CN112624974A - Cinnamomum cassia carboxylate compound and application thereof - Google Patents

Cinnamomum cassia carboxylate compound and application thereof Download PDF

Info

Publication number
CN112624974A
CN112624974A CN201910950256.1A CN201910950256A CN112624974A CN 112624974 A CN112624974 A CN 112624974A CN 201910950256 A CN201910950256 A CN 201910950256A CN 112624974 A CN112624974 A CN 112624974A
Authority
CN
China
Prior art keywords
radical
alkyl
cycloalkyl
alkoxy
heterocyclic ring
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.)
Granted
Application number
CN201910950256.1A
Other languages
Chinese (zh)
Other versions
CN112624974B (en
Inventor
孙冰
杨辉斌
商璐
英君伍
马宏娟
秦博
梁爽
崔东亮
王刚
裴和瑛
陈霖
张帆
王徵
王明欣
李斌
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.)
Jiangsu Yangnong Chemical Co Ltd
Shenyang Sinochem Agrochemicals R&D Co Ltd
Original Assignee
Shenyang Sinochem Agrochemicals 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
Priority to CN201910950256.1A priority Critical patent/CN112624974B/en
Application filed by Shenyang Sinochem Agrochemicals R&D Co Ltd filed Critical Shenyang Sinochem Agrochemicals R&D Co Ltd
Priority to CA3154030A priority patent/CA3154030C/en
Priority to CN202080059844.7A priority patent/CN114787134B/en
Priority to US17/754,670 priority patent/US20230157290A1/en
Priority to MX2022004231A priority patent/MX2022004231A/en
Priority to BR112022006856A priority patent/BR112022006856A2/en
Priority to PCT/CN2020/119168 priority patent/WO2021068820A1/en
Priority to EP20874773.3A priority patent/EP4043441A4/en
Priority to AU2020363069A priority patent/AU2020363069B2/en
Publication of CN112624974A publication Critical patent/CN112624974A/en
Application granted granted Critical
Publication of CN112624974B publication Critical patent/CN112624974B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members 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
    • C07D231/18—One oxygen or sulfur atom
    • C07D231/20—One oxygen atom attached in position 3 or 5
    • 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
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/06—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a chain containing hetero atoms as chain links

Landscapes

  • 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)

Abstract

The invention discloses a cinnamic carboxylic ester compound and application of agriculturally acceptable salt thereof as a herbicide, wherein the compound is shown as a general formula (I):

Description

Cinnamomum cassia carboxylate compound and application thereof
Technical Field
The invention belongs to the field of herbicides. In particular to a cinnamic carboxylic ester compound and application thereof.
Background
Due to succession and transition of weed populations and generation and rapid development of chemical pesticide resistance, people continuously strengthen the awareness of ecological environment protection, and continuously increase the attention to chemical pesticide pollution, understanding of the influence of pesticides on non-target organisms and problems of lodging in the pesticide ecological environment. With the diminishing area of cultivated land in the world, the increasing population and the increasing demand for food, people are forced to rapidly develop agricultural production techniques, improve the complete cultivation system, and need to continuously invent novel and improved herbicidal compounds and compositions.
DE 2513750a1 reports that certain benzoylpyrazoles have herbicidal activity, for example compound No. 79 (KC) among them:
Figure BDA0002225413090000011
the cinnamic carboxylic acid ester compounds shown in the invention are not disclosed.
Disclosure of Invention
The invention aims to provide a cinnamyl carboxylate compound which is novel in structure and safe to crops and application thereof as a herbicide.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a cinnamic carboxylate compound is shown in the general formula I:
Figure BDA0002225413090000012
in the formula:
X1selected from hydrogen, cyano, nitro, halogen, C1-C6Alkylsulfonyl radical, C1-C6Haloalkylsulfonyl group, C1-C6Alkylsulfinyl radical, C1-C6Haloalkylsulfinyl radical, C1-C6Alkylthio radical, C1-C6Haloalkylthio, C1-C6Alkyl radical, C1-C6Haloalkyl, C1-C6Alkoxy radical, C1-C6Haloalkoxy, C1-C6Alkoxy radical C1-C3Alkyl radical, C1-C6Alkoxy radical C1-C3Alkoxy radical, C1-C6Alkoxy radical C1-C3Alkoxy radical C1-C3Alkyl radical, C3-C6Cycloalkyl radical, C3-C6Cycloalkyl radical C1-C3Alkyl radical, C3-C6Cycloalkyl radical C1-C3Alkoxy radical, C3-C6Cycloalkyl oxy, C2-C6Alkenyl radical, C2-C6Alkynyl, phenyl unsubstituted or substituted by 1 to 5 substituents2-C6Alkenylsulfonyl radical, C2-C6Alkynylsulfonyl, phenylsulfonyl, C2-C6Alkenyloxy radical, C2-C6Alkynyloxy, phenyloxy, C2-C6Alkenylthio radical, C2-C6Alkynylthio, phenylthio, 5-7 membered aliphatic heterocyclic ring containing 1-4 hetero atoms, 5-7 membered aromatic heterocyclic ring containing 1-4 hetero atoms, 5-7 membered aliphatic heterocyclic ring containing 1-4 hetero atoms C1-C6Alkyl or 5-to 7-membered heteroaromatic ring C containing 1 to 4 heteroatoms1-C6Alkyl, the following substituents are selected from nitro, halogen and C1-C6Alkyl radical, C1-C6Haloalkyl, C1-C6Alkoxy radical, C1-C6Haloalkoxy or C3-C6A cycloalkyl group;
w is selected from N or CX2；
X2Selected from hydrogen, cyano, nitro, halogen, C1-C6Alkyl radical, C1-C6Haloalkyl, C3-C6Cycloalkyl radical, C3-C6Cycloalkyl radical C1-C6Alkyl radical, C3-C6Halogenocycloalkyl C1-C6Alkyl radical, Y1Oxy radical, Y1Thio radical, Y1Y2Amino group, Y1Sulfinyl radical, Y1Sulfonyl radical, Y1Oxy radical C1-C6Alkyl radical, Y1Thio radical C1-C6Alkyl radical, Y1Y2Amino group C1-C6Alkyl radical, Y1Sulfinyl radical C1-C6Alkyl radical, Y1Sulfonyl radical C1-C6Alkyl, COY1、COOY1、OCOOY1、NY1COOY2、C(O)N Y1Y2、NY1C(O)N Y1Y2、OC(O)NY1Y2、C(O)N(Y1)OY2、NY1SO2Y2、NY1COY2、OSO2Y1、CH＝NOY1、C1-C6alkyl-CH-NOY1、C1-C6alkyl-O-N ═ CY1Y2Phenyl which is unsubstituted or substituted by 1 to 5 substituents containing 1 to 4 heteroatoms5-7 membered aliphatic heterocyclic ring of (A), 5-7 membered aromatic heterocyclic ring containing 1-4 hetero atoms, 5-7 membered aliphatic heterocyclic ring containing 1-4 hetero atoms C1-C6Alkyl or 5-to 7-membered heteroaromatic ring C containing 1 to 4 heteroatoms1-C6Alkyl, the following substituents are selected from nitro, halogen and C1-C6Alkyl radical, C1-C6Haloalkyl, C1-C6Alkoxy radical, C1-C6Haloalkoxy, C3-C6Cycloalkyl radical, C3-C6Cycloalkoxy, C2-C6Alkenyl radical, C2-C6Alkynyl, phenyl or halophenyl;
Y1、Y2each independently selected from C1-C6Alkyl radical, C1-C6Haloalkyl, C3-C6Cycloalkyl radical, C3-C6Cycloalkyl radical C1-C6Alkyl radical, C1-C6Alkoxy radical C1-C6Alkyl, phenyl unsubstituted or substituted by 1 to 5 substituents, a 5-to 7-membered aliphatic heterocyclic ring containing 1 to 4 hetero atoms, a 5-to 7-membered aromatic heterocyclic ring containing 1 to 4 hetero atoms, a 5-to 7-membered aliphatic heterocyclic ring containing 1 to 4 hetero atoms C1-C6Alkyl or 5-to 7-membered heteroaromatic ring C containing 1 to 4 heteroatoms1-C6Alkyl, the following substituents are selected from nitro, halogen and C1-C6Alkyl radical, C1-C6Haloalkyl, C1-C6Alkoxy radical, C1-C6Haloalkoxy, C3-C6Cycloalkyl radical, C3-C6Cycloalkoxy, C2-C6Alkenyl radical, C2-C6Alkynyl, phenyl or halophenyl;
X3selected from hydrogen, cyano, halogen, C1-C6Alkylsulfonyl radical, C1-C6Haloalkylsulfonyl group, C1-C6Alkylsulfinyl radical, C1-C6Haloalkylsulfinyl radical, C1-C6Alkylthio radical, C1-C6Haloalkylthio, C1-C6Alkyl radical, C1-C6Haloalkyl, C1-C6Alkoxy radical, C1-C6Haloalkoxy, C1-C6Alkoxy radical C1-C3Alkyl radical, C1-C6Alkoxy radical C1-C3Alkoxy radical, C1-C6Alkoxy radical C1-C3Alkoxy radical C1-C3Alkyl radical, C3-C6Cycloalkyl radical, C3-C6Cycloalkyl radical C1-C3Alkyl radical, C3-C6Cycloalkyl radical C1-C3Alkoxy radical, C3-C6Cycloalkyl oxy, C2-C6Alkenyl radical, C2-C6Alkynyl, phenyl unsubstituted or substituted by 1 to 5 substituents2-C6Alkenylsulfonyl radical, C2-C6Alkynylsulfonyl, phenylsulfonyl, C2-C6Alkenyloxy radical, C2-C6Alkynyloxy, phenyloxy, C2-C6Alkenylthio radical, C2-C6Alkynylthio, phenylthio, 5-7 membered aliphatic heterocyclic ring containing 1-4 hetero atoms, 5-7 membered aromatic heterocyclic ring containing 1-4 hetero atoms, 5-7 membered aliphatic heterocyclic ring containing 1-4 hetero atoms C1-C6Alkyl or 5-to 7-membered heteroaromatic ring C containing 1 to 4 heteroatoms1-C6Alkyl, the following substituents are selected from nitro, halogen and C1-C6Alkyl radical, C1-C6Haloalkyl, C1-C6Alkoxy radical, C1-C6Haloalkoxy or C3-C6A cycloalkyl group;
when X is present1Selected from chlorine, X3When selected from methanesulfonyl, X2Is not thiazolyl;
Z1is selected from C1-C6Alkyl radical, C3-C6Cycloalkyl radical, C3-C6Cycloalkyl radical C1-C6Alkyl radical, C3-C6Alkenyl radical, C3-C6Alkynyl, C1-C6Alkylsulfonyl radical C1-C6Alkyl or phenyl;
Z2selected from H, C1-C6Alkyl radical, C3-C6Cycloalkyl radical, C1-C6Haloalkyl, phenyl unsubstituted or substituted with at least one of the following substituents; the following substituents are selected from: halogen, cyano, nitro, C1-C6Alkyl radical, C3-C6Cycloalkyl or C1-C6A haloalkyl group;
R1to R5Each independently selected from hydrogen, cyano, nitro, halogen, phenyl, C1-C6Alkyl radical, C1-C6Haloalkyl, C2-C6Alkenyl radical, C2-C6Haloalkenyl, C2-C6Alkynyl, C2-C6Halogenated alkynyl, C1-C6Alkoxy radical, C1-C6Haloalkoxy, C1-C6Alkylthio or benzyloxy;
wherein R is1And R2Can form a benzene ring, a 5-7 membered aliphatic heterocyclic ring containing 1-3 heteroatoms or a 5-7 membered aromatic heterocyclic ring containing 1-3 heteroatoms together with the carbon atoms on the benzene ring to which they are attached;
R2and R3Can form a benzene ring, a 5-7 membered aliphatic heterocyclic ring with 1-3 heteroatoms or a 5-7 membered aromatic heterocyclic ring with 1-3 heteroatoms together with the carbon atoms on the benzene ring connected with the benzene ring;
stereoisomers of the compounds of formula I above; or, the compound of the general formula I and the isomer agriculturally acceptable salt thereof.
Preferably said compound, of formula I:
X1selected from hydrogen, cyano, nitro, halogen, C1-C6Alkylsulfonyl radical, C1-C6Alkylsulfinyl radical, C1-C6Alkylthio radical, C1-C6Haloalkylthio, C1-C6Alkyl radical, C1-C6Haloalkyl, C1-C6Alkoxy radical, C1-C6Alkoxy radical C1-C3Alkyl radical, C1-C6Alkoxy radical C1-C3Alkoxy radical, C1-C6Alkoxy radical C1-C3Alkoxy radical C1-C3Alkyl radical, C3-C6Cycloalkyl radical, C3-C6Cycloalkyl radical C1-C3Alkyl radical, C3-C6Cycloalkyl radical C1-C3Alkoxy radical, C3-C6Cycloalkyl oxy, C2-C6Alkenyl radical, C2-C6Alkynyl, phenyl which is unsubstituted or substituted by 1 to 5 substituents described below, phenylsulfonyl, C2-C6Alkenyloxy, phenyloxy, 5-7 membered aliphatic heterocyclic ring containing 1-4 heteroatoms, 5-7 membered aromatic heterocyclic ring containing 1-4 heteroatoms, the following substituents are selected from nitro, halogen, C1-C6Alkyl radical, C1-C6Haloalkyl, C1-C6Alkoxy radical, C1-C6Haloalkoxy or C3-C6A cycloalkyl group;
w is selected from N or CX2；
X2Selected from hydrogen, cyano, nitro, halogen, C1-C6Alkyl radical, C1-C6Haloalkyl, C3-C6Cycloalkyl radical, C3-C6Cycloalkyl radical C1-C6Alkyl radical, C3-C6Halogenocycloalkyl C1-C6Alkyl radical, Y1Oxy radical, Y1Thio radical, Y1Y2Amino group, Y1Sulfinyl radical, Y1Sulfonyl radical, Y1Oxy radical C1-C6Alkyl radical, Y1Thio radical C1-C6Alkyl radical, Y1Y2Amino group C1-C6Alkyl radical, Y1Sulfinyl radical C1-C6Alkyl radical, Y1Sulfonyl radical C1-C6Alkyl, COY1、COOY1、OCOOY1、NY1COOY2、C(O)N Y1Y2、NY1C(O)N Y1Y2、OC(O)NY1Y2、C(O)N(Y1)OY2、NY1SO2Y2、NY1COY2、OSO2Y1、CH＝NOY1、C1-C6alkyl-CH-NOY1、C1-C6alkyl-O-N ═ CY1Y2Phenyl which is unsubstituted or substituted by 1 to 5 substituents, a 5-to 7-membered aliphatic heterocyclic ring containing 1 to 4 hetero atoms, a 5-to 7-membered aromatic heterocyclic ring containing 1 to 4 hetero atoms, a 5-to 7-membered aliphatic heterocyclic ring containing 1 to 4 hetero atoms C1-C6Alkyl or 5-to 7-membered heteroaromatic ring C containing 1 to 4 heteroatoms1-C6Alkyl, the following substituents are selected from nitro, halogen and C1-C6Alkyl radical, C1-C6Haloalkyl, C1-C6Alkoxy radical, C1-C6Haloalkoxy, C3-C6Cycloalkyl radical, C3-C6A cycloalkoxy group;
Y1、Y2each independently selected from C1-C6Alkyl radical, C1-C6Haloalkyl, C3-C6Cycloalkyl radical, C3-C6Cycloalkyl radical C1-C6Alkyl radical, C1-C6Alkoxy radical C1-C6Alkyl, phenyl unsubstituted or substituted by 1 to 5 substituents, a 5-to 7-membered aliphatic heterocyclic ring containing 1 to 4 hetero atoms, a 5-to 7-membered aromatic heterocyclic ring containing 1 to 4 hetero atoms, a 5-to 7-membered aliphatic heterocyclic ring containing 1 to 4 hetero atoms C1-C6Alkyl or 5-to 7-membered heteroaromatic ring C containing 1 to 4 heteroatoms1-C6Alkyl, the following substituents are selected from nitro, halogen and C1-C6Alkyl radical, C1-C6Haloalkyl, C1-C6Alkoxy radical, C1-C6Haloalkoxy, C3-C6Cycloalkyl radical, C3-C6A cycloalkoxy group;
X3selected from hydrogen, cyano, halogen, C1-C6Alkylsulfonyl radical, C1-C6Alkylsulfinyl radical, C1-C6Alkylthio radical, C1-C6Haloalkylthio, C1-C6Alkyl radical, C1-C6Haloalkyl, C1-C6Alkoxy radical, C1-C6Alkoxy radical C1-C3Alkyl, aryl, heteroaryl, and heteroaryl,C1-C6Alkoxy radical C1-C3Alkoxy radical, C1-C6Alkoxy radical C1-C3Alkoxy radical C1-C3Alkyl radical, C3-C6Cycloalkyl radical, C3-C6Cycloalkyl radical C1-C3Alkyl radical, C3-C6Cycloalkyl radical C1-C3Alkoxy radical, C3-C6Cycloalkyl oxy, C2-C6Alkenyl radical, C2-C6Alkynyl, phenyl which is unsubstituted or substituted by 1 to 5 substituents described below, phenylsulfonyl, C2-C6Alkenyloxy, phenyloxy, 5-7 membered aliphatic heterocyclic ring containing 1-4 heteroatoms, 5-7 membered aromatic heterocyclic ring containing 1-4 heteroatoms, the following substituents are selected from nitro, halogen, C1-C6Alkyl radical, C1-C6Haloalkyl, C1-C6Alkoxy radical, C1-C6Haloalkoxy or C3-C6A cycloalkyl group;
when X is present1Selected from chlorine, X3When selected from methanesulfonyl, X2Is not thiazolyl;
Z1is selected from C1-C6Alkyl radical, C3-C6Cycloalkyl radical, C3-C6Cycloalkyl radical C1-C6Alkyl radical, C3-C6Alkenyl radical, C3-C6Alkynyl or phenyl;
Z2selected from H, C1-C6Alkyl radical, C1-C6Haloalkyl, phenyl unsubstituted or substituted with at least one of the following substituents; the following substituents are selected from: halogen, cyano, nitro, C1-C6Alkyl radical, C3-C6Cycloalkyl or C1-C6A haloalkyl group;
R1to R5Each independently selected from hydrogen, cyano, nitro, halogen, phenyl, C1-C6Alkyl radical, C2-C6Alkenyl radical, C2-C6Alkynyl, C1-C6Alkoxy radical, C1-C6Alkylthio or benzyloxy;
wherein R is1And R2Can form a benzene ring, a 5-7 membered aliphatic heterocyclic ring containing 1-3 heteroatoms or a 5-7 membered aromatic heterocyclic ring containing 1-3 heteroatoms together with the carbon atoms on the benzene ring to which they are attached;
R2and R3Can form a benzene ring, a 5-7 membered aliphatic heterocyclic ring with 1-3 heteroatoms or a 5-7 membered aromatic heterocyclic ring with 1-3 heteroatoms together with the carbon atoms on the benzene ring connected with the benzene ring;
stereoisomers of the compounds of the general formula I.
Further preferred are said compounds of formula I wherein:
X1selected from hydrogen, cyano, nitro, halogen, C1-C3Alkylsulfonyl radical, C1-C3Alkylsulfinyl radical, C1-C3Alkylthio radical, C1-C3Haloalkylthio, C1-C3Alkyl radical, C1-C3Haloalkyl, C1-C3Alkoxy radical, C1-C3Alkoxy radical C1-C3Alkyl radical, C1-C3Alkoxy radical C1-C3Alkoxy radical, C1-C3Alkoxy radical C1-C3Alkoxy radical C1-C3Alkyl radical, C3-C6Cycloalkyl or C3-C6A cycloalkyloxy group;
w is selected from N or CX2；
X2Selected from hydrogen, cyano, nitro, halogen, C1-C3Alkyl radical, C1-C3Haloalkyl, C3-C6Cycloalkyl radical, C3-C6Cycloalkyl radical C1-C3Alkyl radical, C3-C6Halogenocycloalkyl C1-C3Alkyl radical, Y1Oxy radical, Y1Thio radical, Y1Y2Amino group, Y1Sulfinyl radical, Y1Sulfonyl radical, Y1Oxy radical C1-C3Alkyl radical, Y1Thio radical C1-C3Alkyl radical, Y1Y2Amino group C1-C3Alkyl radical, Y1Sulfinyl radical C1-C3Alkyl radical, Y1Sulfonyl radical C1-C3Alkyl, COY1、COOY1、OCOOY1、NY1COOY2、C(O)N Y1Y2、NY1C(O)N Y1Y2、OC(O)N Y1Y2、NY1SO2Y2、NY1COY2、OSO2Y1、CH＝NOY1、C1-C6alkyl-CH-NOY1Phenyl which is unsubstituted or substituted by 1 to 5 substituents, a 5-to 7-membered aliphatic heterocyclic ring containing 1 to 4 hetero atoms, a 5-to 7-membered aromatic heterocyclic ring containing 1 to 4 hetero atoms, a 5-to 7-membered aliphatic heterocyclic ring containing 1 to 4 hetero atoms C1-C3Alkyl or 5-to 7-membered heteroaromatic ring C containing 1 to 4 heteroatoms1-C3Alkyl, the following substituents are selected from nitro, halogen and C1-C3Alkyl radical, C1-C3Haloalkyl, C1-C3Alkoxy radical, C3-C6Cycloalkyl or C3-C6A cycloalkoxy group;
Y1、Y2each independently selected from C1-C6Alkyl radical, C1-C6Haloalkyl, C3-C6Cycloalkyl radical, C3-C6Cycloalkyl radical C1-C6Alkyl radical, C1-C6Alkoxy radical C1-C6Alkyl, phenyl unsubstituted or substituted by 1 to 5 substituents, a 5-to 7-membered aliphatic heterocyclic ring containing 1 to 4 hetero atoms, a 5-to 7-membered aromatic heterocyclic ring containing 1 to 4 hetero atoms, a 5-to 7-membered aliphatic heterocyclic ring containing 1 to 4 hetero atoms C1-C6Alkyl or 5-to 7-membered heteroaromatic ring C containing 1 to 4 heteroatoms1-C6Alkyl, the following substituents are selected from nitro, halogen and C1-C6Alkyl radical, C1-C6Haloalkyl, C1-C6Alkoxy radical, C1-C6Haloalkoxy, C3-C6Cycloalkyl or C3-C6A cycloalkoxy group;
X3selected from hydrogen, cyano, halogen, C1-C3Alkylsulfonyl radical, C1-C3Alkylsulfinyl radical, C1-C3Alkylthio radical, C1-C3Haloalkylthio, C1-C3Alkyl radical, C1-C3Haloalkyl, C1-C3Alkoxy radical, C1-C3Alkoxy radical C1-C3Alkyl radical, C1-C3Alkoxy radical C1-C3Alkoxy radical, C1-C3Alkoxy radical C1-C3Alkoxy radical C1-C3Alkyl radical, C3-C6Cycloalkyl or C3-C6A cycloalkyloxy group;
when X is present1Selected from chlorine, X3When selected from methanesulfonyl, X2Is not thiazolyl;
Z1is selected from C1-C6Alkyl radical, C3-C6Cycloalkyl radical, C3-C6Alkenyl radical, C3-C6Alkynyl or phenyl;
Z2selected from H, C1-C6Alkyl radical, C1-C6Haloalkyl, phenyl, or phenyl substituted with one or more substituents selected from: halogen, cyano, nitro, C1-C6Alkyl radical, C3-C6Cycloalkyl or C1-C6A haloalkyl group;
R1to R5Each independently selected from hydrogen, hydroxyl, cyano, nitro, halogen, phenyl and C1-C6Alkyl radical, C2-C6Alkenyl radical, C2-C6Alkynyl, C1-C6Alkoxy or benzyloxy; wherein
R1And R2A benzene ring or a 5-to 7-membered aliphatic heterocyclic ring having 1 to 3 hetero atoms which may be combined together with the carbon atoms on the benzene ring to which they are bonded;
R2and R3A benzene ring or a 5-to 7-membered aliphatic heterocyclic ring having 1 to 3 hetero atoms which may be combined together with the carbon atoms on the benzene ring to which they are bonded;
stereoisomers of the compounds of the general formula I.
In a further preferred said compound, formula I:
X1selected from hydrogen, cyano, nitro, halogen, C1-C3Alkylsulfonyl radical, C1-C3Alkyl radical, C1-C3A haloalkyl group;
w is selected from N or CX2；
X2Selected from hydrogen, halogen, C1-C3Alkyl radical, C1-C3Haloalkyl, C3-C6Cycloalkyl radical, C3-C6Cycloalkyl radical C1-C3Alkyl radical, C3-C6Halogenocycloalkyl C1-C3Alkyl radical, Y1Oxy radical, Y1Thio radical, Y1Y2Amino group, Y1Sulfonyl radical, Y1Oxy radical C1-C3Alkyl radical, Y1Thio radical C1-C3Alkyl radical, Y1Y2Amino group C1-C3Alkyl radical, Y1Sulfonyl radical C1-C3Alkyl, COY1、COOY1、OCOOY1、NY1COOY2、C(O)N Y1Y2、NY1C(O)N Y1Y2、NY1SO2Y2、NY1COY2、OSO2Y1、CH＝NOY1、C1-C6alkyl-CH-NOY1Phenyl which is unsubstituted or substituted by 1 to 5 substituents, a 5-to 7-membered aliphatic heterocyclic ring containing 1 to 4 hetero atoms, a 5-to 7-membered aromatic heterocyclic ring containing 1 to 4 hetero atoms, a 5-to 7-membered aliphatic heterocyclic ring containing 1 to 4 hetero atoms C1-C3Alkyl or 5-to 7-membered heteroaromatic ring C containing 1 to 4 heteroatoms1-C3Alkyl, the following substituents are selected from nitro, halogen and C1-C3Alkyl radical, C1-C3Haloalkyl, C1-C3Alkoxy radical, C3-C6Cycloalkyl or C3-C6A cycloalkoxy group;
Y1、Y2each independently selected from C1-C6Alkyl radical, C1-C6Haloalkyl, C3-C6Cycloalkyl radical, C3-C6Cycloalkyl radical C1-C6Alkyl radical, C1-C6Alkoxy radical C1-C6Alkyl, phenyl unsubstituted or substituted by 1 to 5 substituents, a 5-to 7-membered aliphatic heterocyclic ring containing 1 to 4 hetero atoms, a 5-to 7-membered aromatic heterocyclic ring containing 1 to 4 hetero atoms, a 5-to 7-membered aliphatic heterocyclic ring containing 1 to 4 hetero atoms C1-C6Alkyl or 5-to 7-membered heteroaromatic ring C containing 1 to 4 heteroatoms1-C6Alkyl, the following substituents are selected from nitro, halogen and C1-C6Alkyl radical, C1-C6Haloalkyl, C1-C6Alkoxy radical, C1-C6Haloalkoxy, C3-C6Cycloalkyl or C3-C6A cycloalkoxy group;
X3selected from hydrogen, cyano, halogen, C1-C3Alkylsulfonyl radical, C1-C3Alkyl radical, C1-C3A haloalkyl group;
when X is present1Selected from chlorine, X3When selected from methanesulfonyl, X2Is not thiazolyl;
Z1is selected from C1-C3Alkyl or phenyl;
Z2selected from H, C1-C3Alkyl radical, C1-C3Haloalkyl or C3-C6A cycloalkyl group;
R1to R5Each independently selected from hydrogen, hydroxy, cyano, nitro, halogen, phenyl, methyl, ethyl, propyl, ethenyl, propenyl, ethynyl, propynyl, methoxy, ethoxy, benzyloxy, trifluoromethyl or trifluoromethoxy;
R1and R2Selected from the group consisting of benzene rings together with the carbon atoms of the benzene rings to which they are attached;
R2and R3Selected from the group consisting of a benzene ring, a1, 3-dioxane ring or a1, 4-dioxane ring together with the carbon atoms of the benzene ring to which they are attached;
trans stereoisomers of the compounds of formula I above.
In the definitions of the compounds of the general formula I given above, the terms used are collectively defined as follows:
alkyl means straight or branched chain forms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, n-hexyl and the like. Cycloalkyl is meant to include cyclic chain forms such as cyclopropyl, methylcyclopropyl, cyclopropylcyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and the like. Alkenyl means straight or branched chain alkenyl groups such as ethenyl, 1-propenyl, 2-propenyl, butenyl, pentenyl and hexenyl. Alkynyl means straight or branched chain alkynyl groups such as 1-propynyl, 2-propynyl, butynyl, pentynyl, hexynyl and the like. Alkoxy means a group having an oxygen atom attached to the terminal of an alkyl group, such as methoxy, ethoxy, n-propoxy, isopropoxy, t-butoxy, and the like. The 5-to 7-membered aliphatic heterocyclic ring containing 1 to 4 hetero atoms means a 5-to 7-membered heterocyclic compound containing 1 to 4 hetero atoms and having no aromatic character, such as ethylene oxide, tetrahydrofuran, imidazolidinone, caprolactam, 1, 3-dioxane ring, 1, 4-dioxane ring, etc. The 5-7 membered aromatic heterocyclic ring containing 1-4 hetero atoms refers to a 5-7 membered heterocyclic compound containing 1-4 hetero atoms and having aromatic characteristics, such as furan, thiophene, pyrazole, pyridine and the like. Stereoisomers refer to those in formula I in which the hydrogen atoms on the carbon-carbon double bond B are on the same side of the B bond (cis) or on both sides of the B bond (trans).
The compounds of formula I of the present invention can be prepared by the following process:
Figure BDA0002225413090000061
the compound of the general formula II and the compound of the general formula III react in a proper solvent at the temperature of-10 ℃ to the boiling point of the proper solvent for 0.5 to 48 hours to prepare the target compound I. Suitable solvents are selected from dichloromethane, 1, 2-dichloroethane, chloroform, carbon tetrachloride, hexane, benzene, toluene, ethyl acetate, acetonitrile, acetic acid, tetrahydrofuran, dioxane, N-dimethylformamide or dimethyl sulfoxide, and the like.
The addition of suitable alkali substances is beneficial to the reaction. Suitable bases are selected from organic bases such as triethylamine, N-dimethylaniline or pyridine, etc., or inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, sodium methoxide, sodium tert-butoxide or potassium tert-butoxide, etc.
The compounds of formula III can be prepared from the corresponding acids, which are commercially available or referenced: modern pesticides, 10(5),16-20, 23; 2011.
The preparation of the compounds of formula II is as follows:
Figure BDA0002225413090000062
the general formula IV in the formula is reacted in a proper solvent at the temperature of minus 10 ℃ to the boiling point of the proper solvent for 0.5 to 48 hours under the action of alkali and a catalyst to prepare the compound of the general formula II. Suitable solvents are selected from dichloromethane, 1, 2-dichloroethane, chloroform, carbon tetrachloride, hexane, benzene, toluene, ethyl acetate, acetonitrile, acetic acid, tetrahydrofuran, dioxane, N-dimethylformamide or dimethyl sulfoxide, and the like. Suitable bases are selected from sodium carbonate, potassium carbonate or triethylamine and the like. Suitable catalysts are selected from sodium carbonate, potassium carbonate, acetone cyanohydrin, azide, quaternary ammonium azide, metal cyanide or DMAP, and the like.
The preparation of the compound of formula IV is as follows:
Figure BDA0002225413090000071
the compound of formula V is reacted with a compound of formula VI (prepared by a method described in commercially available or reference EP 0240001) in a suitable solvent at a temperature of from-10 ℃ to the boiling point of the suitable solvent for a period of from 0.5 to 24 hours to produce a compound of formula IV. Suitable solvents are selected from dichloromethane, 1, 2-dichloroethane, chloroform, carbon tetrachloride, hexane, benzene, toluene, ethyl acetate, acetonitrile, acetic acid, tetrahydrofuran, dioxane, N-dimethylformamide or dimethyl sulfoxide, and the like.
The addition of suitable alkali substances is beneficial to the reaction. Suitable bases are selected from organic bases such as triethylamine, N-dimethylaniline or pyridine, etc., or inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, sodium methoxide, sodium tert-butoxide or potassium tert-butoxide, etc.
The starting carboxylic acid (commercially available) corresponding to the compound of formula V is reacted with an acid halogenating agent in a suitable solvent at a temperature of from-10 deg.C to the boiling point of the suitable solvent for a period of from 0.5 to 48 hours to produce the compound of formula V. The acyl halide reagent is selected from oxalyl chloride, thionyl chloride, phosphorus oxychloride, phosphorus trichloride, phosphorus pentachloride and the like. Suitable solvents are selected from dichloromethane, 1, 2-dichloroethane, hexane, benzene, toluene, acetonitrile, acetic acid, dioxane or liquid acid acylating agents and the like.
The compound of the general formula I, the stereoisomer thereof or the agriculturally acceptable salt of the compound of the general formula I and the isomer thereof has herbicidal activity and can be used for controlling various weeds in agriculture.
The invention also comprises a weeding composition which takes the compound shown in the general formula I, the stereoisomer thereof or the agriculturally acceptable salt of the compound shown in the general formula I and the isomer thereof as an active component. The weight percentage of the active components in the weeding composition is 1-99%. The herbicidal composition also includes an agriculturally acceptable carrier.
The herbicidal compositions of the present invention can be applied in the form of various formulations. The compounds of the present invention are typically formulated to be more easily dispersed for use as herbicides by dissolving or dispersing the compounds in a carrier. For example: the chemical preparation can be prepared into wettable powder or missible oil and the like. Thus, in these compositions, at least one liquid or solid carrier is added, and it is generally necessary to add a suitable surfactant.
The present invention also provides an implementation method for controlling weeds, which comprises applying a herbicidally effective amount of the herbicidal composition of the present invention to the weeds or to the locus where the weeds grow or to the surface of a growth medium thereof. Preferably, the effective dose is from 1 to 1000 grams per hectare, preferably from 10 to 500 grams per hectare. For certain applications, one or more additional herbicides may be added to the herbicidal compositions of the present invention, thereby providing additional advantages and benefits.
The compounds of the present invention can be used alone or in combination with other known insecticides, fungicides, plant growth regulators or fertilizers.
Compared with the prior art, the cinnamic carboxylic acid ester compound of the invention not only has excellent herbicidal activity, but also is safe to crops.
It should be understood that various changes and modifications may be made within the scope of the present invention as defined by the claims.
Detailed Description
The following examples and biological test results are provided to further illustrate the invention and are not meant to limit the invention.
Synthesis examples
Example 1, synthesis of compound 1-1:
(1) synthesis of 2-methylsulfonyl-4-trifluoromethylbenzoyl chloride
Figure BDA0002225413090000081
2-methanesulfonyl-4-trifluoromethylbenzoic acid (30 g, 112 mmol) and toluene (200 ml) were added to a reaction flask, sulfoxide chloride (53 g, 447 mmol) was slowly added thereto, the mixture was heated under reflux for 4 hours, and the solvent was evaporated off under reduced pressure to give 32 g of a yellow solid, which was directly used in the next step.
(2) Synthesis of 2-methanesulfonyl-4-trifluoromethylbenzoic acid (1, 3-dimethylpyrazol-5-yl) ester
Figure BDA0002225413090000082
To a reaction flask, 1, 3-dimethyl-5-hydroxypyrazole (13 g, 112 mmol), 1, 2-dichloroethane (200 ml), and triethylamine (34 g, 336 mmol) were added, and a solution of the above 2-methanesulfonyl-4-trifluoromethylbenzoyl chloride in 1, 2-dichloroethane (100 ml) was added dropwise. After stirring at room temperature for 1 hour, the solvent was evaporated off under reduced pressure, ethyl acetate (1000 ml) was added to the residue, water (500 ml) was added for liquid-phase extraction, the organic phase was washed successively with saturated brine (500 ml), dried over anhydrous magnesium sulfate, the solvent was evaporated off under reduced pressure, and the residue was separated by column chromatography to give 28 g of a yellow solid, yield: 68 percent.
(3) Synthesis of 1, 3-dimethyl-4- (2-methanesulfonyl-4-trifluoromethylbenzoyl) -5-hydroxypyrazole
Figure BDA0002225413090000083
Adding 1, 3-dimethylpyrazol-5-yl 2-methanesulfonyl-4-trifluoromethylbenzoate (6 g, 16.6 mmol), 1, 2-dichloroethane (50 ml), triethylamine (15 g, 148 mmol) and acetone cyanohydrin (1 ml) into a reaction flask, keeping the mixture at 60 ℃ for 6 hours, cooling to room temperature, adding water (100 ml) into the reaction solution, fully shaking for layering, adjusting the pH of the aqueous phase to 2-3 with 20% hydrochloric acid, extracting the aqueous phase twice with ethyl acetate (100 ml), washing the organic phase with saturated saline (50 ml), drying over anhydrous magnesium sulfate, and evaporating the solvent under reduced pressure to obtain 5.4 g of red oil, wherein the yield is as follows: 90 percent.
(4) Synthesis of cinnamoyl chloride
Figure BDA0002225413090000091
Cinnamic acid (0.17 g, 1.1 mmol), dichloromethane (30 ml) and DMF (1 drop) were added to the reaction flask, oxalyl chloride (0.7 g, 5.5 mmol) was added slowly, the mixture was stirred at room temperature for 1 hour, the solvent was evaporated under reduced pressure, toluene (15 ml) was added to the residue, and after stirring for 3 minutes, the solvent was evaporated under reduced pressure to give 0.18 g of a pale yellow solid which was used directly in the next step.
(5) Synthesis of Compound 1-1
Figure BDA0002225413090000092
To a reaction flask, 1, 3-dimethyl-4- (2-methanesulfonyl-4-trifluoromethylbenzoyl) -5-hydroxypyrazole (0.4 g, 1.1 mmol), dichloromethane (20 ml), and triethylamine (0.22 g, 2.2 mmol) were added, and a dichloromethane solution (15 ml) of cinnamoyl chloride of the above step was added dropwise. After stirring at room temperature for 1 hour, the solvent was evaporated under reduced pressure, ethyl acetate (100 ml) was added to the residue, water (50 ml) was added for liquid-phase extraction, the organic phase was washed successively with saturated brine (50 ml), dried over anhydrous magnesium sulfate, the solvent was evaporated under reduced pressure, and the residue was separated by column chromatography to give 0.35 g of compound 1 as a white solid with a purity of 99.3%, yield: and 64 percent.
Example 2, synthesis of compounds 1-7:
(1) synthesis of 3,4- (methylenedioxy) cinnamoyl chloride
Figure BDA0002225413090000093
3,4- (methylenedioxy) cinnamic acid (0.21 g, 1.1 mmol), dichloromethane (30 ml) and DMF (1 drop) were added to a reaction flask, oxalyl chloride (0.7 g, 5.5 mmol) was added slowly, the mixture was stirred at room temperature for 1 hour, the solvent was evaporated under reduced pressure, toluene (15 ml) was added to the residue and after stirring for 3 minutes, the solvent was evaporated under reduced pressure to give 0.23 g of a pale yellow solid which was used directly in the next step.
(2) Synthesis of Compounds 1 to 7
Figure BDA0002225413090000094
To a reaction flask was added 1, 3-dimethyl-4- (2-methanesulfonyl-4-trifluoromethylbenzoyl) -5-hydroxypyrazole (0.4 g, 1.1 mmol, for its preparation see example 1, step 3), dichloromethane (20 ml), triethylamine (0.22 g, 2.2 mmol), and a dichloromethane solution of step 3,4- (methylenedioxy) cinnamoyl chloride (15 ml) was added dropwise. After stirring at room temperature for 1 hour, the solvent was evaporated under reduced pressure, ethyl acetate (100 ml) was added to the residue, water (50 ml) was added for liquid-phase extraction, the organic phase was washed successively with saturated brine (50 ml), dried over anhydrous magnesium sulfate, the solvent was evaporated under reduced pressure, and the residue was separated by column chromatography to give 0.38 g of pale yellow solid compound 7, purity 94.6%, yield: 60.7 percent.
Example 3, synthesis of compounds 1-16:
(1) synthesis of 2-chloro-3-methoxymethyl-4-methylsulfonylbenzoyl chloride
Figure BDA0002225413090000101
2-methanesulfonyl-4-trifluoromethylbenzoic acid (4 g, 14.35 mmol), dichloromethane (30 ml) and DMF were added to the reaction flask one drop, oxalyl chloride (9.11 g, 71.8 mmol) was added slowly, the mixture was stirred at room temperature for 40 minutes, the solvent was evaporated under reduced pressure, toluene (15 ml) was added to the residue and after stirring for 3 minutes, the solvent was evaporated under reduced pressure to give 4.26 g of a yellow solid, which was taken directly to the next step.
(2) Synthesis of 2-chloro-3-methoxymethyl-4-methylsulfonylbenzoic acid (1, 3-dimethylpyrazol-5-yl) ester
Figure BDA0002225413090000102
To a reaction flask, 1, 3-dimethyl-5-hydroxypyrazole (1.77 g, 15.79 mmol), dichloromethane (100 ml), and triethylamine (2.9 g, 28.7 mmol) were added, and a dichloromethane solution (30 ml) of the above-obtained 2-chloro-3-methoxymethyl-4-methanesulfonylbenzoyl chloride was added dropwise. After stirring at room temperature for 1 hour, the solvent was evaporated under reduced pressure, ethyl acetate (100 ml) was added to the residue, water (100 ml) was added for liquid-phase extraction, the organic phase was washed successively with saturated brine (100 ml), dried over anhydrous magnesium sulfate, the solvent was evaporated under reduced pressure, and the residue was separated by column chromatography to give 3.4 g of an off-white solid, yield: and (3.5).
(3) Synthesis of 1, 3-dimethyl-4- (2-chloro-3-methoxymethyl-4-methanesulfonylbenzoyl) -5-hydroxypyrazole
Figure BDA0002225413090000103
To a reaction flask were added 2-chloro-3-methoxymethyl-4-methylsulfonylbenzoic acid (1, 3-dimethylpyrazol-5-yl) ester (3.4 g, 9.12 mmol), dichloromethane (100 ml), triethylamine (1.38 g, 13.68 mmol), and acetone cyanohydrin (1 ml), reacted at room temperature for 12 hours, water was added to the reaction solution to extract (50 ml × 3), the aqueous phase was collected and then adjusted to pH 2 to 3 with 20% hydrochloric acid, the aqueous phase was extracted twice with ethyl acetate (100 ml), the organic phase was washed with saturated saline (50 ml), dried over anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure to give 3.26 g of a yellow solid, yield: 96 percent.
(5) Synthesis of Compounds 1 to 16
Figure BDA0002225413090000111
To a reaction flask was added 1, 3-dimethyl-4- (2-chloro-3-methoxymethyl-4-methanesulfonylbenzoyl) -5-hydroxypyrazole (0.4 g, 1.07 mmol), dichloromethane (20 ml), triethylamine (0.22 g, 2.15 mmol), and a dichloromethane solution of cinnamoyl chloride of the above step (15 ml, for preparation see step 4 of example 1) was added dropwise. After stirring at room temperature for 1 hour, the solvent was evaporated under reduced pressure, ethyl acetate (100 ml) was added to the residue, water (50 ml) was added for liquid-phase extraction, the organic phase was washed successively with saturated brine (50 ml), dried over anhydrous magnesium sulfate, the solvent was evaporated under reduced pressure, and the residue was separated by column chromatography to give 0.31 g of compound 16 as a white solid with a purity of 93.2%, yield: 53.5 percent.
Replacing the starting material according to the above-described procedure to obtain additional compounds of formula I, wherein some of the compounds of formula I are shown in tables 1 and 2; wherein, in Table 1, W is selected from CX2And the stereoconfiguration is trans; in Table 2, W is selected from N, and the steric configuration is trans.
A compound of the formula I, wherein W is CX2And the stereoconfiguration is trans.
Figure BDA0002225413090000112
Table 1 structural and physical properties of some compounds of formula I
Figure BDA0002225413090000113
Figure BDA0002225413090000121
Figure BDA0002225413090000131
Figure BDA0002225413090000141
Figure BDA0002225413090000151
Figure BDA0002225413090000161
Figure BDA0002225413090000171
Figure BDA0002225413090000181
Figure BDA0002225413090000191
Figure BDA0002225413090000201
Figure BDA0002225413090000211
Figure BDA0002225413090000221
Figure BDA0002225413090000231
Figure BDA0002225413090000241
Figure BDA0002225413090000251
Figure BDA0002225413090000261
Figure BDA0002225413090000271
Figure BDA0002225413090000281
Figure BDA0002225413090000291
Figure BDA0002225413090000301
Figure BDA0002225413090000311
Figure BDA0002225413090000321
Figure BDA0002225413090000331
Figure BDA0002225413090000341
Figure BDA0002225413090000351
Of partial compounds1The H NMR data are as follows:
compound 1-1(600MHz, DMSO-d)6)：8.11(s,2H),7.63-7.67(m,3H),7.42-7.51(m,4H),6.28(d,1H),3.57(s,3H),3.34(s,3H),2.33(s,3H)。
Compounds 1-7(600MHz, CDCl)3)：8.18(s,1H),7.81(d,1H),7.45(d,1H),7.37(d,1H),6.96(dd,1H),6.90(s,1H),6.82(d,1H),6.03(s,2H),5.76(d,1H),3.57(s,3H),3.26(s,3H),2.42(s,3H)。
Compounds 1-16(600MHz, CDCl)3)：8.03(d,1H),7.59(d,1H),7.37-7.48(m,6H),6.09(d,1H),4.98(s,2H),3.61(s,3H),3.47(s,3H),2.81(s,3H),2.47(s,3H)。
Compounds 1-18(600MHz, DMSO-d)6)：7.98(d,1H),7.56-7.65(m,4H),6.98(d,2H),6.15(d,1H),4.86(s,2H),3.82(s,3H),3.57(s,3H),3.34(s,3H),2.94(s,3H),2.35(s,3H)。
Compound 1-20(600MHz, DMSO-d)6)：7.98(d,1H),7.90(d,2H),7.78(d,2H),7.70(d,1H),7.60(d,1H),6.50(d,1H),4.84(s,2H),3.60(s,3H),3.32(s,3H),3.01(s,3H),2.34(s,3H)。
Compounds 1-21(600MHz, DMSO-d)6)：8.00(d,1H),7.74-7.79(m,6H),7.68(d,1H),7.61(d,1H),7.50(t,2H),7.42(t,1H),6.38(d,1H),4.86(s,2H),3.60(s,3H),3.34(s,3H),2.97(s,3H),2.34(s,3H)。
Compounds 1-22(600MHz, DMSO-d)6)：7.98(d,1H),7.58(d,1H),7.52(d,1H),7.33(s,1H),7.19(d,1H),6.97(d,1H),6.18(d,1H),6.11(s,2H),4.86(s,2H),3.57(s,3H),3.35(s,3H),2.99(s,3H),2.34(s,3H)。
Compounds 1-31(600MHz, CDCl)3)：8.01(d,1H),7.63(d,1H),7.44-7.49(m,5H),7.28(d,1H),6.03(d,1H),3.62(s,3H),2.84(s,3H),2.67(s,3H),2.45(s,3H)。
Compound 1-37(600MHz, DMSO-d)6)：7.92(d,1H),7.55(d,1H),7.42(d,1H),7.37(s,1H),7.22(d,1H),6.98(d,1H),6.21(d,1H),6.11(s,2H),3.56(s,3H),2.99(s,3H),2.59(s,3H),2.33(s,3H)。
Compound 1-76(600MHz, DMSO-d)6)：7.99(d,1H),7.60-7.70(m,4H),7.43-7.51(m,3H),6.34(d,1H),4.95(s,2H),3.65(t,2H),3.60(s,3H),3.47(t,2H),3.23(s,3H),2.99(s,3H),2.34(s,3H)。
Compound 1-223(600MHz, DMSO-d)6)：7.97(d,2H),7.65-7.71(m,4H),7.44-7.48(m,3H),6.40(d,1H),3.60(s,3H),2.93(s,3H),2.32(s,3H)。
Compound 1-226(600MHz, DMSO-d)6)：8.01(s,1H),7.90(d,1H),7.62(d,1H),7.55(d,1H),7.37(s,1H),7.21(d,1H),6.97(d,1H),6.24(d,1H),6.11(s,2H),3.58(s,3H),2.99(s,3H),2.33(s,3H)。
Compound 1-229(600MHz, DMSO-d)6)：7.73(d,2H),7.60(d,1H),7.56(d,1H),7.46-7.52(m,3H),7.43(dd,1H),7.36(d,1H),6.39(d,1H),3.59(s,3H),2.33(s,3H)。
Compound 1-232(600MHz, DMSO-d)6)：7.59(s,1H),7.46(d,1H),7.40-7.43(m,2H),7.34(d,1H),7.22(d,1H),7.00(d,1H),6.23(d,1H),6.12(s,2H),3.57(s,3H),2.32(s,3H)。
Compound 1-235(600MHz, DMSO-d)6)：8.58(s,1H),8.36(d,1H),7.84(d,1H),7.69(d,2H),7.62(d,1H),7.44-7.51(m,3H),6.37(d,1H),3.58(s,3H),3.01(s,3H),2.35(s,3H)。
Compounds 1-238(600MHz, DMSO-d)6)：8.58(s,1H),8.34(d,1H),7.82(d,1H),7.51(d,1H),7.36(s,1H),7.20(d,1H),6.98(d,1H),6.20(d,1H),6.12(s,2H),3.55(s,3H),3.07(s,3H),2.36(s,3H)。
Compound 1-259(600MHz, DMSO-d)6)：7.68-7.70(m,3H),7.62(d,1H),7.48(t,1H),7.42-7.44(m,2H),7.23(d,1H),6.40(d,1H),4.01(t,2H),3.62(t,2H),3.59(s,3H),3.30(s,3H),2.88(s,3H),2.34(s,3H),2.17(s,3H)。
Compounds 1-262(600MHz, CDCl)3)：7.78(d,1H),7.44(d,1H),7.13(d,1H),6.93-6.96(m,2H),6.81(d,1H),6.01(s,2H),5.83(d,1H),4.09(t,2H),3.69(t,2H),3.58(s,3H),3.40(s,3H),2.96(s,3H),2.39(s,3H),2.26(s,3H)。
Compounds 1-367(600MHz, CDCl)3)：8.04(s,1H),7.46-7.60(m,7H),7.33(d,1H),6.06(d,1H),3.58(s,3H),2.47(s,3H)。
A compound of formula I wherein W is N and the stereoconfiguration is trans.
Figure BDA0002225413090000361
Table 2 structural and physical properties of part of compounds of formula I
Figure BDA0002225413090000362
Figure BDA0002225413090000371
Figure BDA0002225413090000381
Figure BDA0002225413090000391
Figure BDA0002225413090000401
Figure BDA0002225413090000411
Figure BDA0002225413090000421
Figure BDA0002225413090000431
Examples of bioassay
Example 4 determination of herbicidal Activity
Sowing seeds of broad-leaved weeds (zinnia elegans and abutilon) or grassy weeds (green bristlegrass and barnyard grass) in a paper cup with the diameter of 7cm and containing nutrient soil, covering soil for 1cm after sowing, compacting, spraying water, culturing in a greenhouse according to a conventional method, and spraying stems and leaves after 2-3 leaf periods of the weeds.
After the original drug is dissolved by acetone, the solution to be tested with the required concentration is prepared by using 1 per mill of Tween 80 to stand tap water according to the test requirements. The spray treatment (spray pressure 1.95 kg/cm) was carried out on a crawler-type crop sprayer (Engineer Research Ltd. in England) at the experimental design dose2The amount of the liquid spray is 500L/hm2And the track speed is 1.48 km/h). The experiment was repeated 3 times. After being treated, the test material is placed in an operation hall, after the liquid medicine is naturally dried in the shade, the test material is placed in a greenhouse for management according to a conventional method, the reaction condition of weeds to the agent is observed and recorded, the weed control effect of the test agent to weeds is regularly observed and visually observed after the treatment, the weed control effect is expressed by 0-100%, and the weed control effect is expressed by 0% to 100%, and the weed control effect is expressed by 100%.
The test result shows that the compound of the general formula I has higher control effect on various weeds. Of some of the compounds tested, compound 1-1, for example, was administered at a dose of 600g a.i./hm2Has better prevention effect on zinnia elegans, piemarker, green bristlegrass or cockspur grass, and the prevention effect is more than or equal to 90 percent.
The compound of the general formula is safe to crops such as wheat, rice or corn.
The compound of the general formula has herbicidal activity, is safe to crops, and can be used for preventing and controlling various weeds in agriculture.

Claims (7)

1. A cinnamic carboxylate compound is characterized in that: the compound is shown as a general formula I:
Figure FDA0002225413080000011
in the formula:
X1selected from hydrogen, cyano, nitro, halogen, C1-C6Alkylsulfonyl radical, C1-C6Haloalkylsulfonyl group, C1-C6Alkylsulfinyl radical, C1-C6Haloalkylsulfinyl radical, C1-C6Alkylthio radical, C1-C6Haloalkylthio, C1-C6Alkyl radical, C1-C6Haloalkyl, C1-C6Alkoxy radical, C1-C6Haloalkoxy, C1-C6Alkoxy radical C1-C3Alkyl radical, C1-C6Alkoxy radical C1-C3Alkoxy radical, C1-C6Alkoxy radical C1-C3Alkoxy radical C1-C3Alkyl radical, C3-C6Cycloalkyl radical, C3-C6Cycloalkyl radical C1-C3Alkyl radical, C3-C6Cycloalkyl radical C1-C3Alkoxy radical, C3-C6Cycloalkyl oxy, C2-C6Alkenyl radical, C2-C6Alkynyl, phenyl unsubstituted or substituted by 1 to 5 substituents2-C6Alkenylsulfonyl radical, C2-C6Alkynylsulfonyl, phenylsulfonyl, C2-C6Alkenyloxy radical, C2-C6Alkynyloxy, phenyloxy, C2-C6Alkenylthio radical, C2-C6Alkynylthio, phenylthio, 5-7 membered aliphatic heterocyclic ring containing 1-4 hetero atoms, 5-7 membered aromatic heterocyclic ring containing 1-4 hetero atoms, 5-7 membered aliphatic heterocyclic ring containing 1-4 hetero atoms C1-C6Alkyl or 5-to 7-membered heteroaromatic ring C containing 1 to 4 heteroatoms1-C6Alkyl, the following substituents are selected from nitro, halogen and C1-C6Alkyl radical, C1-C6Haloalkyl, C1-C6Alkoxy radical, C1-C6Haloalkoxy or C3-C6A cycloalkyl group;
w is selected from N or CX2；
X2Selected from hydrogen, cyano, nitro, halogen, C1-C6Alkyl radical, C1-C6Haloalkyl, C3-C6Cycloalkyl radical, C3-C6Cycloalkyl radical C1-C6Alkyl radical, C3-C6Halogenocycloalkyl C1-C6Alkyl radical, Y1Oxy radical, Y1Thio radical, Y1Y2Amino group, Y1Sulfinyl radical, Y1Sulfonyl radical, Y1Oxy radical C1-C6Alkyl radical, Y1Thio radical C1-C6Alkyl radical, Y1Y2Amino group C1-C6Alkyl radical, Y1Sulfinyl radical C1-C6Alkyl radical, Y1Sulfonyl radical C1-C6Alkyl, COY1、COOY1、OCOOY1、NY1COOY2、C(O)N Y1Y2、NY1C(O)N Y1Y2、OC(O)NY1Y2、C(O)N(Y1)OY2、NY1SO2Y2、NY1COY2、OSO2Y1、CH＝NOY1、C1-C6alkyl-CH-NOY1、C1-C6alkyl-O-N ═ CY1Y2Phenyl unsubstituted or substituted by 1 to 5 substituents, 5-to 7-membered aliphatic heterocyclic ring containing 1 to 4 hetero atoms, 5-to 7-membered aromatic heterocyclic ring containing 1 to 4 hetero atoms, 1 to 4 hetero atoms5-7 membered aliphatic heterocyclic ring of son1-C6Alkyl or 5-to 7-membered heteroaromatic ring C containing 1 to 4 heteroatoms1-C6Alkyl, the following substituents are selected from nitro, halogen and C1-C6Alkyl radical, C1-C6Haloalkyl, C1-C6Alkoxy radical, C1-C6Haloalkoxy, C3-C6Cycloalkyl radical, C3-C6Cycloalkoxy, C2-C6Alkenyl radical, C2-C6Alkynyl, phenyl or halophenyl;
Y1、Y2each independently selected from C1-C6Alkyl radical, C1-C6Haloalkyl, C3-C6Cycloalkyl radical, C3-C6Cycloalkyl radical C1-C6Alkyl radical, C1-C6Alkoxy radical C1-C6Alkyl, phenyl unsubstituted or substituted by 1 to 5 substituents, a 5-to 7-membered aliphatic heterocyclic ring containing 1 to 4 hetero atoms, a 5-to 7-membered aromatic heterocyclic ring containing 1 to 4 hetero atoms, a 5-to 7-membered aliphatic heterocyclic ring containing 1 to 4 hetero atoms C1-C6Alkyl or 5-to 7-membered heteroaromatic ring C containing 1 to 4 heteroatoms1-C6Alkyl, the following substituents are selected from nitro, halogen and C1-C6Alkyl radical, C1-C6Haloalkyl, C1-C6Alkoxy radical, C1-C6Haloalkoxy, C3-C6Cycloalkyl radical, C3-C6Cycloalkoxy, C2-C6Alkenyl radical, C2-C6Alkynyl, phenyl or halophenyl;
X3selected from hydrogen, cyano, halogen, C1-C6Alkylsulfonyl radical, C1-C6Haloalkylsulfonyl group, C1-C6Alkylsulfinyl radical, C1-C6Haloalkylsulfinyl radical, C1-C6Alkylthio radical, C1-C6Haloalkylthio, C1-C6Alkyl radical, C1-C6Haloalkyl, C1-C6Alkoxy radical, C1-C6Haloalkoxy, C1-C6Alkoxy radical C1-C3Alkyl radical, C1-C6Alkoxy radical C1-C3Alkoxy radical, C1-C6Alkoxy radical C1-C3Alkoxy radical C1-C3Alkyl radical, C3-C6Cycloalkyl radical, C3-C6Cycloalkyl radical C1-C3Alkyl radical, C3-C6Cycloalkyl radical C1-C3Alkoxy radical, C3-C6Cycloalkyl oxy, C2-C6Alkenyl radical, C2-C6Alkynyl, phenyl unsubstituted or substituted by 1 to 5 substituents2-C6Alkenylsulfonyl radical, C2-C6Alkynylsulfonyl, phenylsulfonyl, C2-C6Alkenyloxy radical, C2-C6Alkynyloxy, phenyloxy, C2-C6Alkenylthio radical, C2-C6Alkynylthio, phenylthio, 5-7 membered aliphatic heterocyclic ring containing 1-4 hetero atoms, 5-7 membered aromatic heterocyclic ring containing 1-4 hetero atoms, 5-7 membered aliphatic heterocyclic ring containing 1-4 hetero atoms C1-C6Alkyl or 5-to 7-membered heteroaromatic ring C containing 1 to 4 heteroatoms1-C6Alkyl, the following substituents are selected from nitro, halogen and C1-C6Alkyl radical, C1-C6Haloalkyl, C1-C6Alkoxy radical, C1-C6Haloalkoxy or C3-C6A cycloalkyl group;
when X is present1Selected from chlorine, X3When selected from methanesulfonyl, X2Is not thiazolyl;
Z1is selected from C1-C6Alkyl radical, C3-C6Cycloalkyl radical, C3-C6Cycloalkyl radical C1-C6Alkyl radical, C3-C6Alkenyl radical, C3-C6Alkynyl, C1-C6Alkylsulfonyl radical C1-C6Alkyl or phenyl;
Z2selected from H, C1-C6Alkyl radical, C3-C6Cycloalkyl radical, C1-C6A halogenated alkyl group,Phenyl unsubstituted or substituted by at least one of the following substituents; the following substituents are selected from: halogen, cyano, nitro, C1-C6Alkyl radical, C3-C6Cycloalkyl or C1-C6A haloalkyl group;
R1to R5Each independently selected from hydrogen, cyano, nitro, halogen, phenyl, C1-C6Alkyl radical, C1-C6Haloalkyl, C2-C6Alkenyl radical, C2-C6Haloalkenyl, C2-C6Alkynyl, C2-C6Halogenated alkynyl, C1-C6Alkoxy radical, C1-C6Haloalkoxy, C1-C6Alkylthio or benzyloxy;
wherein R is1And R2Can form a benzene ring, a 5-7 membered aliphatic heterocyclic ring containing 1-3 heteroatoms or a 5-7 membered aromatic heterocyclic ring containing 1-3 heteroatoms together with the carbon atoms on the benzene ring to which they are attached;
R2and R3Can form a benzene ring, a 5-7 membered aliphatic heterocyclic ring with 1-3 heteroatoms or a 5-7 membered aromatic heterocyclic ring with 1-3 heteroatoms together with the carbon atoms on the benzene ring connected with the benzene ring;
stereoisomers of the compounds of formula I above; or, the compound of the general formula I and the isomer agriculturally acceptable salt thereof.
2. A compound according to claim 1, wherein in formula I:
X1selected from hydrogen, cyano, nitro, halogen, C1-C6Alkylsulfonyl radical, C1-C6Alkylsulfinyl radical, C1-C6Alkylthio radical, C1-C6Haloalkylthio, C1-C6Alkyl radical, C1-C6Haloalkyl, C1-C6Alkoxy radical, C1-C6Alkoxy radical C1-C3Alkyl radical, C1-C6Alkoxy radical C1-C3Alkoxy radical, C1-C6Alkoxy radical C1-C3Alkoxy radicalC1-C3Alkyl radical, C3-C6Cycloalkyl radical, C3-C6Cycloalkyl radical C1-C3Alkyl radical, C3-C6Cycloalkyl radical C1-C3Alkoxy radical, C3-C6Cycloalkyl oxy, C2-C6Alkenyl radical, C2-C6Alkynyl, phenyl which is unsubstituted or substituted by 1 to 5 substituents described below, phenylsulfonyl, C2-C6Alkenyloxy, phenyloxy, 5-7 membered aliphatic heterocyclic ring containing 1-4 heteroatoms, 5-7 membered aromatic heterocyclic ring containing 1-4 heteroatoms, the following substituents are selected from nitro, halogen, C1-C6Alkyl radical, C1-C6Haloalkyl, C1-C6Alkoxy radical, C1-C6Haloalkoxy or C3-C6A cycloalkyl group;
w is selected from N or CX2；
X2Selected from hydrogen, cyano, nitro, halogen, C1-C6Alkyl radical, C1-C6Haloalkyl, C3-C6Cycloalkyl radical, C3-C6Cycloalkyl radical C1-C6Alkyl radical, C3-C6Halogenocycloalkyl C1-C6Alkyl radical, Y1Oxy radical, Y1Thio radical, Y1Y2Amino group, Y1Sulfinyl radical, Y1Sulfonyl radical, Y1Oxy radical C1-C6Alkyl radical, Y1Thio radical C1-C6Alkyl radical, Y1Y2Amino group C1-C6Alkyl radical, Y1Sulfinyl radical C1-C6Alkyl radical, Y1Sulfonyl radical C1-C6Alkyl, COY1、COOY1、OCOOY1、NY1COOY2、C(O)N Y1Y2、NY1C(O)N Y1Y2、OC(O)NY1Y2、C(O)N(Y1)OY2、NY1SO2Y2、NY1COY2、OSO2Y1、CH＝NOY1、C1-C6alkyl-CH＝NOY1、C1-C6alkyl-O-N ═ CY1Y2Phenyl which is unsubstituted or substituted by 1 to 5 substituents, a 5-to 7-membered aliphatic heterocyclic ring containing 1 to 4 hetero atoms, a 5-to 7-membered aromatic heterocyclic ring containing 1 to 4 hetero atoms, a 5-to 7-membered aliphatic heterocyclic ring containing 1 to 4 hetero atoms C1-C6Alkyl or 5-to 7-membered heteroaromatic ring C containing 1 to 4 heteroatoms1-C6Alkyl, the following substituents are selected from nitro, halogen and C1-C6Alkyl radical, C1-C6Haloalkyl, C1-C6Alkoxy radical, C1-C6Haloalkoxy, C3-C6Cycloalkyl radical, C3-C6A cycloalkoxy group;
Y1、Y2each independently selected from C1-C6Alkyl radical, C1-C6Haloalkyl, C3-C6Cycloalkyl radical, C3-C6Cycloalkyl radical C1-C6Alkyl radical, C1-C6Alkoxy radical C1-C6Alkyl, phenyl unsubstituted or substituted by 1 to 5 substituents, a 5-to 7-membered aliphatic heterocyclic ring containing 1 to 4 hetero atoms, a 5-to 7-membered aromatic heterocyclic ring containing 1 to 4 hetero atoms, a 5-to 7-membered aliphatic heterocyclic ring containing 1 to 4 hetero atoms C1-C6Alkyl or 5-to 7-membered heteroaromatic ring C containing 1 to 4 heteroatoms1-C6Alkyl, the following substituents are selected from nitro, halogen and C1-C6Alkyl radical, C1-C6Haloalkyl, C1-C6Alkoxy radical, C1-C6Haloalkoxy, C3-C6Cycloalkyl radical, C3-C6A cycloalkoxy group;
X3selected from hydrogen, cyano, halogen, C1-C6Alkylsulfonyl radical, C1-C6Alkylsulfinyl radical, C1-C6Alkylthio radical, C1-C6Haloalkylthio, C1-C6Alkyl radical, C1-C6Haloalkyl, C1-C6Alkoxy radical, C1-C6Alkoxy radical C1-C3Alkyl radical, C1-C6Alkoxy radical C1-C3Alkoxy radical, C1-C6Alkoxy radical C1-C3Alkoxy radical C1-C3Alkyl radical, C3-C6Cycloalkyl radical, C3-C6Cycloalkyl radical C1-C3Alkyl radical, C3-C6Cycloalkyl radical C1-C3Alkoxy radical, C3-C6Cycloalkyl oxy, C2-C6Alkenyl radical, C2-C6Alkynyl, phenyl which is unsubstituted or substituted by 1 to 5 substituents described below, phenylsulfonyl, C2-C6Alkenyloxy, phenyloxy, 5-7 membered aliphatic heterocyclic ring containing 1-4 heteroatoms, 5-7 membered aromatic heterocyclic ring containing 1-4 heteroatoms, the following substituents are selected from nitro, halogen, C1-C6Alkyl radical, C1-C6Haloalkyl, C1-C6Alkoxy radical, C1-C6Haloalkoxy or C3-C6A cycloalkyl group;
when X is present1Selected from chlorine, X3When selected from methanesulfonyl, X2Is not thiazolyl;
Z1is selected from C1-C6Alkyl radical, C3-C6Cycloalkyl radical, C3-C6Cycloalkyl radical C1-C6Alkyl radical, C3-C6Alkenyl radical, C3-C6Alkynyl or phenyl;
Z2selected from H, C1-C6Alkyl radical, C1-C6Haloalkyl, phenyl unsubstituted or substituted with at least one of the following substituents; the following substituents are selected from: halogen, cyano, nitro, C1-C6Alkyl radical, C3-C6Cycloalkyl or C1-C6A haloalkyl group;
R1to R5Each independently selected from hydrogen, cyano, nitro, halogen, phenyl, C1-C6Alkyl radical, C2-C6Alkenyl radical, C2-C6Alkynyl, C1-C6Alkoxy radical, C1-C6Alkylthio or benzyloxy;
whereinR1And R2Can form a benzene ring, a 5-7 membered aliphatic heterocyclic ring containing 1-3 heteroatoms or a 5-7 membered aromatic heterocyclic ring containing 1-3 heteroatoms together with the carbon atoms on the benzene ring to which they are attached;
R2and R3Can form a benzene ring, a 5-7 membered aliphatic heterocyclic ring with 1-3 heteroatoms or a 5-7 membered aromatic heterocyclic ring with 1-3 heteroatoms together with the carbon atoms on the benzene ring connected with the benzene ring;
stereoisomers of the compounds of the general formula I.
3. A compound according to claim 2, wherein in formula I:
X1selected from hydrogen, cyano, nitro, halogen, C1-C3Alkylsulfonyl radical, C1-C3Alkylsulfinyl radical, C1-C3Alkylthio radical, C1-C3Haloalkylthio, C1-C3Alkyl radical, C1-C3Haloalkyl, C1-C3Alkoxy radical, C1-C3Alkoxy radical C1-C3Alkyl radical, C1-C3Alkoxy radical C1-C3Alkoxy radical, C1-C3Alkoxy radical C1-C3Alkoxy radical C1-C3Alkyl radical, C3-C6Cycloalkyl or C3-C6A cycloalkyloxy group;
w is selected from N or CX2；
X2Selected from hydrogen, cyano, nitro, halogen, C1-C3Alkyl radical, C1-C3Haloalkyl, C3-C6Cycloalkyl radical, C3-C6Cycloalkyl radical C1-C3Alkyl radical, C3-C6Halogenocycloalkyl C1-C3Alkyl radical, Y1Oxy radical, Y1Thio radical, Y1Y2Amino group, Y1Sulfinyl radical, Y1Sulfonyl radical, Y1Oxy radical C1-C3Alkyl radical, Y1Thio radical C1-C3Alkyl radical, Y1Y2Amino group C1-C3Alkyl radical, Y1Sulfinyl radical C1-C3Alkyl radical, Y1Sulfonyl radical C1-C3Alkyl, COY1、COOY1、OCOOY1、NY1COOY2、C(O)N Y1Y2、NY1C(O)N Y1Y2、OC(O)N Y1Y2、NY1SO2Y2、NY1COY2、OSO2Y1、CH＝NOY1、C1-C6alkyl-CH-NOY1Phenyl which is unsubstituted or substituted by 1 to 5 substituents, a 5-to 7-membered aliphatic heterocyclic ring containing 1 to 4 hetero atoms, a 5-to 7-membered aromatic heterocyclic ring containing 1 to 4 hetero atoms, a 5-to 7-membered aliphatic heterocyclic ring containing 1 to 4 hetero atoms C1-C3Alkyl or 5-to 7-membered heteroaromatic ring C containing 1 to 4 heteroatoms1-C3Alkyl, the following substituents are selected from nitro, halogen and C1-C3Alkyl radical, C1-C3Haloalkyl, C1-C3Alkoxy radical, C3-C6Cycloalkyl or C3-C6A cycloalkoxy group;
Y1、Y2each independently selected from C1-C6Alkyl radical, C1-C6Haloalkyl, C3-C6Cycloalkyl radical, C3-C6Cycloalkyl radical C1-C6Alkyl radical, C1-C6Alkoxy radical C1-C6Alkyl, phenyl unsubstituted or substituted by 1 to 5 substituents, a 5-to 7-membered aliphatic heterocyclic ring containing 1 to 4 hetero atoms, a 5-to 7-membered aromatic heterocyclic ring containing 1 to 4 hetero atoms, a 5-to 7-membered aliphatic heterocyclic ring containing 1 to 4 hetero atoms C1-C6Alkyl or 5-to 7-membered heteroaromatic ring C containing 1 to 4 heteroatoms1-C6Alkyl, the following substituents are selected from nitro, halogen and C1-C6Alkyl radical, C1-C6Haloalkyl, C1-C6Alkoxy radical, C1-C6Haloalkoxy, C3-C6Cycloalkyl or C3-C6A cycloalkoxy group;
X3selected from hydrogen, cyano, halogen, C1-C3Alkylsulfonyl radical, C1-C3Alkylsulfinyl radical, C1-C3Alkylthio radical, C1-C3Haloalkylthio, C1-C3Alkyl radical, C1-C3Haloalkyl, C1-C3Alkoxy radical, C1-C3Alkoxy radical C1-C3Alkyl radical, C1-C3Alkoxy radical C1-C3Alkoxy radical, C1-C3Alkoxy radical C1-C3Alkoxy radical C1-C3Alkyl radical, C3-C6Cycloalkyl or C3-C6A cycloalkyloxy group;
when X is present1Selected from chlorine, X3When selected from methanesulfonyl, X2Is not thiazolyl;
Z1is selected from C1-C6Alkyl radical, C3-C6Cycloalkyl radical, C3-C6Alkenyl radical, C3-C6Alkynyl or phenyl;
Z2selected from H, C1-C6Alkyl radical, C1-C6Haloalkyl, phenyl, or phenyl substituted with one or more substituents selected from: halogen, cyano, nitro, C1-C6Alkyl radical, C3-C6Cycloalkyl or C1-C6A haloalkyl group;
R1to R5Each independently selected from hydrogen, hydroxyl, cyano, nitro, halogen, phenyl and C1-C6Alkyl radical, C2-C6Alkenyl radical, C2-C6Alkynyl, C1-C6Alkoxy or benzyloxy; wherein
R1And R2A benzene ring or a 5-to 7-membered aliphatic heterocyclic ring having 1 to 3 hetero atoms which may be combined together with the carbon atoms on the benzene ring to which they are bonded;
R2and R3A benzene ring or a 5-to 7-membered aliphatic heterocyclic ring having 1 to 3 hetero atoms which may be combined together with the carbon atoms on the benzene ring to which they are bonded;
stereoisomers of the compounds of the general formula I.
4. A compound according to claim 3, wherein in formula I:
X1selected from hydrogen, cyano, nitro, halogen, C1-C3Alkylsulfonyl radical, C1-C3Alkyl radical, C1-C3A haloalkyl group;
w is selected from N or CX2；
X2Selected from hydrogen, halogen, C1-C3Alkyl radical, C1-C3Haloalkyl, C3-C6Cycloalkyl radical, C3-C6Cycloalkyl radical C1-C3Alkyl radical, C3-C6Halogenocycloalkyl C1-C3Alkyl radical, Y1Oxy radical, Y1Thio radical, Y1Y2Amino group, Y1Sulfonyl radical, Y1Oxy radical C1-C3Alkyl radical, Y1Thio radical C1-C3Alkyl radical, Y1Y2Amino group C1-C3Alkyl radical, Y1Sulfonyl radical C1-C3Alkyl, COY1、COOY1、OCOOY1、NY1COOY2、C(O)N Y1Y2、NY1C(O)N Y1Y2、NY1SO2Y2、NY1COY2、OSO2Y1、CH＝NOY1、C1-C6alkyl-CH-NOY1Phenyl which is unsubstituted or substituted by 1 to 5 substituents, a 5-to 7-membered aliphatic heterocyclic ring containing 1 to 4 hetero atoms, a 5-to 7-membered aromatic heterocyclic ring containing 1 to 4 hetero atoms, a 5-to 7-membered aliphatic heterocyclic ring containing 1 to 4 hetero atoms C1-C3Alkyl or 5-to 7-membered heteroaromatic ring C containing 1 to 4 heteroatoms1-C3Alkyl, the following substituents are selected from nitro, halogen and C1-C3Alkyl radical, C1-C3Haloalkyl, C1-C3Alkoxy radical, C3-C6Cycloalkyl or C3-C6A cycloalkoxy group;
Y1、Y2each independently selected from C1-C6Alkyl radical, C1-C6Haloalkyl, C3-C6Cycloalkyl radical, C3-C6Cycloalkyl radical C1-C6Alkyl radical, C1-C6Alkoxy radical C1-C6Alkyl, phenyl unsubstituted or substituted by 1 to 5 substituents, a 5-to 7-membered aliphatic heterocyclic ring containing 1 to 4 hetero atoms, a 5-to 7-membered aromatic heterocyclic ring containing 1 to 4 hetero atoms, a 5-to 7-membered aliphatic heterocyclic ring containing 1 to 4 hetero atoms C1-C6Alkyl or 5-to 7-membered heteroaromatic ring C containing 1 to 4 heteroatoms1-C6Alkyl, the following substituents are selected from nitro, halogen and C1-C6Alkyl radical, C1-C6Haloalkyl, C1-C6Alkoxy radical, C1-C6Haloalkoxy, C3-C6Cycloalkyl or C3-C6A cycloalkoxy group;
X3selected from hydrogen, cyano, halogen, C1-C3Alkylsulfonyl radical, C1-C3Alkyl radical, C1-C3A haloalkyl group;
when X is present1Selected from chlorine, X3When selected from methanesulfonyl, X2Is not thiazolyl;
Z1is selected from C1-C3Alkyl or phenyl;
Z2selected from H, C1-C3Alkyl radical, C1-C3Haloalkyl or C3-C6A cycloalkyl group;
R1to R5Each independently selected from hydrogen, hydroxy, cyano, nitro, halogen, phenyl, methyl, ethyl, propyl, ethenyl, propenyl, ethynyl, propynyl, methoxy, ethoxy, benzyloxy, trifluoromethyl or trifluoromethoxy;
R1and R2Selected from the group consisting of benzene rings together with the carbon atoms of the benzene rings to which they are attached;
R2and R3Selected from the group consisting of a benzene ring, a1, 3-dioxane ring or a1, 4-dioxane ring together with the carbon atoms of the benzene ring to which they are attached;
trans stereoisomers of the compounds of formula I above.
5. Use of a compound of formula I according to claim 1, characterized in that: the compound of the general formula I, the stereoisomer thereof or the agriculturally acceptable salt of the compound of the general formula I and the isomer thereof are applied to controlling weeds.
6. A herbicidal composition characterized by: the herbicidal composition is an active substance and an agriculturally acceptable carrier, and the active ingredient is a compound containing the compound shown in the general formula I and a stereoisomer thereof as claimed in claim 1, or an agriculturally acceptable salt of the compound shown in the general formula I and the stereoisomer thereof; the weight percentage of the active components in the composition is 1-99%.
7. A method of controlling weeds with a composition according to claim 5, wherein: applying a herbicidally effective dose of the herbicidal composition of claim 5 to the weeds or to a growth medium or locus of the weeds.
CN201910950256.1A 2019-10-08 2019-10-08 Cinnamate compound and application thereof Active CN112624974B (en)

Priority Applications (9)

Application Number Priority Date Filing Date Title
CN201910950256.1A CN112624974B (en) 2019-10-08 2019-10-08 Cinnamate compound and application thereof
CN202080059844.7A CN114787134B (en) 2019-10-08 2020-09-30 Carboxylic ester compound containing alkene and application thereof
US17/754,670 US20230157290A1 (en) 2019-10-08 2020-09-30 Alkene-containing carboxylate compound and use thereof
MX2022004231A MX2022004231A (en) 2019-10-08 2020-09-30 Alkene-containing carboxylate compound and use thereof.
CA3154030A CA3154030C (en) 2019-10-08 2020-09-30 Alkene-containing carboxylic ester compound and application thereof
BR112022006856A BR112022006856A2 (en) 2019-10-08 2020-09-30 CARBOXYLATE COMPOUND CONTAINING ALKENE AND ITS USE
PCT/CN2020/119168 WO2021068820A1 (en) 2019-10-08 2020-09-30 Alkene-containing carboxylate compound and use thereof
EP20874773.3A EP4043441A4 (en) 2019-10-08 2020-09-30 Alkene-containing carboxylate compound and use thereof
AU2020363069A AU2020363069B2 (en) 2019-10-08 2020-09-30 Alkene-containing carboxylate compound and use thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910950256.1A CN112624974B (en) 2019-10-08 2019-10-08 Cinnamate compound and application thereof

Publications (2)

Publication Number Publication Date
CN112624974A true CN112624974A (en) 2021-04-09
CN112624974B CN112624974B (en) 2024-01-30

Family

ID=75283049

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910950256.1A Active CN112624974B (en) 2019-10-08 2019-10-08 Cinnamate compound and application thereof

Country Status (1)

Country Link
CN (1) CN112624974B (en)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4063925A (en) * 1974-03-28 1977-12-20 Sankyo Company Limited Herbicidal compositions
US4643757A (en) * 1985-05-20 1987-02-17 Nissan Chemical Industries, Ltd. Herbicidal 4-benzoyl-1-methyl-5-hydroxypyrazoles
WO2000003993A1 (en) * 1998-07-16 2000-01-27 Ishihara Sangyo Kaisha Ltd. Pyrazole-type compounds, process for producing the same and herbicides containing the same
CN1250447A (en) * 1997-01-17 2000-04-12 巴斯福股份公司 4-(3-heterocyclyl-1-benzoyl) pyrazoles and their use as herbicides

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4063925A (en) * 1974-03-28 1977-12-20 Sankyo Company Limited Herbicidal compositions
US4643757A (en) * 1985-05-20 1987-02-17 Nissan Chemical Industries, Ltd. Herbicidal 4-benzoyl-1-methyl-5-hydroxypyrazoles
CN1250447A (en) * 1997-01-17 2000-04-12 巴斯福股份公司 4-(3-heterocyclyl-1-benzoyl) pyrazoles and their use as herbicides
WO2000003993A1 (en) * 1998-07-16 2000-01-27 Ishihara Sangyo Kaisha Ltd. Pyrazole-type compounds, process for producing the same and herbicides containing the same

Also Published As

Publication number Publication date
CN112624974B (en) 2024-01-30

Similar Documents

Publication Publication Date Title
CN112624989B (en) Amide compound and application thereof
CN111303126B (en) Pyrazole amide compound and application thereof as herbicide
CN115279738B (en) Pyrazole carboxylic ester compound and application thereof
CN113387926B (en) Heterocyclic carboxylic ester compound and application thereof as herbicide
CN112624973B (en) Carboxylic acid ester compound and application thereof
CN112624974B (en) Cinnamate compound and application thereof
CN112390727B (en) Oxime carboxylate compound and application thereof
CN111303062B (en) Benzamide compound and application thereof as herbicide
CN113387888B (en) Cycloolefin carboxylic ester compound and application thereof
CN109553615B (en) Pyrimidine salt compound and application thereof
CN112939958B (en) Condensed ring acyl compound and application thereof
CN112624991A (en) Cinnamide compound and application thereof
CN112939953B (en) Benzamide compound and application thereof as herbicide
JP2833817B2 (en) 4-Ethyl-3- (substituted phenyl) -1- (3-trifluoromethylphenyl) -2-pyrrolidinone derivative, process for producing the same, and herbicide containing these as active ingredients
CN113831299A (en) Benzoate compound and application thereof
CN109867624B (en) 3-fluoro-5-chloropyridinyloxy phenoxypropanamide compound and application thereof
CN113387900A (en) Cycloalkenylamide compound and application thereof
CN116120234A (en) Benzoyl pyrazole compound and application thereof
CN114787134B (en) Carboxylic ester compound containing alkene and application thereof
KR0149513B1 (en) Uracil derivatives and pesticides containing the same as active ingredient
CN114787138B (en) Amide compound containing alkene and application thereof
CN116120235A (en) Phenoxyacetyl pyrazole compound and application thereof
CN116217487A (en) Benzoyl pyrazole compound and application thereof
CN113831298A (en) Optically active carboxylic ester compound and application thereof
JPH0667925B2 (en) Pyridylpyrimidine derivative and plant disease controlling agent containing the same

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
TA01 Transfer of patent application right

Effective date of registration: 20210609

Address after: 110021 Shenyang Liaodong Road, Tiexi District, Shenyang, Liaoning 8-1

Applicant after: SHENYANG SINOCHEM AGROCHEMICALS R&D Co.,Ltd.

Applicant after: JIANGSU YANGNONG CHEMICAL Co.,Ltd.

Address before: 110021 Shenyang Liaodong Road, Tiexi District, Shenyang, Liaoning 8-1

Applicant before: SHENYANG SINOCHEM AGROCHEMICALS R&D Co.,Ltd.

TA01 Transfer of patent application right
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant