons 33Naphthenic base, heterocycle, aryl or heteroaryl can be formed together with two adjacent carbon atoms；Or iv) p >=2 when, two R on adjacent carbons 55Naphthenic base, heterocycle, aryl or heteroaryl can be formed together with two adjacent carbon atoms；
For naphthenic base, heterocycle, aryl or heteroaryl；
Wherein, Optionally R is selected from by 1,2,3 or 4 6Substituent group replaced；
Wherein, R 5And R 6It is each independently hydrogen, halogen, hydroxyl, cyano, nitro, amino, carboxyl, C 1-6Alkyl, C 2-6Alkenyl, C 2-6Alkynyl, halogenated C 1-6Alkyl, halogenated C 2-6Alkenyl, halogenated C 2-6Alkynyl, C 1-6Alkoxy, halogenated C 1-6Alkoxy, C 1-6Alkoxy-(C=O)-, C 1-6Alkoxy -C 1-6Alkyl-, C 1-6Alkyl-(C=O)-O-, C 1-6Alkyl-(C=O)-, C 1-6Alkyl-SO 2-、C 1-6Alkyl amino, C 1-6Alkyl amino-(C=O)-, C 1-6Alkyl amino-SO 2-、C 3-6Naphthenic base, C 2-6Heterocycle, C 6-10Aryl or C 1-6Heteroaryl.
In some embodiments, R 1And R 2It is each independently hydrogen, C 1-6Alkyl, C 2-6Alkenyl, C 2-6Alkynyl, C 3-8Naphthenic base, C 2-6Heterocycle, C 6-10Aryl, C 1-6Heteroaryl, C 3-8Naphthenic base-C 1-6Alkyl-, C 2-6Heterocycle-C 1-6Alkyl-, C 6-10Aryl-C 1-6Alkyl-or C 1-6Heteroaryl-C 1-6Alkyl-；
Or R 1、R 2C is formed together with connected nitrogen-atoms 2-6Heterocycle or 5-12 unit's heteroaryl；
Wherein, by R 1、R 2The C being formed together with connected nitrogen-atoms 2-6Heterocycle or 5-12 unit's heteroaryl are optionally selected from R by one or more 5Substituent group replaced；
Y is hydrogen, F, Cl, Br, I, hydroxyl, cyano, nitro, amino, carboxyl, C 1-6Alkyl, C 2-6Alkenyl, C 2-6Alkynyl, halogenated C 1-6Alkyl, halogenated C 2-6Alkenyl, halogenated C 2-6Alkynyl, C 6-10Aryl, C 6-10Aryl-C 1-6Alkyl-, halogenated C 6-10Aryl or halogenated C 6-10Aryl-C 1-6Alkyl-；
L 1And L 2It is each independently-(CR 3R 4) n-、-(CR 11R 22) m-O-、-(CR 33R 44) o-NR nOr-(CR 55R 66) p-S(O) q-；
Wherein, R 3And R 4It is each independently hydrogen, F, Cl, Br, I, amino, hydroxyl, cyano, nitro, C 1-6Alkyl, C 2-6Alkenyl, C 2-6Alkynyl, halogenated C 1-6The C that alkyl, amino replace 1-6The C that alkyl, hydroxyl replace 1-6The C that alkyl, cyano replace 1-6The C that alkyl or nitro replace 1-6Alkyl；
Or R 3、R 4C=O can be formed with the carbon atom being connected；
R 11、R 22、R 33、R 44、R 55And R 66It is each independently hydrogen, C 1-6Alkyl or halogenated C 1-6Alkyl；
R nFor hydrogen or C 1-6Alkyl；
Wherein, 0,1,2,3,4 or 5 n；
M, o and p is each independently 0,1,2,3 or 4；
Q is 0,1 or 2；
Or i) n >=2 when, two R on adjacent carbons 3C can be formed together with two adjacent carbon atoms 3-6Naphthenic base, C 2-6Heterocycle, C 6-10Aryl or 5-10 unit's heteroaryl；Or ii) m >=2 when, two R on adjacent carbons 11C can be formed together with two adjacent carbon atoms 3-6Naphthenic base, C 2-6Heterocycle, C 6-10Aryl or 5-10 unit's heteroaryl；Or iii) o >=2 when, two R on adjacent carbons 33C can be formed together with two adjacent carbon atoms 3-6Naphthenic base, C 2-6Heterocycle, C 6-10Aryl or 5-10 unit's heteroaryl；Or iv) p >=2 when, two R on adjacent carbons 55C can be formed together with two adjacent carbon atoms 3-6Naphthenic base, C 2-6Heterocycle, C 6-10Aryl or 5-10 unit's heteroaryl；
For C 3-8Naphthenic base, C 2-6Heterocycle, C 6-10Aryl or 5-12 unit's heteroaryl；
Wherein, Optionally R is selected from by 1,2,3 or 4 6Substituent group replaced；
Wherein, R 5And R 6It is each independently hydrogen, F, Cl, Br, I, hydroxyl, cyano, nitro, amino, carboxyl, C 1-4Alkyl, C 2-4Alkenyl, C 2-4Alkynyl, halogenated C 1-4Alkyl, halogenated C 2-4Alkenyl, halogenated C 2-4Alkynyl, C 1-4Alkoxy, halogenated C 1-4Alkoxy, C 1-4Alkoxy-(C=O)-, C 1-4Alkoxy -C 1-3Alkyl-, C 1-4Alkyl-(C=O)-O-, C 1-4Alkyl-(C=O)-, C 1-4Alkyl-SO 2-、C 1-4Alkyl amino, C 1-4Alkyl amino-(C=O)-, C 1-4Alkyl amino-SO 2-、C 3-6Naphthenic base, C 2-6Heterocycle, C 6-10Aryl or C 1-4Heteroaryl.
In some embodiments, R 1And R 2It is each independently hydrogen, C 1-4Alkyl, C 2-4Alkenyl, C 2-4Alkynyl, C 3-6Naphthenic base, C 2-6Heterocycle, C 6-10Aryl, C 1-5Heteroaryl, C 3-6Naphthenic base-C 1-4Alkyl-, C 2-5Heterocycle-C 1-4Alkyl-, C 6-10Aryl-C 1-4Alkyl-or C 1-5Heteroaryl-C 1-4Alkyl-.
In some embodiments, R 1、R 2C is formed together with connected nitrogen-atoms 2-5Heterocycle or 5-10 unit's heteroaryl；
Wherein, R 1、R 2The C being formed together with connected nitrogen-atoms 2-5Heterocycle or 5-10 unit's heteroaryl are optionally selected from R by one or more 5Substituent group replaced；
R 5For hydrogen, F, Cl, Br, hydroxyl, cyano, nitro, amino, carboxyl, C 1-4Alkyl or halogenated C 1-4Alkyl.
In some embodiments, Y is hydrogen, F, Cl, Br, hydroxyl, cyano, nitro, amino, carboxyl, C 1-4Alkyl, C 2-4Alkenyl, C 2-4Alkynyl, halogenated C 1-4Alkyl, halogenated C 2-4Alkenyl, halogenated C 2-4Alkynyl, C 6-10Aryl, C 6-10Aryl-C 1-4Alkyl-, halogenated C 6-10Aryl or halogenated C 6-10Aryl-C 1-4Alkyl-.
In other embodiments, R 1And R 2It is each independently hydrogen ,-CH 3、-CH 2CH 3、-CH 2CH 2CH 3、-CH(CH 3) 2, cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, benzyl, 4- luorobenzyl or 4- cyanobenzyls.
In other embodiments, R 1、R 2Following subformula is formed together with connected nitrogen-atoms:
In other embodiments, Y is hydrogen, F, Cl, Br, hydroxyl, cyano, nitro, amino, carboxyl ,-CH 3、-CHF 2、-CH 2F、-CF 3、-CH 2CH 3、-CH 2CH 2F、-CH 2CHF 2、-CH 2CH 2CH 3、-CH(CH 3) 2、-C(CH 3) 3, phenyl, 2- fluorophenyl, 3- fluorophenyl or 4- fluorophenyl.
In some embodiments, L 1And L 2It is each independently-(CR 3R 4) n-；
Wherein, R 3And R 4It is each independently hydrogen, F, Cl, Br, I, amino, hydroxyl, cyano, nitro, C 1-4Alkyl, halogenated C 1-4The C that alkyl, amino replace 1-4The C that alkyl, hydroxyl replace 1-4The C that alkyl, cyano replace 1-4The C that alkyl or nitro replace 1-4Alkyl；
Wherein, 0,1,2,3,4 or 5 n.
Also in other embodiments, R 3、R 4C=O can be formed with the carbon atom being connected.
In other embodiments, L 1And L 2It is each independently-(CR 3R 4) nOr-(CR 11R 22) m-O-；
R 11And R 22It is each independently hydrogen, C 1-4Alkyl or halogenated C 1-4Alkyl；
M is 0,1,2,3 or 4；
Wherein, R 3、R 4There is meaning of the present invention with n.
Also in other embodiments, L 1And L 2It is each independently-(CR 3R 4) nOr-(CR 33R 44) o-NR n-；
R 33And R 44It is each independently hydrogen, C 1-4Alkyl or halogenated C 1-4Alkyl；
O is 0,1,2,3 or 4；
R nFor hydrogen or C 1-4Alkyl；
Wherein, R 3、R 4There is meaning of the present invention with n.
Also in other embodiments, L 1And L 2It is each independently-(CR 3R 4) nOr-(CR 55R 66) p-S(O) q-；
R 55And R 66It is each independently hydrogen, C 1-4Alkyl or halogenated C 1-4Alkyl；
P is 0,1,2,3 or 4；
Q is 0,1 or 2；
Wherein, R 3、R 4There is meaning of the present invention with n.
In some embodiments, two R when n >=2, on adjacent carbons 3C can be formed together with two adjacent carbon atoms 3-6Naphthenic base or C 6-10Aryl.
Also in some embodiments, two R when m >=2, on adjacent carbons 11C can be formed together with two adjacent carbon atoms 3-6Naphthenic base or C 6-10Aryl.
In other embodiments, two R when o >=2, on adjacent carbons 33C can be formed together with two adjacent carbon atoms 3-6Naphthenic base or C 6-10Aryl.
Also in other embodiments, two R when p >=2, on adjacent carbons 55C can be formed together with two adjacent carbon atoms 3-6Naphthenic base or C 6-10Aryl.
In some embodiments, For C 3-6Naphthenic base, C 2-5Heterocycle, C 6-10Aryl or 5-10 unit's heteroaryl；
Wherein, Optionally R is selected from by 1,2,3 or 4 6Substituent group replaced；
R 6For hydrogen, F, Cl, Br, I, amino, hydroxyl, cyano, nitro, carboxyl, C 1-4Alkyl, halogenated C 1-4Alkyl, C 1-4Alkoxy, halogenated C 1-4Alkoxy, C 1-4Alkoxy-(C=O)-or C 1-4Alkyl-(C=O)-O-.
Also in some embodiments, For C 3-6Naphthenic base, C 2-5Heterocycle, C 6-10Aryl or 5-6 unit's heteroaryl；
Wherein, Optionally R is selected from by 1,2,3 or 4 6Substituent group replaced；
R 6For hydrogen, F, Cl, Br, I, amino, hydroxyl, cyano, nitro, carboxyl, C 1-4Alkyl, halogenated C 1-4Alkyl, C 1-4Alkoxy, halogenated C 1-4Alkoxy, C 1-4Alkoxy-(C=O)-or C 1-4Alkyl-(C=O)-O-.
In other embodiments, For following subformula:
Wherein, R 7For hydrogen or C 1-4Alkyl；
X 1、X 2、X 3、X 4、X 5And X 6It is each independently N or CR 8；
R 8For hydrogen, F, Cl, Br, I, C 1-4Alkyl, halogenated C 1-4Alkyl or C 1-4Alkoxy-(C=O)-.
Also in other embodiments, For following subformula:
In some embodiments, For following subformula:
Also in some embodiments, the present invention relates to a kind of compound, the compound with one of following structure or the stereoisomer with one of following structural compounds, nitrogen oxides and salt:
On the one hand, the present invention relates to a kind of compositions, and it includes one or more compounds of the present invention.
In some embodiments, composition of the invention further includes acceptable surfactant and/or carrier in Pesticide Science.
On the other hand, the application the present invention relates to a kind of composition comprising the compounds of this invention in control of plant disease.
Content noted earlier only outlines certain aspects of the invention, but is not limited to these aspects and otherwise content for more specific complete description below.
Detailed description of the invention
Definition and general terms
It will now be described in more detail certain embodiments of the present invention, the example is by the structural formula and chemical formula explanation that are appended.The invention is intended to cover all replacement, modification and equivalent technical solutions, they are included in the scope of the invention defined such as claim.Those skilled in the art will appreciate that many can be used in the practice present invention with similar or equivalent method and material of the present invention.The present invention is not limited to method of the present invention and material.Document, patent and the similar material combined one or more from the application is different or contradicts in the case where (including but not limited to defined in term, term application, described technology, etc.), be subject to the application.
It will further be appreciated that certain features of the invention, be it is clearly visible, be described in a number of independent embodiments, but can also provide in combination in a single embodiment.Conversely, various features of the invention are described in a single embodiment for brevity, but can also be individually or with the offer of any suitable sub-portfolio.
Unless otherwise stated, all scientific and technical terminologies used in the present invention, which have, is generally understood identical meaning with those skilled in the art of the invention.All patents of the present invention and public publication are integrally incorporated the present invention by reference.
Unless otherwise stated, following definition used in the present invention should be applied.For purposes of the present invention, chemical element and periodic table of elements CAS editions, and " Handbook of Chemistry and Physics ", the 75th edition, 1994 is consistent.Furthermore, organic chemistry General Principle can refer to " Organic Chemistry ", Thomas Sorrell, University Science Books, Sausalito:1999, and " March's Advanced Organic Chemistry " by Michael B.Smith and Jerry March, John Wiley & Sons, description in New York:2007, entire contents are incorporated by reference into the present invention.
There is apparent conflict unless otherwise indicated or in context, the article " one " used herein, " one (kind) " and " described " are intended to include "at least one" or " one or more ".Therefore, these articles used herein refer to the article of one or more than one (i.e. at least one) object.For example, " component " refers to one or more components, it is possible to there is more than one component to be taken into account in the embodiment of the embodiment and use or use.
Term "comprising" is open language, that is, includes content specified by the present invention, but otherwise content is not precluded.
" stereoisomer " refers to identical chemical constitution, but atom or the group spatially different compound of arrangement mode.Stereoisomer includes enantiomter, diastereoisomer, conformer (rotational isomer), geometric isomer (cis/trans) isomers, atropisomer, etc..
" enantiomter " refers to two isomers that cannot be overlapped but be mutually mirror of a compound.
" diastereoisomer " refer to there are two or multiple chiral centres and its molecule not stereoisomer of mirror image each other.Diastereoisomer has different physical properties, such as fusing point, boiling point, spectral property and reactivity.Non-enantiomer mixture can be operated such as electrophoresis and chromatography, such as HPLC by high resolution analysis and be separated.
Stereochemical definitions used in the present invention and rule generally follow 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, the description in 1994.
Many organic compounds exist with optical active forms, i.e., they have the ability for rotating the plane of linearly polarized light.When describing optically active compound, absolute configuration of the molecule about one or more chiral centre is indicated using prefix D and L or R and S.Prefix d and l or (+) and (-) are the symbols for the rotation of linearly polarized light caused by appointed compound, wherein (-) or l indicate that compound is left-handed.Prefix is (+) or the compound of d is dextrorotation.A kind of specific stereoisomer is enantiomter, and the mixture of this isomers is referred to as enantiomeric mixture.The 50:50 mixture of enantiomter is known as racemic mixture or racemic modification, when chemical reaction or in the process without stereoselectivity or stereospecificity when, may occur in which such case.
As described in the invention, the compound of the present invention can be optionally replaced one or more substituent groups, such as general formula compound above, or as example special inside embodiment, subclass, and a kind of compound that the present invention is included.It should be appreciated that this term can be used interchangeably " optionally replacing " this term with " substituted or non-substituted ".In general, " substituted " the one or more hydrogen atoms indicated in given structure of term are replaced specific substituent group.Unless otherwise indicated, an optional substituent group can be replaced at various substitutable position of that group.When more than one position can be replaced one or more substituent groups selected from specific group identical or differently, then substituent group can replace at various locations in given structural formula.Wherein the substituent group can be, but it is not limited to, deuterium, fluorine, chlorine, bromine, iodine, cyano, hydroxyl, nitro, amino, carboxyl, alkyl, alkoxy, alkoxyalkyl, alkyloxy-alkoxy, alkoxy alkylamino, aryloxy group, heteroaryl oxygroup, heterocycle oxygroup, alkoxy aryl, heteroarylalkoxy, heterocyclylalkoxy, cycloalkyl alkoxy, alkylamino, alkyl amino alkyl, alkylamino alkylamino, cycloalkyl amino, amino-n-cycloalkyl, alkylthio group, halogenated alkyl, halogenated alkoxy, the alkyl that hydroxyl replaces, the alkylamino that hydroxyl replaces, the alkyl that cyano replaces, the alkoxy that cyano replaces, the alkylamino that cyano replaces, the alkyl that amino replaces, alkyl acyl, miscellaneous alkyl, naphthenic base, cycloalkenyl, cycloalkyl-alkyl, heterocycle, heterocyclylalkyl group, heterocyclylacyl, aryl, aryl alkyl, Fragrant amino, heteroaryl, heteroaryl alkyl, heteroaryl amino, amide groups, sulfonyl, amino-sulfonyl etc..
In addition, it should be noted that, unless otherwise explicitly pointing out, used describing mode " each ... independently to be " and " ... be each independently " and " ... independently be " can be interchanged in the present invention, it shall be understood in a broad sense, either referring among the different groups, do not influenced mutually between expressed specific option between the same symbol, it can also indicate in the same group, not influenced mutually between expressed specific option between the same symbol.
It is disclosed in the substituent group of each section of this specification, disclosed compound of present invention according to radical species or range.It particularly points out, the present invention includes each independent sub-combinations thereof of each member of these radical species and range.For example, term " C 1-C 6Alkyl " or " C 1-6Alkyl " refers in particular to the methyl being individually disclosed, ethyl, C 3Alkyl, C 4Alkyl, C 5Alkyl and C 6Alkyl.
Terminology used in the present invention " alkyl " or " alkyl group " indicate to contain 1 to 20 carbon atom, the linear chain or branched chain univalent hydrocarbyl group of saturation；Replaced the substituent group that wherein alkyl group is optionally described by one or more present invention.Unless otherwise detailed instructions, alkyl group contains 1-20 carbon atom.In one embodiment, alkyl group contains 1-12 carbon atom；In one embodiment, alkyl group contains 1-8 carbon atom；In another embodiment, alkyl group contains 1-6 carbon atom；In yet another embodiment, alkyl group contains 1-4 carbon atom；Also in one embodiment, alkyl group contains 1-3 carbon atom.
The example of alkyl group includes, but is not limited to, methyl (Me ,-CH 3), ethyl (Et ,-CH 2CH 3), n-propyl (n-Pr ,-CH 2CH 2CH 3), isopropyl (i-Pr ,-CH (CH 3) 2), normal-butyl (n-Bu ,-CH 2CH 2CH 2CH 3), isobutyl group (i-Bu ,-CH 2CH(CH 3) 2), sec-butyl (s-Bu ,-CH (CH 3)CH 2CH 3), tert-butyl (t-Bu ,-C (CH 3) 3), n-pentyl (- CH 2CH 2CH 2CH 2CH 3), 2- amyl (- CH (CH 3)CH 2CH 2CH 3), 3- amyl (- CH (CH 2CH 3) 2), 2- methyl -2- butyl (- C (CH 3) 2CH 2CH 3), 3- methyl -2- butyl (- CH (CH 3)CH(CH 3) 2), 3- methyl-1-butyl (- CH 2CH 2CH(CH 3) 2), 2-methyl-1-butene base (- CH 2CH(CH 3)CH 2CH 3), etc..
Term " alkenyl " indicates the linear chain or branched chain monovalent hydrocarbon containing 2-12 carbon atom, wherein at least one unsaturated sites have a carbon-to-carbon sp 2Double bond, wherein the alkenyl group can be optionally replaced one or more substituent groups described in the invention comprising the positioning of " cis " and " tans ", or the positioning of " E " and " Z ".In one embodiment, alkenyl group includes 2-8 carbon atom；In another embodiment, alkenyl group includes 2-6 carbon atom；In yet another embodiment, alkenyl group includes 2-4 carbon atom.The example of alkenyl group includes, but is not limited to, vinyl (- CH=CH 2), allyl (- CH 2CH=CH 2), acrylic (CH 3- CH=CH-), the cyclobutenyl (CH of oxo 3- C (=O)-CH=CH-) etc..
Term " alkynyl " indicates the linear chain or branched chain monovalent hydrocarbon containing 2-12 carbon atom, tri- key of wherein at least one carbon-to-carbon sp.
Term " alkoxy " indicates that alkyl group is connected by oxygen atom with molecule rest part, and wherein alkyl group has meaning as described in the present invention.The example of alkoxy base includes, but is not limited to, methoxyl group (MeO ,-OCH 3), ethyoxyl (EtO ,-OCH 2CH 3), 1- propoxyl group (n-PrO, n- propoxyl group ,-OCH 2CH 2CH 3), 2- propoxyl group (i-PrO, i- propoxyl group ,-OCH (CH 3) 2) etc..
Term " naphthenic base " indicates containing 3-12 carbon atom, monovalent or multivalence saturation monocyclic, bicyclic or tricyclic system.In one embodiment, naphthenic base includes 3-10 carbon atom；In another embodiment, naphthenic base includes 3-8 carbon atom；In yet another embodiment, naphthenic base includes 3-6 carbon atom.The group of naphthene base is optionally replaced one or more substituent groups described in the invention.Such example includes, but is not limited to, cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, suberyl, cyclooctyl, cyclononyl, cyclodecyl, ring undecyl, cyclo-dodecyl, etc..
Term " cycloalkyl-alkyl " indicates alkyl group replaced one or more groups of naphthene base, and wherein alkyl group and group of naphthene base have meaning as described in the present invention.
Term " heterocycle " and " heterocycle " are used interchangeably here, all refer to the unsaturated monocyclic, bicyclic or tricyclic of saturation or part comprising 3-15 annular atom, aromatic rings is not included in monocyclic, bicyclic or tricyclic wherein, and at least one annular atom is selected from nitrogen, sulphur and oxygen atom.Unless otherwise stated, heterocycle can be carbon-based or nitrogen base, and-CH 2Group can be substituted optionally by-C (=O)-.The sulphur atom of ring can optionally be oxidized to S- oxide.The nitrogen-atoms of ring can optionally be oxidized to N- oxygen compound.The example of heterocycle includes, but it is not limited to, Oxyranyle, azelidinyl, oxetanylmethoxy, thietanyl, pyrrolidinyl (such as 2- pyrrolidinyl), 2- pyrrolinyl, 3- pyrrolinyl, pyrazolidinyl, imidazolinyl, imidazolidinyl, tetrahydrofuran base, dihydrofuryl, tetrahydro-thienyl, dihydrothiophene, 1, 3- dioxy cyclopenta, two sulphur cyclopenta, THP trtrahydropyranyl, dihydro pyranyl, 2H- pyranose, 4H- pyranose, tetrahydro thiapyran base, piperidyl (2- piperidyl, 3- piperidyl, 4- piperidyl), morpholinyl, thio-morpholinyl, (1- oxo)-thio-morpholinyl, (1, 1- dioxo)-thio-morpholinyl, piperazinyl, dioxanes base, dithianyl, thiophene oxane base, high piperazine base, homopiperidinyl, oxepane alkyl, thia cycloheptane Base, 2- oxa- -5- azabicyclo [2.2.1] hept- 5- base, tetrahydro pyridyl.- CH in heterocycle 2Group includes, but are not limited to 2- oxo-pyrrolidine base, oxo -1,3-thiazoles alkyl, 2- piperidone base, 3,5- dioxy piperazine piperidinyls by-C (=the O)-example replaced.The example that sulphur atom is oxidized in heterocycle includes, but are not limited to sulfolane base, 1,1- dioxothiomorpholinyl.The heterocyclyl groups are optionally replaced one or more substituent groups described in the invention.
Term " heterocyclylalkyl group " refers to alkyl group replaced one or more heterocyclyl groups, and wherein alkyl group and heterocyclyl groups have meaning as described in the present invention.
Term " hetero atom " refers to O, S, N, P and Si, the form including any oxidation state of N, S and P；The form of primary, secondary, tertiary amine and quaternary ammonium salt；Or the substituted form of hydrogen in heterocycle on nitrogen-atoms, for example, N (as the N in 3,4- dihydro-2 h-pyrrole base), NH (as the NH in pyrrolidinyl) or NR (NR in pyrrolidinyl replaced as N-).
Term " halogen " refers to fluorine (F), chlorine (Cl), bromine (Br) or iodine (I).
Term " aryl " indicates to contain 6-14 annular atom, or 6-12 annular atom, or monocycle, bicyclic and tricyclic the carbocyclic ring system of 6-10 annular atom, wherein, at least one ring system is aromatic, wherein each ring system includes 3-7 former molecular ring, and has one or more attachment points to be connected with the rest part of molecule.Term " aryl " can be used interchangeably with term " aromatic rings ".The example of aryl group may include phenyl, indenyl, naphthalene and anthryl.The aryl group is optionally replaced one or more substituent groups described in the invention.
Term " aryl alkyl " indicates alkyl group replaced one or more aryl groups, such as benzyl.
Term " heteroaryl " indicates to contain 5-12 annular atom, or 5-10 annular atom, or monocycle, the bicyclic and three-ring system of 5-6 annular atom, wherein at least one ring system is aromatic, and at least one ring system includes one or more hetero atoms, wherein each ring system includes 5-7 former molecular ring, and has one or more attachment points to be connected with molecule rest part.Term " heteroaryl " can be used interchangeably with term " hetero-aromatic ring " or " heteroaromatics ".The heteroaryl groups are optionally replaced one or more substituent groups described in the invention.In one embodiment, 5-10 former molecular heteroaryl includes 1,2,3 or 4 hetero atom for being independently selected from O, S and N.
The example of heteroaryl groups includes, but it is not limited to, 2- furyl, 3- furyl, TMSIM N imidazole base, 2- imidazole radicals, 4- imidazole radicals, 5- imidazole radicals, 3- isoxazolyl, 4- isoxazolyl, 5- isoxazolyl, 2- oxazolyl, 4- oxazolyl, 5- oxazolyl, N- pyrrole radicals, 2- pyrrole radicals, 3- pyrrole radicals, 2- pyridyl group, 3- pyridyl group, 4- pyridyl group, 2- pyrimidine radicals, 4- pyrimidine radicals, 5- pyrimidine radicals, pyridazinyl (such as 3- pyridazinyl), 2- thiazolyl, 4- thiazolyl, 5- thiazolyl, tetrazole radical (such as 5- tetrazole radical), triazolyl (such as 2- triazolyl and 5- triazolyl), 2- thienyl, 3- thienyl, pyrazolyl, isothiazolyl, 1, 2, 3- oxadiazoles base, 1, 2, 5- oxadiazoles base, 1, 2, 4- Oxadiazoles base, 1,2,3-triazoles base, 1,2,3- thio biphosphole base, 1,3,4- thio biphosphole base, 1,2,5- thio biphosphole base, pyrazinyl, 1,3,5-triazines base, pyrimidine ketone group, pyriconyl；It also include below bicyclic, but it is bicyclic to be not limited to these: benzimidazolyl, benzofuranyl, benzo tetrahydrofuran base, indyl (such as 2- indyl), 3,4- dihydro-isoquinoline -2 (1H)-base, 6,7- dihydro-thiophenes [3,2-c] and pyridine -5 (4H)-base etc..
Term " heteroaryl alkyl " refers to alkyl group replaced one or more heteroaryl groups.
Term " alkoxyalkyl " refers to alkyl group replaced one or more alkoxy bases.
Term " alkyl amino " refers to amino group replaced one or two alkyl group.
Term " halogenated alkyl " refers to alkyl group replaced one or more halogens.
Term " halogenated alkenyl " refers to alkenyl group replaced one or more halogens.
Term " halo alkynyl " refers to alkynyl group replaced one or more halogens.
Term " halogenated aryl " refers to aryl group replaced one or more halogens.
Term " haloarylalkyl " refers to aromatic yl alkyl group replaced one or more halogens.
Term " halogenated alkoxy " refers to alkoxy base replaced one or more halogens.
The salt of compound of the present invention, including derived from those of alkali or alkaline earth metal and it is derived from those of ammonia and amine.Preferred cation includes sodium, potassium, magnesium and has chemical formula N +(R AR BR CR D) ammonium cation, wherein R A、R B、R CAnd R DIndependently selected from hydrogen, C 1-C 6Alkyl and C 1-C 6Hydroxy alkyl.The salt of compound with chemical formula (I) can be prepared by being handled with metal hydroxides (such as sodium hydroxide) or amine (such as ammonia, trimethylamine, diethanol amine, 2- methyl mercapto propylamine, diallyl amine, 2- butoxyethylamine, morpholine, ring lauryl amine or benzylamine) the compound with chemical formula (I).
When the compound of the present invention includes an alkali part, acceptable salt can be formed by organic acid and inorganic acid, such as acetic acid, propionic acid, lactic acid, citric acid, tartaric acid, succinic acid, fumaric acid, maleic acid, malonic acid, mandelic acid, malic acid, phthalic acid, hydrochloric acid, hydrobromic acid, phosphoric acid, nitric acid, sulfuric acid, methanesulfonic acid, naphthalene sulfonic acids, benzene sulfonic acid, toluenesulfonic acid, camphorsulfonic acid and similarly known acceptable acid.
The composition and preparation of the compounds of this invention
The compound of the present invention also typically includes acceptable surfactant and/or carrier in Pesticide Science generally useful as the fungicidal activity ingredient in composition, that is, preparation.
Above-mentioned surfactant can be various surfactants well known to formulations of pesticide field, and the present invention is preferably one of emulsifier, dispersing agent and wetting agent or a variety of.
Other carriers in addition to above-mentioned surfactant can be various carriers well known to formulations of pesticide field, including various silicates, carbonate, Sulfates, oxide-based, phosphoric acid salt, plant vector class, synthetic vectors class.Specifically, such as: white carbon black, kaolin, diatomite, clay, talcum, organobentonite, float stone, titanium dioxide, dextrin, cellulose powder, precipitated calcium carbonate, soluble starch, cornstarch, sawdust powder, urea, amine fertilizer, the mixture of urea and amine fertilizer, glucose, maltose, sucrose, Anhydrous potassium carbonate, natrium carbonicum calcinatum, Carbon Dioxide hydrogen potassium, anhydrous sodium bicarbonate, attapulgite, the mixture and natrium carbonicum calcinatum of Anhydrous potassium carbonate and Carbon Dioxide hydrogen potassium and anhydrous sodium bicarbonate one of mixture or a variety of.
Mentioned emulsifier can be various emulsifiers well known to formulations of pesticide field, specifically, the emulsifier can be calcium dodecyl benzene sulfonate, three phenethyl phenol polyoxyethylene ether phosphates, fatty alcohol polyoxyethylene ether, alkyl phenol polyoxyethylene ether, alkylphenol-polyethenoxy polyethenoxy ether, fatty amine, the ethylene oxide adduct of fatty acid amide, polyoxyethylene carboxylate, rosin acid ethylene oxide adduct, polyol fatty acid ester and its ethylene oxide adduct, styryl phenyl polyoxyethylene ether, alkyl phenol formaldehyde resin polyoxyethylene ether, terminal hydroxy group polyoxyethylene poly-oxygen propylene aether, one of styrylphenol formaldehyde resin Polyoxyethylene polyoxypropylene ether and castor oil polyoxyethylene ether are a variety of.
Above-mentioned dispersing agent can be various dispersing agents well known to formulations of pesticide field, specifically, which is one of acrylate homopolymer sodium salt, Malaysia acid disodium salt, naphthalene sulfonic acid-formaldehyde condensation product sodium salt, rosin segmented polyoxyethylene ether polyoxypropylene ether sulfonate, terminal hydroxy group polyoxyethylene poly-oxygen propylene aether block copolymer, three phenethyl phenol polyoxyethylene ether phosphates, aliphatic alcohol polyoxyvinethene phosphate and p-hydroxyphenyl lignin sulfonic acid sodium salt or a variety of.
Above-mentioned wetting agent can be various wetting agents well known to formulations of pesticide field, specifically, which can be one of lauryl sodium sulfate, Teepol, neopelex, fatty alcohol polyoxyethylene ether, alkylnaphthalene sulfonate, alkyl phenol resin polyoxyethylene ether sulfate or a variety of.
Microbicide compositions according to the present invention; the microbicide compositions can also contain various preparation used additives commonly used by formulations of pesticide field; specifically, said preparation used additives can be one of solvent, cosolvent, thickener, antifreezing agent, capsule material, protective agent, defoaming agent, disintegrating agent, stabilizer, preservative and binder or a variety of.
Above-mentioned solvent can be various solvents well known to formulations of pesticide field, and specifically, which can be one of organic solvent, vegetable oil, mineral oil, solvent naphtha and water or a variety of.
Wherein, the organic solvent includes N-Methyl pyrrolidone, tetrahydrofuran, dimethyl sulfoxide, N, N- dimethyldecamide, N, dinethylformamide, trimethylbenzene, durene, dimethylbenzene, toluene, octane, heptane, methanol, isopropanol, n-butanol, tetrahydrofurfuryl alcohol, tributyl phosphate, Isosorbide-5-Nitrae-one of dioxane and cyclohexanone or a variety of.
The vegetable oil includes methylated vegetable oils, turpentine-based vegetable oil, turpentine oil, one of epoxidized soybean oil, soybean oil, peanut oil, rapeseed oil, castor oil, corn oil and pine-seed oil or a variety of.
The mineral oil includes one of liquid wax, machine oil, kerosene and lubricating oil or a variety of.
Meanwhile above-mentioned solvent can also be used as cosolvent use.
Above-mentioned antifreezing agent can be various antifreezing agents well known to formulations of pesticide field, and the present invention is preferably one of ethylene glycol, propylene glycol, glycerol and urea or a variety of.
Above-mentioned thickener can be various thickeners well known to formulations of pesticide field, specifically, which can be one of xanthan gum, polyvinyl alcohol, POLYPROPYLENE GLYCOL, polyethylene glycol, white carbon black, diatomite, kaolin, clay, sodium alginate, aluminum magnesium silicate, lagoriolite, carboxymethyl cellulose, hydroxypropyl cellulose sodium and organobentonite or a variety of.
Above-mentioned capsule material can be various capsule materials well known to formulations of pesticide field, and the present invention is preferably one of polyurethane, polyureas and Lauxite or a variety of.
Above-mentioned protective agent can be various protective agents well known to formulations of pesticide field, and the present invention is preferably polyvinyl alcohol and/or polyethylene glycol.
Above-mentioned defoaming agent can be various defoaming agents well known to formulations of pesticide field, and the present invention is preferably one of organosiloxane, tributyl phosphate and silicone or a variety of.
Above stabilizer is selected from one of triphenyl phosphite, epoxychloropropane and aceticanhydride or a variety of.
Foregoing preservatives are selected from one of benzoic acid, sodium benzoate, 1,2- benzisothiazole-3-ketone (abbreviation BIT), Kathon CG and potassium sorbate or a variety of.
The present invention also provides a kind of preparation as prepared by above-mentioned microbicide compositions, the dosage form of the preparation is missible oil, aqueous emulsion, microemulsion, soluble liquid, aqueous suspension agent, suspoemulsion, ultra-low volume spray agent, oil-suspending agent, microcapsule suspending agent, water surface film-spreading oil solution, wettable powder, water-dispersible granules, dry suspending agent, soluble powder, soluble granula, emulsifiable pulvis, emulsifiable granule, granule, solid microcapsule formulation, effervescent tablet, effervescent, water floating dispersible granule or seed coat agent.Above-mentioned dosage form can be prepared by the conventional method of this field.
The preparation method of above-mentioned cream preparation for example may include that the mixing of each active component, solvent, cosolvent and emulsifier is formed it into homogeneous transparent oil phase, and cream preparation can be obtained.
Above-mentioned method for producing aqueous emulsion for example may include mixing active constituent, emulsifier, cosolvent and solvent, become homogeneous oil phase；Water, thickener, antifreezing agent etc. are mixed, make it at uniform water phase.Under high speed shear, water phase is added to oily phase or oil is added to water phase, forms the aqueous emulsion of favorable dispersibility.
The preparation method of above-mentioned microemulsion for example can be active constituent, emulsifier, and solvent is mixed into homogeneous and transparent oily phase.Under stirring conditions, water is gradually added, forms it into homogeneous and transparent microemulsion.
The preparation method of above-mentioned water/oil-suspending agent: it for example can be with water or oil as medium, the auxiliary agents such as active component, surfactant be added in sand milling kettle, are carried out after being ground to certain partial size, filter.The thickener measured is added in ground mother liquor again, shearing is uniformly dispersed.Oil-suspending agent or aqueous suspension agent is made.
The preparation method of above-mentioned water-dispersible granules and soluble granula: it will be uniformly mixed each active component, dispersing agent, wetting agent, carrier such as can be; then pass through air-flow crushing to certain partial size; water is added to be mediated; it is eventually adding in pelletizer and is granulated, water-dispersible granules or soluble granula can be obtained after dry.
The preparation method of above-mentioned soluble powder and wettable powder: filler each active component, various auxiliary agents and other carriers is sufficiently mixed such as can be, uses ultra-fine pulverizer disintegrating.
Microbicide compositions of the invention can be provided in the form of finished product preparation, i.e., each substance has mixed in composition；It can also be provided, voluntarily be mixed in bucket or tank using preceding, and selectively mixed and be diluted with water according to the concentration of required active material with independent dosage form.
The application of the compounds of this invention and composition
The compound of the present invention can be used as plant disease-controlling agent.Therefore; the present invention may also include the method for controlling the plant disease as caused by plant pathogenic fungi, and the method includes applying a effective amount of the compound of the present invention or Fungicidal composition comprising the compound to plant to be protected or part thereof or to vegetable seeds to be protected.The compound of the present invention and/or composition can provide control to the disease as caused by Basidiomycetes, Ascomycetes, Oomycete and deuteromycetes broad-spectrum plant disease fungus.They can efficiently control the blade pathogen of broad-spectrum plant disease, especially ornamental crops, turf crop, vegetable crop, field crop, cereal crops and fruit tree crop.These pathogen include: Oomycete, including Phytophthora (Phytophthora) disease such as phytophthora infestans (Phytophthora infestans), phytophthora sojae kaufmann&gerdemann (Phytophthora megasperma), foot rot of citrus bacterium (Phytophthora parasitica), the disease of camphor tree phytophthora (Phytophthora cinnamomi) and phytophthora capsici (Phytophthora capsici), the careless rotten mould withered disease for belonging to (Pythium) species disease such as level ground grass Pythium aphanidermatu (Pythium aphanidermatum), and Peronosporaceae (Pero Nosporaceae) species disease such as Plasmopara viticola (Plasmopara viticola), Peronospora disease (Peronospora spp.) (including Peronosporatabacina (Peronospora tabacina) and Peronospora parasitic bacterium (Peronospora parasitica)), Pseudoperonospora (Pseudoperonospora spp.) disease (including bacterium of downy mildew of cucumber (Pseudoperonospora cubensis) and disk stalk mould germ (Bremia lactucae))；Sac fungus (including Alternaria (Alternaria) germ such as tomato early blight bacterium (Alternaria solani) and black spot of cabbage bacterium (Alternaria brassicae), ball seat Pseudomonas (Guignardia) disease such as black rot of grape bacterium (Guignardia bidwell), Venturia (Venturia) disease such as apple black star bacteria (Venturia inaequalis), Septoria (Septoria) disease such as glume blight bacterium (Septoria nodorum) and leaf spoting bacteria (Septoria tritici), white powder (powdery mildew) disease is for example white Powder Pseudomonas germ (Erysiphe spp.) (including wheat powdery mildew (Erysiphe graminis) and trailing plants Powdery Mildew (Erysiphe polygoni)), grape powdery mildew (Uncinula necatur), cucumber powdery mildew's pathogen (Sphaerotheca fuligena) and apple mildew bacterium (Podosphaera leucotricha), wheat Phyllostachys pubescens (Pseudocercosporella herpotrichoides), grey mold Pseudomonas (Botrytis) disease such as Botrytis cinerea germ (Botrytis cinerea), Monilinia fructicola (Mo Nilinia fructicola), sclerotium Pseudomonas (Sclerotinia) disease such as Sclerotinia sclerotiorum (Sclerotinia sclerotiorum), Pyricularia oryzae (Magnaporthe grisea), grape branch-rot bacterium (Phomopsis viticola), compacted shape Pseudomonas (Helminthosporium) disease such as Exserohilum turcicum (Helminthosporium tritici repentis), reticulate pattern germ (Pyrenophora teres), anthrax bacteria such as black fruit bacterium (Glomerella) or colletotrichum (Colletotrichu M spp.) disease (such as fine strain of millet anthrax bacteria (Colletotrichum graminicola) and watermelon anthrax bacteria (Colletotrichum orbiculare)) and gaeumannomyces graminis (Gaeumannomyces graminis)；Basidiomycetes, including the rest fungus disease as caused by Rust (Puccinia spp.) (such as Puccinia recondita (Puccinia recondita), strip rust bacteria (Puccinia striiformis), leaf rust (Puccinia hordei), puccinia graminis bacterium (Puccinia graminis) and handle rest fungus (Puccinia arachidis)), coffee rest fungus (Hemileia vastatrix) and phakopsora pachyrhizi sydow (Phakopsora pachyrhizi)；Other pathogen include Rhizoctonia species (Rhizoctonia spp.) (such as Rhizoctonia solani Kuhn (Rhizoctonia solani))；Fusarium (Fusarium) species disease such as Fusarlum roseum (Fusarium roseum), Fusarium graminearum (Fusarium graminearum) and Fusarium oxysporum (Fusarium oxysporum)；Verticillium dahliae (Verticillium dahliae)；Sclerotiumrolfsii (Sclerotium rolfsii)；Moire bacterium (Rynchosporium secalis)；Black puckery germ (Cercosporidium personatum), alternaria (Cercospora arachidicola) and brown patch germ (Cercospora beticola)；And other and the closely related classification of these pathogen and strain.Other than their Fungicidally active, the composition or combination also have resistance activity to bacterium such as erwinia amylovora (Erwinia amylovora), xanthomonas campestris (Xanthomonas campestris), pseudomonas syringae (Pseudomonas syringae) and other strains.
The application method of microbicide compositions of the invention is simple, before plant disease sprouting or after sprouting, it is applied according to a conventional method to the place of crop and plant growth, such as mix soil, spraying, injection, casting, its amount of application is depending on weather conditions or crop condition, it applies 10-5000g per acre under normal circumstances, is diluted to 10-400mg/L (preferably 100-300mg/L) application.Diluent is preferably water.
Microbicide compositions of the invention, bactericidal effect is usually related with extraneous factor such as weather, but can slow down the influence of weather by using dosage form appropriate.
Composition of the invention can be also used in mixed way with other compounds with sterilization, desinsection or activity of weeding, can also be used in mixed way with nematicide, acaricide, arthropodicides, safener, plant growth regulator, fertilizer or soil conditioner etc..
General synthesis process
In the present specification, if there are any difference between chemical name and chemical structure, structure is dominant.Generally, the compound of the present invention described method can be prepared through the invention, and unless there are further instruction, wherein the definition of substituent group such as (I) is shown.Following synthetic schemes and embodiment 1-11 is for being further illustrated the contents of the present invention.
The use of logogram word below is through the present invention:
CDCl 3Deuterated chloroform；DMF N,N-dimethylformamide；G grams；Mg milligrams；Mol moles；Mmol mMs；L liter；ML milliliters.
Synthetic schemes
Synthetic schemes 1
Formula (I) compound represented can be synthesized by method disclosed in synthetic schemes 1, wherein R 1、R 2、Y、L 1、L 2There is meaning of the present invention with ring A.Formula (a) compound obtains formula (b) compound with chlorine reaction in acid condition；Formula (b) compound reacts to obtain formula (d) compound under alkaline condition with formula (c) compound；Formula (d) compound reacts to obtain formula (I) compound under alkaline condition with formula (e) compound.
Synthetic schemes 2
Formula (I) compound represented can also be synthesized by method disclosed in synthetic schemes 2, wherein R 1、R 2、Y、L 1、L 2There is meaning of the present invention with ring A.Formula (f) compound reacts to obtain formula (I) compound with formula (c) compound in alkaline condition.
Embodiment
Intermediate: the synthesis of 1- (N, N- dimethyl methyl acyl group) -1H-1,2,4- triazole -3- sulfonic acid chloride
Step 1: the synthesis of 1,2- bis- (1H-1,2,4- triazole -3- base) disulfide
By 3- sulfydryl -1,2,4- triazole (101.0g, 1.00mol) is dissolved in methylene chloride (300mL), and pyridine (79.0g is added, 1.00mol), it is stirred at 0 DEG C, benzene sulfonyl chloride (88.30g, 0.25mol) is slowly added dropwise, after 2 hours are added dropwise, stir 18 hours at room temperature.Steaming vibrating dichloromethane is depressurized with Rotary Evaporators, residue is added water (500mL) under mechanical stirring, stirs 1 hour, filtering, filter residue are washed with water (800mL) and ethyl acetate (300mL) respectively, are air-dried, yellow powder 95.2g is obtained, yield: 95.2%.
MS(ES-API,pos.ion)m/z:201.1[M+1] +。
Step 2: the synthesis of 3,3'- dithiobis (N, N- dimethyl -1H-1,2,4- triazole -1- sulfonamide)
Under nitrogen protection, by 1,2-, bis- (1H-1; 2,4- triazole -3- bases) disulfide (60.0g, 0.30mol) is dissolved in N; in dinethylformamide (300mL); it is added potassium carbonate (69.0g, 0.50mol), after being stirred at 0 DEG C; it is slowly dropped into N; TMSDMA N dimethylamine base sulfonic acid chloride (93.34g, 0.65mol), the reaction was continued 6 hours after being added dropwise within 2 hours.Reaction solution is poured slowly into water, is stirred 1 hour, filtering, solid air-dries, and obtains white powder 107.2g, yield: 86.3%.
MS(ES-API,pos.ion)m/z:415.0[M+1] +。
Step 3: the synthesis of 1- (N, N- dimethyl methyl acyl group) -1H-1,2,4- triazole -3- sulfonic acid chloride
By 3,3'- dithiobis (N, N- dimethyl -1H-1,2,4- triazole -1- sulfonamide) (41.40g, 0.10mol) be dissolved in 1, in 2- dichloroethanes (300mL), it is added water (300mL), is cooled to 0 DEG C, be added acetic acid (100mL), temperature is controlled at 10 DEG C to 25 DEG C, stirring was passed through chlorine (35.50g, 0.50mol) after 2 hours, and the reaction was continued half an hour.After the reaction was completed, solution is transferred to separatory funnel, stands liquid separation, and organic phase is washed three times with water (30mL), boils off solvent with Rotary Evaporators decompression, obtains white powder 48.11g, yield: 87.8%.
MS(ES-API,pos.ion)m/z:274.8[M+1] +。
Intermediate: the synthesis of the bromo- 4,5,6,7- thiophane of 2- simultaneously [3,2-c] pyridine
By 4,5,6,7- thiophane simultaneously [3,2-c] pyridine (3.00g, it 21.6mmol) is added in 250mL single-necked flask, methylene chloride (80mL) then is added, is cooled to -5 DEG C, stirring 10 minutes, then it will be slowly added dropwise in reaction solution containing methylene chloride (20mL) suspension of N- bromo-succinimide (3.89g, 21.6mmol) by constant pressure funnel, after 1 hour drips off, continuation is stirred 12 hours at a temperature of -5 DEG C, it is evaporated under reduced pressure with Rotary Evaporators and removes solvent, obtain yellow solid powder 4.46g, yield: 95.1%.
MS(ES-API,pos.ion)m/z:217.9[M+1] +。
Intermediate: the synthesis of the chloro- 4,5,6,7- thiophane of 2- simultaneously [3,2-c] pyridine
By 4,5,6,7- thiophane simultaneously [3,2-c] pyridine (3.00g, it 21.6mmol) is added in 250mL single-necked flask, methylene chloride (80mL) then is added, is cooled to -5 DEG C, stirring 10 minutes, then it will be slowly added dropwise in reaction solution containing methylene chloride (20mL) suspension of N- chlorosuccinimide (2.88g, 21.6mmol) by constant pressure funnel, after 1 hour drips off, continuation is stirred 12 hours at a temperature of -5 DEG C, it is evaporated under reduced pressure with Rotary Evaporators and removes solvent, obtain yellow solid powder 3.51g, yield: 93.8%.
MS(ES-API,pos.ion)m/z:174.0[M+1] +。
Intermediate: the synthesis of 2- (tert-butyl) -4,5,6,7- thiophane simultaneously [3,2-c] pyridine
By 4,5,6,7- thiophanes simultaneously [3,2-c] pyridine (3.00g, it 21.6mmol) is added in 250mL single-necked flask, the tert-butyl alcohol (3.70g, 50.0mmol) then is added, stirring 10 minutes, then 50% dilute sulfuric acid (20mL) is added dropwise in reaction solution by constant pressure funnel, after 0.5 hour drips off, is heated to 50 DEG C and stirs 1 hour.25 DEG C are cooled to, reactant sodium hydroxide solution adjusts pH=10, and ethyl acetate extracts (50mL), liquid separation is stood, organic phase is washed three times with water (30mL), is evaporated under reduced pressure with Rotary Evaporators and removes solvent, obtain yellow solid powder 3.50g, yield: 82.7%.
MS(ES-API,pos.ion)m/z:196.1[M+1] +。
The synthesis of embodiment 1:3- ((3,4- dihydro-isoquinoline -2 (1H)-yl) sulfonyl)-N, N- dimethyl -1H-1,2,4- triazole -1- sulfonamide
Step 1: the synthesis of 1H-1,2,4- triazole -3- sulfonic acid chloride
At room temperature, by 3- sulfydryl -1,2,4,-triazole (12.0g, 0.12mol) is dissolved in hydrochloric acid solution (2N, 0.12L), mixture is down to 0 DEG C, is passed through chlorine reaction 40 minutes, 30 minutes are stood at 0 DEG C, filtering, obtains white solid, and ice water washs (500mL x 3), white solid 14.5g is obtained, yield: 72.5%.
Step 2: the synthesis of 2- ((1H-1,2,4- triazole -3- base) sulfonyl) -1,2,3,4- tetrahydroisoquinoline
By 1,2,3,4- tetrahydroisoquinoline (1.33g, 9.98mmol) and triethylamine (1.5g, 14.82mmol) is dissolved in tetrahydrofuran (5mL), after stirring 30 minutes at room temperature, it is slowly dropped into 1H-1, the tetrahydrofuran solution (5mL) of 2,4- triazole -3- sulfonic acid chlorides (1.67g, 9.96mmol), after being added dropwise, it is stirred at room temperature 10 hours.Filtrate is concentrated under reduced pressure in filtering, and dilute hydrochloric acid (0.5N, 10mL) is added in residue, stirs 30 minutes, filtering, and filter cake obtains white solid 2.1g, yield: 79.5% with petroleum ether (50mL x 3).
Step 3: the synthesis of 3- ((3,4- dihydro-isoquinoline -2 (1H)-yl) sulfonyl)-N, N- dimethyl -1H-1,2,4- triazole -1- sulfonamide
By 2- ((1H-1; 2,4- triazole -3- bases) sulfonyl) -1,2; 3; 4- tetrahydroisoquinoline (0.53g, 2.00mmol) is dissolved in pyridine (20mL), after stirring 30 minutes at room temperature; it is slowly dropped into dimethylamino sulfonic acid chloride (0.86g; 5.99mmol), it after being added dropwise to complete, is stirred at room temperature 24 hours.It is concentrated under reduced pressure and removes pyridine, saturated sodium bicarbonate solution (10mL) adjusts pH=7, and ethyl acetate extracts (50mL x 3), anhydrous sodium sulfate is dry, filtering is concentrated under reduced pressure filtrate, obtains yellow solid, with petrol ether/ethyl acetate mixed solution dissolved solid [petrol ether/ethyl acetate (v/v)=5/1,200mL], filtrate is concentrated under reduced pressure in filtering, white powder 0.21g is obtained, yield: 56.4%.
MS(ES-API,pos.ion)m/z:372.0[M+1] +；
1H NMR(400MHz,CDCl 3) δ (ppm): 8.7 (s, 1H), 7.2~7.1 (m, 4H), 4.6 (s, 2H), 3.8 (m, 2H), 3.1 (m, 2H), 2.83 (s, 6H).
Embodiment 2:3- ((6,7- dihydro-thiophene [3,2-c] and pyridine -5 (4H)-yl) sulfonyl)-N, the synthesis of N- dimethyl -1H-1,2,4- triazole -1- sulfonamide
Step 1: the synthesis of 5- ((1H-1,2,4- triazole -3- base) sulfonyl) -4,5,6,7- thiophane [3,2-c] and pyridine
By 4,5,6,7- thiophane [3,2-c] and pyridine (1.39g, 10.0mmol) and triethylamine (1.5g, (5mL) 15.0mmol) is dissolved in tetrahydrofuran, after stirring 30 minutes at room temperature, it is slowly dropped into 1H-1,2,4- triazole -3- sulfonic acid chloride (1.67g, tetrahydrofuran solution (5mL) 10.0mmol) after being added dropwise to complete, is stirred at room temperature 10 hours.Filtrate is concentrated under reduced pressure in filtering, and dilute hydrochloric acid (0.5N, 10mL) is added in residue, stirs 30 minutes, filtering, and filter cake obtains white solid 2.23g, yield: 82.6% with petroleum ether (50mL x 3).
Step 2: 3- ((6,7- dihydro-thiophene [3,2-c] and pyridine -5 (4H)-yl) sulfonyl)-N, the synthesis of N- dimethyl -1H-1,2,4- triazole -1- sulfonamide
By 5- ((1H-1,2,4- triazole -3- bases) sulfonyl) -4; 5; 6,7- thiophanes [3,2-c] and pyridine (0.81g; (10mL) 3.0mmol) is dissolved in pyridine; after stirring 30 minutes at room temperature, it is slowly dropped into dimethylamino sulfonic acid chloride (0.47g, 3.3mmol); after being added dropwise to complete, it is stirred at room temperature 24 hours.It is concentrated under reduced pressure and removes pyridine, saturated sodium bicarbonate solution (10mL) adjusts pH=7, and ethyl acetate extracts (50mL x 3), anhydrous sodium sulfate is dry, filtering is concentrated under reduced pressure filtrate, obtains yellow solid, with petrol ether/ethyl acetate mixed solution dissolved solid [petrol ether/ethyl acetate (v/v)=5/1,200mL], filtrate is concentrated under reduced pressure in filtering, white powder 0.91g is obtained, yield: 80.4%.
MS(ES-API,pos.ion)m/z:378.0[M+1] +；
1H NMR(400MHz,CDCl 3)δ(ppm):9.4(s,1H),7.3(d,1H),6.9(d,1H),4.4(s,2H),3.7(t,2H),3.0(t,2H),2.90(s,6H)。
The synthesis of embodiment 3:3- ((3,4- dihydroquinoline -1 (2H)-yl) sulfonyl)-N, N- dimethyl -1H-1,2,4- triazole -1- sulfonamide
Under nitrogen protection, by 1,2; 3,4- tetrahydroquinolines (0.66g, 5.0mmol); pyridine (0.48g, 6.0mmol)) and tetrahydrofuran (10mL) be added in 100mL there-necked flask, stirred at 0 DEG C; 1- (N is added dropwise in 10 minutes; TMSDMA N dimethylamine base sulfonyl) -1H-1,2,4- triazole -3- sulfonic acid chloride (1.38g; tetrahydrofuran (10mL) solution 5.0mmol), reacts at room temperature 2 hours after being added dropwise.It is filtered to remove solid, solvent is removed under reduced pressure with Rotary Evaporators in filtrate, obtains faint yellow solid, recrystallizes (ethyl acetate/petroleum ether (v/v)=2/1), obtains white solid 1.27g, yield: 69.4%.
MS(ES-API,pos.ion)m/z:372.1[M+1] +；
1H NMR(400MHz,CDCl 3)δ(ppm):8.71(s,1H),7.31-7.16(m,4H),4.24(t,2H),3.69(t,2H),2.91(s,6H),2.02(m,2H)。
According to the preparation method of embodiment 3, using different material and intermediate 1- (N, TMSDMA N dimethylamine base sulfonyl) -1H-1,2,4- triazole -3- sulfonic acid chlorides are reacted, and the target compound in table 1 can be obtained.
Table 1
Active testing
In following tests example, inventor has detected the compounds of this invention to the prophylactic-therapeutic effect of harmful fungoid by taking part of compounds of the invention as an example.
Test example 1
Test target: Rhizoctonia solani Kuhn, botrytis cinerea pers, bacterium of downy mildew of cucumber, cucumber powdery mildew's pathogen
Test process: it is spare that compound with DMF is dissolved into 1%EC.Using living body pot-culture method, these compounds are evaluated at different dosages to 4 experiment target target bactericidal activities.
1) bacterium of downy mildew of cucumber test (Pseudoperonospora cubensis)
Select 1 consistent potting cucumber seedling of leaf period (plucking growing point) growing way, naturally dry after spraying treatment, it is inoculated with after 24 hours after processing, take fresh cucumber downy mildew disease leaf, the lower sick leaf back sporangium of distillation washing is dipped with writing brush, is made into sporangia suspension (2-3x 10 5A/mL).With inoculation sprayer (pressure 0.1MPa), even spraying is inoculated on cucumber seedling, test material after inoculation moves to phjytotron, keep relative humidity 100%, temperature is 21 DEG C or so, 21 DEG C of temperature or so are kept after 24 hours, 95% or so moisturizing of relative humidity induces, and backsight blank control incidence carries out classification investigation within 5 days, refers to calculating preventive effect by disease.
2) cucumber powdery mildew's pathogen test (Sphaerotheca fuliginea)
A leaf period, the consistent cucumber seedling of growing way are selected, is dried in the shade 24 hours after spraying treatment.The fresh Powdery Mildew spore taken on cucumber leaves is washed, is filtered with double gauze, the suspension that spore concentration is 100,000/mL or so, spray inoculation is made.Test material after inoculation moves into artificial climate, and relative humidity is maintained between 60~70%, and temperature is kept for 21~23 DEG C, carries out classification investigation depending on blank control incidence within 10 days or so, refers to calculating preventive effect by disease.
3) botrytis cinerea pers (Botrytis cinerea)
Using blade bacterination process.The consistent potting cucumber seedling of two leaf period growing ways is selected to connect bacteria cake on blade after reagent spray dries.24~26 DEG C after half-light moisturizing 24 hours, are restored natural lighting moisturizing culture about 3 days.Each vaccination lesion diameter is measured with slide calliper rule after the onset of wait compare sufficiently, calculates preventive effect.
4) Rhizoctonia solani Kuhn (Rhizoctonia solani)
Select two leaves wholeheartedly, the consistent potting maize seedling of growing way, naturally dry after spraying treatment is inoculated with, after reagent spray dries, connects bacteria cake on blade for 24 hours or so.25~26 DEG C after half-light moisturizing 24 hours, are restored natural lighting moisturizing culture about 3 days.Each vaccination scab length is measured with slide calliper rule after the onset of wait compare sufficiently, calculates preventive effect.
Test result: test result is as shown in table 2-5.
2 the compounds of this invention of table is under 200mg/L dosage to the preventive effect of cucumber downy mildew (%)
Embodiment number Control efficiency (%)
Embodiment 1 100
Embodiment 2 100
Embodiment 3 100
Embodiment 4 100
Embodiment 5 100
Embodiment 6 98
Embodiment 7 100
Embodiment 8 100
Embodiment 9 100
Embodiment 10 100
3 the compounds of this invention of table is under 100mg/L dosage to the preventive effect of cucumber downy mildew (%)
Embodiment number Control efficiency (%)
Embodiment 2 100
Embodiment 4 85
Embodiment 5 100
Embodiment 6 100
Embodiment 7 80
Embodiment 8 100
4 the compounds of this invention of table is under 50mg/L dosage to the preventive effect of cucumber downy mildew (%)
Embodiment number Control efficiency (%)
Embodiment 2 80
Embodiment 5 80
Embodiment 6 80
Embodiment 8 100
5 the compounds of this invention of table is under 25mg/L dosage to the preventive effect of cucumber downy mildew (%)
Embodiment number Control efficiency (%)
Embodiment 8 100
Cyazofamid 20
Amisulbrom 85
Test result shows, the compounds of this invention all has good preventive effect to bacterium of downy mildew of cucumber at different dosages, and more preferably control efficiency is shown to bacterium of downy mildew of cucumber under low dosage, such as embodiment 8 is 100% to the preventive effect of cucumber downy mildew under 25mg/L dosage, and cyazofamid and amisulbrom are respectively 20% and 85% to the preventive effect of cucumber downy mildew.In addition the compounds of this invention also has certain control efficiency to Rhizoctonia solani Kuhn, botrytis cinerea pers and cucumber powdery mildew's pathogen.
The preferred embodiment of the present invention has been described above in detail; but the present invention is not limited to the specific details in the above embodiment, within the scope of the technical concept of the present invention; can be with various simple variants of the technical solution of the present invention are made, these simple variants all belong to the scope of protection of the present invention.

Claims (11)

  1. A kind of compound is stereoisomer, nitrogen oxides and the salt of the compound as shown in formula (I) compound represented or formula (I):
    Wherein,
    R 1And R 2It is each independently hydrogen, alkyl, alkenyl, alkynyl, naphthenic base, heterocycle, aryl, heteroaryl, cycloalkyl-alkyl, heterocyclylalkyl group, aryl alkyl or heteroaryl alkyl；
    Or R 1、R 2Heterocycle or heteroaryl are formed together with connected nitrogen-atoms；
    Wherein, by R 1、R 2The heterocycle or heteroaryl being formed together with connected nitrogen-atoms are optionally selected from R by one or more 5Substituent group replaced；
    Y is hydrogen, halogen, hydroxyl, cyano, nitro, amino, carboxyl, alkyl, alkenyl, alkynyl, halogenated alkyl, halogenated alkenyl, halo alkynyl, aryl, aryl alkyl, halogenated aryl or haloarylalkyl；
    L 1And L 2It is each independently-(CR 3R 4) n-、-(CR 11R 22) m-O-、-(CR 33R 44) o-NR nOr-(CR 55R 66) p-S(O) q-；
    Wherein, R 3And R 4It is each independently the alkyl that alkyl, the cyano that alkyl, the hydroxyl that hydrogen, halogen, amino, hydroxyl, cyano, nitro, alkyl, alkenyl, alkynyl, halogenated alkyl, amino replace replace replace or the alkyl that nitro replaces；
    Or R 3、R 4C=O can be formed with the carbon atom being connected；
    R 11、R 22、R 33、R 44、R 55And R 66It is each independently hydrogen, alkyl or halogenated alkyl；
    R nFor hydrogen or alkyl；
    Wherein, 0,1,2,3,4 or 5 n；
    M, o and p is each independently 0,1,2,3 or 4；
    Q is 0,1 or 2；
    Or i) n >=2 when, two R on adjacent carbons 3Naphthenic base, heterocycle, aryl or heteroaryl can be formed together with two adjacent carbon atoms；Or ii) m >=2 when, two R on adjacent carbons 11Naphthenic base, heterocycle, aryl or heteroaryl can be formed together with two adjacent carbon atoms；Or iii) o >=2 when, two R on adjacent carbons 33Naphthenic base, heterocycle, aryl or heteroaryl can be formed together with two adjacent carbon atoms；Or iv) p >=2 when, two R on adjacent carbons 55Naphthenic base, heterocycle, aryl or heteroaryl can be formed together with two adjacent carbon atoms；
    For naphthenic base, heterocycle, aryl or heteroaryl；
    Wherein, Optionally R is selected from by 1,2,3 or 4 6Substituent group replaced；
    Wherein, R 5And R 6It is each independently hydrogen, halogen, hydroxyl, cyano, nitro, amino, carboxyl, C 1-6Alkyl, C 2-6Alkenyl, C 2-6Alkynyl, halogenated C 1-6Alkyl, halogenated C 2-6Alkenyl, halogenated C 2-6Alkynyl, C 1-6Alkoxy, halogenated C 1-6Alkoxy, C 1-6Alkoxy-(C=O)-, C 1-6Alkoxy -C 1-6Alkyl-, C 1-6Alkyl-(C=O)-O-, C 1-6Alkyl-(C=O)-, C 1-6Alkyl-SO 2-、C 1-6Alkyl amino, C 1-6Alkyl amino-(C=O)-, C 1-6Alkyl amino-SO 2-、C 3-6Naphthenic base, C 2-6Heterocycle, C 6-10Aryl or C 1-6Heteroaryl.
  2. Compound according to claim 1, wherein
    R 1And R 2It is each independently hydrogen, C 1-6Alkyl, C 2-6Alkenyl, C 2-6Alkynyl, C 3-8Naphthenic base, C 2-6Heterocycle, C 6-10Aryl, C 1-6Heteroaryl, C 3-8Naphthenic base-C 1-6Alkyl-, C 2-6Heterocycle-C 1-6Alkyl-, C 6-10Aryl-C 1-6Alkyl-or C 1-6Heteroaryl-C 1-6Alkyl-；
    Or R 1、R 2C is formed together with connected nitrogen-atoms 2-6Heterocycle or 5-12 unit's heteroaryl；
    Wherein, by R 1、R 2The C being formed together with connected nitrogen-atoms 2-6Heterocycle or 5-12 unit's heteroaryl are optionally selected from R by one or more 5Substituent group replaced；
    Y is hydrogen, F, Cl, Br, I, hydroxyl, cyano, nitro, amino, carboxyl, C 1-6Alkyl, C 2-6Alkenyl, C 2-6Alkynyl, halogenated C 1-6Alkyl, halogenated C 2-6Alkenyl, halogenated C 2-6Alkynyl, C 6-10Aryl, C 6-10Aryl-C 1-6Alkyl-, halogenated C 6-10Aryl or halogenated C 6-10Aryl-C 1-6Alkyl-；
    L 1And L 2It is each independently-(CR 3R 4) n-、-(CR 11R 22) m-O-、-(CR 33R 44) o-NR nOr-(CR 55R 66) p-S(O) q-；
    Wherein, R 3And R 4It is each independently hydrogen, F, Cl, Br, I, amino, hydroxyl, cyano, nitro, C 1-6Alkyl, C 2-6Alkenyl, C 2-6Alkynyl, halogenated C 1-6The C that alkyl, amino replace 1-6The C that alkyl, hydroxyl replace 1-6The C that alkyl, cyano replace 1-6The C that alkyl or nitro replace 1-6Alkyl；
    Or R 3、R 4C=O can be formed with the carbon atom being connected；
    R 11、R 22、R 33、R 44、R 55And R 66It is each independently hydrogen, C 1-6Alkyl or halogenated C 1-6Alkyl；
    R nFor hydrogen or C 1-6Alkyl；
    Wherein, 0,1,2,3,4 or 5 n；
    M, o and p is each independently 0,1,2,3 or 4；
    Q is 0,1 or 2；
    Or i) n >=2 when, two R on adjacent carbons 3C can be formed together with two adjacent carbon atoms 3-6Naphthenic base, C 2-6Heterocycle, C 6-10Aryl or 5-10 unit's heteroaryl；Or ii) m >=2 when, two R on adjacent carbons 11C can be formed together with two adjacent carbon atoms 3-6Naphthenic base, C 2-6Heterocycle, C 6-10Aryl or 5-10 unit's heteroaryl；Or iii) o >=2 when, two R on adjacent carbons 33C can be formed together with two adjacent carbon atoms 3-6Naphthenic base, C 2-6Heterocycle, C 6-10Aryl or 5-10 unit's heteroaryl；Or iv) p >=2 when, two R on adjacent carbons 55C can be formed together with two adjacent carbon atoms 3-6Naphthenic base, C 2-6Heterocycle, C 6-10Aryl or 5-10 unit's heteroaryl；
    For C 3-8Naphthenic base, C 2-6Heterocycle, C 6-10Aryl or 5-12 unit's heteroaryl；
    Wherein, Optionally R is selected from by 1,2,3 or 4 6Substituent group replaced；
    Wherein, R 5And R 6It is each independently hydrogen, F, Cl, Br, I, hydroxyl, cyano, nitro, amino, carboxyl, C 1-4Alkyl, C 2-4Alkenyl, C 2-4Alkynyl, halogenated C 1-4Alkyl, halogenated C 2-4Alkenyl, halogenated C 2-4Alkynyl, C 1-4Alkoxy, halogenated C 1-4Alkoxy, C 1-4Alkoxy-(C=O)-, C 1-4Alkoxy -C 1-3Alkyl-, C 1-4Alkyl-(C=O)-O-, C 1-4Alkyl-(C=O)-, C 1-4Alkyl-SO 2-、C 1-4Alkyl amino, C 1-4Alkyl amino-(C=O)-, C 1-4Alkyl amino-SO 2-、C 3-6Naphthenic base, C 2-6Heterocycle, C 6-10Aryl or C 1-4Heteroaryl.
  3. Compound according to claim 1 or 2, wherein
    R 1And R 2It is each independently hydrogen, C 1-4Alkyl, C 2-4Alkenyl, C 2-4Alkynyl, C 3-6Naphthenic base, C 2-6Heterocycle, C 6-10Aryl, C 1-5Heteroaryl, C 3-6Naphthenic base-C 1-4Alkyl-, C 2-5Heterocycle-C 1-4Alkyl-, C 6-10Aryl-C 1-4Alkyl-or C 1-5Heteroaryl-C 1-4Alkyl-；
    Or R 1、R 2C is formed together with connected nitrogen-atoms 2-5Heterocycle or 5-10 unit's heteroaryl；
    Wherein, R 1、R 2The C being formed together with connected nitrogen-atoms 2-5Heterocycle or 5-10 unit's heteroaryl are optionally selected from R by one or more 5Substituent group replaced；
    Y is hydrogen, F, Cl, Br, hydroxyl, cyano, nitro, amino, carboxyl, C 1-4Alkyl, C 2-4Alkenyl, C 2-4Alkynyl, halogenated C 1-4Alkyl, halogenated C 2-4Alkenyl, halogenated C 2-4Alkynyl, C 6-10Aryl, C 6-10Aryl-C 1-4Alkyl-, halogenated C 6-10Aryl or halogenated C 6-10Aryl-C 1-4Alkyl-；
    R 5For hydrogen, F, Cl, Br, hydroxyl, cyano, nitro, amino, carboxyl, C 1-4Alkyl or halogenated C 1-4Alkyl.
  4. According to compound described in right 3, wherein
    R 1And R 2It is each independently hydrogen ,-CH 3、-CH 2CH 3、-CH 2CH 2CH 3、-CH(CH 3) 2, cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, benzyl, 4- luorobenzyl or 4- cyanobenzyls；
    Or R 1、R 2Following subformula is formed together with connected nitrogen-atoms:
    Y is hydrogen, F, Cl, Br, hydroxyl, cyano, nitro, amino, carboxyl ,-CH 3、-CHF 2、-CH 2F、-CF 3、-CH 2CH 3、-CH 2CH 2F、-CH 2CHF 2、-CH 2CH 2CH 3、-CH(CH 3) 2、-C(CH 3) 3, phenyl, 2- fluorophenyl, 3- fluorophenyl or 4- fluorophenyl.
  5. Compound according to claim 1 or 2, wherein
    L 1And L 2It is each independently-(CR 3R 4) n-、-(CR 11R 22) m-O-、-(CR 33R 44) o-NR nOr-(CR 55R 66) p-S(O) q-；
    Wherein, R 3And R 4It is each independently hydrogen, F, Cl, Br, I, amino, hydroxyl, cyano, nitro, C 1-4Alkyl, halogenated C 1-4The C that alkyl, amino replace 1-4The C that alkyl, hydroxyl replace 1-4The C that alkyl, cyano replace 1-4The C that alkyl or nitro replace 1-4Alkyl；
    Or R 3、R 4C=O can be formed with the carbon atom being connected；
    R 11、R 22、R 33、R 44、R 55And R 66It is each independently hydrogen, C 1-4Alkyl or halogenated C 1-4Alkyl；
    R nFor hydrogen or C 1-4Alkyl；
    Wherein, 0,1,2,3,4 or 5 n；
    M, o and p is each independently 0,1,2,3 or 4；
    Q is 0,1 or 2；
    Or i) n >=2 when, two R on adjacent carbons 3C can be formed together with two adjacent carbon atoms 3-6Naphthenic base or C 6-10Aryl；Or ii) m >=2 when, two R on adjacent carbons 11C can be formed together with two adjacent carbon atoms 3-6Naphthenic base or C 6-10Aryl；Or iii) o >=2 when, two R on adjacent carbons 33C can be formed together with two adjacent carbon atoms 3-6Naphthenic base or C 6-10Aryl；Or iv) p >=2 when, two R on adjacent carbons 55C can be formed together with two adjacent carbon atoms 3-6Naphthenic base or C 6-10Aryl；
    For C 3-6Naphthenic base, C 2-5Heterocycle, C 6-10Aryl or 5-10 unit's heteroaryl；
    Wherein, Optionally R is selected from by 1,2,3 or 4 6Substituent group replaced；
    R 6For hydrogen, F, Cl, Br, I, amino, hydroxyl, cyano, nitro, carboxyl, C 1-4Alkyl, halogenated C 1-4Alkyl, C 1-4Alkoxy, halogenated C 1-4Alkoxy, C 1-4Alkoxy-(C=O)-or C 1-4Alkyl-(C=O)-O-.
  6. Compound according to claim 5, wherein
    For following subformula:
    Wherein, R 7For hydrogen or C 1-4Alkyl；
    X 1、X 2、X 3、X 4、X 5And X 6It is each independently N or CR 8；
    R 8For hydrogen, F, Cl, Br, I, C 1-4Alkyl, halogenated C 1-4Alkyl or C 1-4Alkoxy-(C=O)-.
  7. Compound according to claim 6, wherein
    For following subformula:
  8. Compound according to claim 1, wherein
    For following subformula:
  9. A kind of compound is the compound with one of following structure or the stereoisomer with one of following structural compounds, nitrogen oxides and salt:
  10. A kind of composition includes acceptable surfactant and carrier on compound described in any one of claim 1-9 and Pesticide Science.
  11. The application of compound described in any one of claim 1-9 or composition described in any one of claim 10 in control of plant disease.
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CN112442018A (en) * 2019-08-27 2021-03-05 东莞市东阳光农药研发有限公司 Triazole-1, 3-disulfonamide derivative and application thereof in agriculture
CN112442018B (en) * 2019-08-27 2024-02-02 东莞市东阳光农药研发有限公司 Triazole-1, 3-disulfonamide derivative and application thereof in agriculture
CN112624988A (en) * 2019-09-24 2021-04-09 东莞市东阳光农药研发有限公司 Novel triazole compound and application thereof in agriculture
CN112624988B (en) * 2019-09-24 2024-01-16 东莞市东阳光农药研发有限公司 New triazole compound and application thereof in agriculture

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