CN112624974B - Cinnamate compound and application thereof - Google Patents

Cinnamate compound and application thereof Download PDF

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Publication number
CN112624974B
CN112624974B CN201910950256.1A CN201910950256A CN112624974B CN 112624974 B CN112624974 B CN 112624974B CN 201910950256 A CN201910950256 A CN 201910950256A CN 112624974 B CN112624974 B CN 112624974B
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alkyl
compound
cycloalkyl
alkoxy
compounds
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CN112624974A (en
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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
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Jiangsu Yangnong Chemical Co Ltd
Shenyang Sinochem Agrochemicals R&D Co Ltd
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Jiangsu Yangnong Chemical Co Ltd
Shenyang Sinochem Agrochemicals R&D Co Ltd
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Application filed by Jiangsu Yangnong Chemical Co Ltd, Shenyang Sinochem Agrochemicals R&D Co Ltd filed Critical Jiangsu Yangnong Chemical Co Ltd
Priority to PCT/CN2020/119168 priority patent/WO2021068820A1/en
Priority to US17/754,670 priority patent/US20230157290A1/en
Priority to EP20874773.3A priority patent/EP4043441A4/en
Priority to AU2020363069A priority patent/AU2020363069B2/en
Priority to BR112022006856A priority patent/BR112022006856A2/en
Priority to CN202080059844.7A priority patent/CN114787134B/en
Priority to CA3154030A priority patent/CA3154030C/en
Priority to MX2022004231A priority patent/MX2022004231A/en
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    • 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

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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)

Abstract

The invention discloses a cinnamyl carboxylate compound and application of agriculturally acceptable salts thereof as herbicides, wherein the compound is shown in a general formula (I):

Description

Cinnamate compound and application thereof
Technical Field
The invention belongs to the field of herbicides. In particular to a cinnamate compound and application thereof.
Background
Due to succession and transition of weed populations and generation and rapid development of drug resistance to chemical pesticides, people continuously strengthen awareness of ecological environment protection, awareness of chemical pesticide pollution and pesticide influence on non-target organisms and importance of homing problems in pesticide ecological environments are continuously improved. With the progressive decrease in the area of cultivated land, the increasing population and the increasing demand for foodstuffs, people are forced to rapidly develop agricultural production technologies, improve and perfect cultivation systems, and there is a continuing need to invent new and improved herbicidal compounds and compositions.
DE 2513750A1 reports that certain benzoylpyrazoles have herbicidal activity, for example compound No. 79 (KC) of them:
the cinnamate compounds shown in the invention are not disclosed.
Disclosure of Invention
The invention aims to provide a cinnamyl carboxylate compound with novel structure and safety to crops and application of the cinnamyl carboxylate compound as herbicide.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
a cinnamate compound is shown in a general formula I:
wherein:
X 1 selected from hydrogen, cyano, nitro, halogen, C 1 -C 6 Alkylsulfonyl, C 1 -C 6 Haloalkyl sulfonyl, C 1 -C 6 Alkylsulfinyl, C 1 -C 6 Haloalkyl sulfinyl, C 1 -C 6 Alkylthio, C 1 -C 6 Haloalkylthio, C 1 -C 6 Alkyl, C 1 -C 6 Haloalkyl, C 1 -C 6 Alkoxy, C 1 -C 6 Haloalkoxy, C 1 -C 6 Alkoxy C 1 -C 3 Alkyl, C 1 -C 6 Alkoxy C 1 -C 3 Alkoxy, C 1 -C 6 Alkoxy C 1 -C 3 Alkoxy C 1 -C 3 Alkyl, C 3 -C 6 Cycloalkyl, C 3 -C 6 Cycloalkyl C 1 -C 3 Alkyl, C 3 -C 6 Cycloalkyl C 1 -C 3 Alkoxy, C 3 -C 6 Cycloalkyl oxy, C 2 -C 6 Alkenyl, C 2 -C 6 Alkynyl, phenyl which is unsubstituted or substituted by 1 to 5 substituents 2 -C 6 Alkenyl sulfonyl, C 2 -C 6 Alkynyl sulfonyl, phenylsulfonyl, C 2 -C 6 Alkenyloxy, C 2 -C 6 Alkynyloxy, phenyloxy, C 2 -C 6 Alkenylthio, C 2 -C 6 Alkynyl thio, phenylthio, 5-7 membered alicyclic ring having 1 to 4 hetero atoms, 5-7 membered aromatic heterocyclic ring having 1 to 4 hetero atoms, 5-7 membered alicyclic heterocyclic ring having 1 to 4 hetero atoms C 1 -C 6 Alkyl or 5-to 7-membered aromatic heterocyclic C containing 1-4 hetero atoms 1 -C 6 Alkyl, the substituents are selected from nitro, halogen and C 1 -C 6 Alkyl, C 1 -C 6 Haloalkyl, C 1 -C 6 Alkoxy, C 1 -C 6 Haloalkoxy or C 3 -C 6 Cycloalkyl;
w is selected from N or CX 2 ；
X 2 Selected from hydrogen, cyano, nitro, halogen, C 1 -C 6 Alkyl, C 1 -C 6 Haloalkyl, C 3 -C 6 Cycloalkyl, C 3 -C 6 Cycloalkyl C 1 -C 6 Alkyl, C 3 -C 6 Halogenated cycloalkyl C 1 -C 6 Alkyl, Y 1 Oxy, Y 1 Thio, Y 1 Y 2 Amino, Y 1 Sulfinyl group, Y 1 Sulfonyl, Y 1 Oxy C 1 -C 6 Alkyl, Y 1 Thio C 1 -C 6 Alkyl, Y 1 Y 2 Amino C 1 -C 6 Alkyl, Y 1 Sulfinyl C 1 -C 6 Alkyl, Y 1 Sulfonyl C 1 -C 6 Alkyl, COY 1 、COOY 1 、OCOOY 1 、NY 1 COOY 2 、C(O)N Y 1 Y 2 、NY 1 C(O)N Y 1 Y 2 、OC(O)NY 1 Y 2 、C(O)N(Y 1 )OY 2 、NY 1 SO 2 Y 2 、NY 1 COY 2 、OSO 2 Y 1 、CH＝NOY 1 、C 1 -C 6 Alkyl-ch= NOY 1 、C 1 -C 6 alkyl-O-n=cy 1 Y 2 Phenyl which is unsubstituted or substituted by 1 to 5 substituents, 5 to 7 membered alicyclic ring containing 1 to 4 hetero atoms, 5 to 7 membered aromatic heterocyclic ring containing 1 to 4 hetero atoms, 5 to 7 membered alicyclic heterocyclic ring C containing 1 to 4 hetero atoms 1 -C 6 Alkyl or 5-to 7-membered aromatic heterocyclic C containing 1-4 hetero atoms 1 -C 6 Alkyl, the substituents are selected from nitro, halogen and C 1 -C 6 Alkyl, C 1 -C 6 Haloalkyl, C 1 -C 6 Alkoxy, C 1 -C 6 Haloalkoxy, C 3 -C 6 Cycloalkyl, C 3 -C 6 Cycloalkoxy radicals C 2 -C 6 Alkenyl, C 2 -C 6 Alkynyl, phenyl or halophenyl;
Y 1 、Y 2 independently selected from C 1 -C 6 Alkyl, C 1 -C 6 Haloalkyl, C 3 -C 6 Cycloalkyl, C 3 -C 6 Cycloalkyl C 1 -C 6 Alkyl, C 1 -C 6 Alkoxy C 1 -C 6 Alkyl, phenyl which is unsubstituted or substituted by 1 to 5 substituents, 5 to 7 membered alicyclic ring containing 1 to 4 hetero atoms, 5 to 7 membered aromatic heterocyclic ring containing 1 to 4 hetero atoms, 5 to 7 membered alicyclic heterocyclic ring C containing 1 to 4 hetero atoms 1 -C 6 Alkyl or 5-to 7-membered aromatic heterocyclic C containing 1-4 hetero atoms 1 -C 6 Alkyl, the substituents are selected from nitro, halogen and C 1 -C 6 Alkyl, C 1 -C 6 Haloalkyl, C 1 -C 6 Alkoxy, C 1 -C 6 Haloalkoxy, C 3 -C 6 Cycloalkyl, C 3 -C 6 Cycloalkoxy radicals C 2 -C 6 Alkenyl, C 2 -C 6 Alkynyl, phenyl or halophenyl;
X 3 selected from hydrogen, cyano, halogen, C 1 -C 6 Alkylsulfonyl, C 1 -C 6 Haloalkyl sulfonyl, C 1 -C 6 Alkylsulfinyl, C 1 -C 6 Haloalkyl sulfinyl, C 1 -C 6 Alkylthio, C 1 -C 6 Haloalkylthio, C 1 -C 6 Alkyl, C 1 -C 6 Haloalkyl, C 1 -C 6 Alkoxy, C 1 -C 6 Haloalkoxy, C 1 -C 6 Alkoxy C 1 -C 3 Alkyl, C 1 -C 6 Alkoxy C 1 -C 3 Alkoxy, C 1 -C 6 Alkoxy C 1 -C 3 Alkoxy C 1 -C 3 Alkyl, C 3 -C 6 Cycloalkyl, C 3 -C 6 Cycloalkyl C 1 -C 3 Alkyl, C 3 -C 6 Cycloalkyl C 1 -C 3 Alkoxy, C 3 -C 6 Cycloalkyl oxy, C 2 -C 6 Alkenyl, C 2 -C 6 Alkynyl groupPhenyl, C, unsubstituted or substituted by 1 to 5 substituents 2 -C 6 Alkenyl sulfonyl, C 2 -C 6 Alkynyl sulfonyl, phenylsulfonyl, C 2 -C 6 Alkenyloxy, C 2 -C 6 Alkynyloxy, phenyloxy, C 2 -C 6 Alkenylthio, C 2 -C 6 Alkynyl thio, phenylthio, 5-7 membered alicyclic ring having 1 to 4 hetero atoms, 5-7 membered aromatic heterocyclic ring having 1 to 4 hetero atoms, 5-7 membered alicyclic heterocyclic ring having 1 to 4 hetero atoms C 1 -C 6 Alkyl or 5-to 7-membered aromatic heterocyclic C containing 1-4 hetero atoms 1 -C 6 Alkyl, the substituents are selected from nitro, halogen and C 1 -C 6 Alkyl, C 1 -C 6 Haloalkyl, C 1 -C 6 Alkoxy, C 1 -C 6 Haloalkoxy or C 3 -C 6 Cycloalkyl;
when X is 1 Selected from chlorine, X 3 X is selected from methylsulfonyl 2 Is not thiazolyl;
Z 1 selected from C 1 -C 6 Alkyl, C 3 -C 6 Cycloalkyl, C 3 -C 6 Cycloalkyl C 1 -C 6 Alkyl, C 3 -C 6 Alkenyl, C 3 -C 6 Alkynyl, C 1 -C 6 Alkylsulfonyl C 1 -C 6 Alkyl or phenyl;
Z 2 selected from H, C 1 -C 6 Alkyl, C 3 -C 6 Cycloalkyl, C 1 -C 6 Haloalkyl, phenyl unsubstituted or substituted with at least one substituent as described below; the following substituents are selected from: halogen, cyano, nitro, C 1 -C 6 Alkyl, C 3 -C 6 Cycloalkyl or C 1 -C 6 A haloalkyl group;
R 1 to R 5 Independently selected from hydrogen, cyano, nitro, halogen, phenyl, C 1 -C 6 Alkyl, C 1 -C 6 Haloalkyl, C 2 -C 6 Alkenyl, C 2 -C 6 Haloalkenyl, C 2 -C 6 Alkynyl, C 2 -C 6 Haloalkynyl, C 1 -C 6 Alkoxy, C 1 -C 6 Haloalkoxy, C 1 -C 6 Alkylthio or benzyloxy;
wherein R is 1 And R is R 2 Can form benzene ring, 5-7 membered aliphatic heterocyclic ring containing 1-3 hetero atoms or 5-7 membered aromatic heterocyclic ring containing 1-3 hetero atoms together with carbon atoms on the benzene ring to which they are attached;
R 2 and R is R 3 Can form benzene ring, 5-7 membered aliphatic heterocyclic ring with 1-3 hetero atoms or 5-7 membered aromatic heterocyclic ring with 1-3 hetero atoms together with carbon atoms on the benzene ring;
stereoisomers of the compounds of formula I; or, the compound of formula I and its isomer thereof are agriculturally acceptable salts.
Preference is given to the compounds described in the general formula I:
X 1 selected from hydrogen, cyano, nitro, halogen, C 1 -C 6 Alkylsulfonyl, C 1 -C 6 Alkylsulfinyl, C 1 -C 6 Alkylthio, C 1 -C 6 Haloalkylthio, C 1 -C 6 Alkyl, C 1 -C 6 Haloalkyl, C 1 -C 6 Alkoxy, C 1 -C 6 Alkoxy C 1 -C 3 Alkyl, C 1 -C 6 Alkoxy C 1 -C 3 Alkoxy, C 1 -C 6 Alkoxy C 1 -C 3 Alkoxy C 1 -C 3 Alkyl, C 3 -C 6 Cycloalkyl, C 3 -C 6 Cycloalkyl C 1 -C 3 Alkyl, C 3 -C 6 Cycloalkyl C 1 -C 3 Alkoxy, C 3 -C 6 Cycloalkyl oxy, C 2 -C 6 Alkenyl, C 2 -C 6 Alkynyl, phenyl which is unsubstituted or substituted by 1 to 5 substituents, phenylsulfonyl, C 2 -C 6 Alkenyloxy, phenyloxy, 5-7 membered alicyclic ring containing 1-4 hetero atoms, 5-7 membered aromatic ring containing 1-4 hetero atoms, the substituents being selected from nitro, halogen, C 1 -C 6 Alkyl, C 1 -C 6 Haloalkyl, C 1 -C 6 Alkoxy, C 1 -C 6 Haloalkoxy or C 3 -C 6 Cycloalkyl;
w is selected from N or CX 2 ；
X 2 Selected from hydrogen, cyano, nitro, halogen, C 1 -C 6 Alkyl, C 1 -C 6 Haloalkyl, C 3 -C 6 Cycloalkyl, C 3 -C 6 Cycloalkyl C 1 -C 6 Alkyl, C 3 -C 6 Halogenated cycloalkyl C 1 -C 6 Alkyl, Y 1 Oxy, Y 1 Thio, Y 1 Y 2 Amino, Y 1 Sulfinyl group, Y 1 Sulfonyl, Y 1 Oxy C 1 -C 6 Alkyl, Y 1 Thio C 1 -C 6 Alkyl, Y 1 Y 2 Amino C 1 -C 6 Alkyl, Y 1 Sulfinyl C 1 -C 6 Alkyl, Y 1 Sulfonyl C 1 -C 6 Alkyl, COY 1 、COOY 1 、OCOOY 1 、NY 1 COOY 2 、C(O)N Y 1 Y 2 、NY 1 C(O)N Y 1 Y 2 、OC(O)NY 1 Y 2 、C(O)N(Y 1 )OY 2 、NY 1 SO 2 Y 2 、NY 1 COY 2 、OSO 2 Y 1 、CH＝NOY 1 、C 1 -C 6 Alkyl-ch= NOY 1 、C 1 -C 6 alkyl-O-n=cy 1 Y 2 Phenyl which is unsubstituted or substituted by 1 to 5 substituents, 5 to 7 membered alicyclic ring containing 1 to 4 hetero atoms, 5 to 7 membered aromatic heterocyclic ring containing 1 to 4 hetero atoms, 5 to 7 membered alicyclic heterocyclic ring C containing 1 to 4 hetero atoms 1 -C 6 Alkyl or 5-to 7-membered aromatic heterocyclic C containing 1-4 hetero atoms 1 -C 6 Alkyl, the substituents are selected from nitro, halogen and C 1 -C 6 Alkyl, C 1 -C 6 Haloalkyl, C 1 -C 6 Alkoxy, C 1 -C 6 Haloalkoxy, C 3 -C 6 Cycloalkyl, C 3 -C 6 A cycloalkoxy group;
Y 1 、Y 2 independently selected from C 1 -C 6 Alkyl, C 1 -C 6 Haloalkyl, C 3 -C 6 Cycloalkyl, C 3 -C 6 Cycloalkyl C 1 -C 6 Alkyl, C 1 -C 6 Alkoxy C 1 -C 6 Alkyl, phenyl which is unsubstituted or substituted by 1 to 5 substituents, 5 to 7 membered alicyclic ring containing 1 to 4 hetero atoms, 5 to 7 membered aromatic heterocyclic ring containing 1 to 4 hetero atoms, 5 to 7 membered alicyclic heterocyclic ring C containing 1 to 4 hetero atoms 1 -C 6 Alkyl or 5-to 7-membered aromatic heterocyclic C containing 1-4 hetero atoms 1 -C 6 Alkyl, the substituents are selected from nitro, halogen and C 1 -C 6 Alkyl, C 1 -C 6 Haloalkyl, C 1 -C 6 Alkoxy, C 1 -C 6 Haloalkoxy, C 3 -C 6 Cycloalkyl, C 3 -C 6 A cycloalkoxy group;
X 3 selected from hydrogen, cyano, halogen, C 1 -C 6 Alkylsulfonyl, C 1 -C 6 Alkylsulfinyl, C 1 -C 6 Alkylthio, C 1 -C 6 Haloalkylthio, C 1 -C 6 Alkyl, C 1 -C 6 Haloalkyl, C 1 -C 6 Alkoxy, C 1 -C 6 Alkoxy C 1 -C 3 Alkyl, C 1 -C 6 Alkoxy C 1 -C 3 Alkoxy, C 1 -C 6 Alkoxy C 1 -C 3 Alkoxy C 1 -C 3 Alkyl, C 3 -C 6 Cycloalkyl, C 3 -C 6 Cycloalkyl C 1 -C 3 Alkyl, C 3 -C 6 Cycloalkyl C 1 -C 3 Alkoxy, C 3 -C 6 Cycloalkyl oxy, C 2 -C 6 Alkenyl, C 2 -C 6 Alkynyl, phenyl which is unsubstituted or substituted by 1 to 5 substituents, phenylsulfonyl, C 2 -C 6 Alkenyloxy, phenyloxy, containing 1-4 hetero atoms5-7 membered alicyclic heterocyclic ring of (2), 5-7 membered aromatic heterocyclic ring containing 1-4 hetero atoms, the substituent is selected from nitro, halogen and C 1 -C 6 Alkyl, C 1 -C 6 Haloalkyl, C 1 -C 6 Alkoxy, C 1 -C 6 Haloalkoxy or C 3 -C 6 Cycloalkyl;
when X is 1 Selected from chlorine, X 3 X is selected from methylsulfonyl 2 Is not thiazolyl;
Z 1 selected from C 1 -C 6 Alkyl, C 3 -C 6 Cycloalkyl, C 3 -C 6 Cycloalkyl C 1 -C 6 Alkyl, C 3 -C 6 Alkenyl, C 3 -C 6 Alkynyl or phenyl;
Z 2 selected from H, C 1 -C 6 Alkyl, C 1 -C 6 Haloalkyl, phenyl unsubstituted or substituted with at least one substituent as described below; the following substituents are selected from: halogen, cyano, nitro, C 1 -C 6 Alkyl, C 3 -C 6 Cycloalkyl or C 1 -C 6 A haloalkyl group;
R 1 to R 5 Independently selected from hydrogen, cyano, nitro, halogen, phenyl, C 1 -C 6 Alkyl, C 2 -C 6 Alkenyl, C 2 -C 6 Alkynyl, C 1 -C 6 Alkoxy, C 1 -C 6 Alkylthio or benzyloxy;
wherein R is 1 And R is R 2 Can form benzene ring, 5-7 membered aliphatic heterocyclic ring containing 1-3 hetero atoms or 5-7 membered aromatic heterocyclic ring containing 1-3 hetero atoms together with carbon atoms on the benzene ring to which they are attached;
R 2 and R is R 3 Can form benzene ring, 5-7 membered aliphatic heterocyclic ring with 1-3 hetero atoms or 5-7 membered aromatic heterocyclic ring with 1-3 hetero atoms together with carbon atoms on the benzene ring;
stereoisomers of the compounds of formula I described above.
Further preferred are said compounds of formula I:
X 1 selected from hydrogen, cyano, nitro, halogen, C 1 -C 3 Alkylsulfonyl, C 1 -C 3 Alkylsulfinyl, C 1 -C 3 Alkylthio, C 1 -C 3 Haloalkylthio, C 1 -C 3 Alkyl, C 1 -C 3 Haloalkyl, C 1 -C 3 Alkoxy, C 1 -C 3 Alkoxy C 1 -C 3 Alkyl, C 1 -C 3 Alkoxy C 1 -C 3 Alkoxy, C 1 -C 3 Alkoxy C 1 -C 3 Alkoxy C 1 -C 3 Alkyl, C 3 -C 6 Cycloalkyl or C 3 -C 6 Cycloalkyl oxy;
w is selected from N or CX 2 ；
X 2 Selected from hydrogen, cyano, nitro, halogen, C 1 -C 3 Alkyl, C 1 -C 3 Haloalkyl, C 3 -C 6 Cycloalkyl, C 3 -C 6 Cycloalkyl C 1 -C 3 Alkyl, C 3 -C 6 Halogenated cycloalkyl C 1 -C 3 Alkyl, Y 1 Oxy, Y 1 Thio, Y 1 Y 2 Amino, Y 1 Sulfinyl group, Y 1 Sulfonyl, Y 1 Oxy C 1 -C 3 Alkyl, Y 1 Thio C 1 -C 3 Alkyl, Y 1 Y 2 Amino C 1 -C 3 Alkyl, Y 1 Sulfinyl C 1 -C 3 Alkyl, Y 1 Sulfonyl C 1 -C 3 Alkyl, COY 1 、COOY 1 、OCOOY 1 、NY 1 COOY 2 、C(O)N Y 1 Y 2 、NY 1 C(O)N Y 1 Y 2 、OC(O)N Y 1 Y 2 、NY 1 SO 2 Y 2 、NY 1 COY 2 、OSO 2 Y 1 、CH＝NOY 1 、C 1 -C 6 Alkyl-ch= NOY 1 Phenyl which is unsubstituted or substituted by 1 to 5 substituents, 5 to 7 membered alicyclic ring containing 1 to 4 hetero atoms, 5 to 7 membered aromatic ring containing 1 to 4 hetero atoms5-7 membered alicyclic heterocyclic C containing 1-4 hetero atoms 1 -C 3 Alkyl or 5-to 7-membered aromatic heterocyclic C containing 1-4 hetero atoms 1 -C 3 Alkyl, the substituents are selected from nitro, halogen and C 1 -C 3 Alkyl, C 1 -C 3 Haloalkyl, C 1 -C 3 Alkoxy, C 3 -C 6 Cycloalkyl or C 3 -C 6 A cycloalkoxy group;
Y 1 、Y 2 independently selected from C 1 -C 6 Alkyl, C 1 -C 6 Haloalkyl, C 3 -C 6 Cycloalkyl, C 3 -C 6 Cycloalkyl C 1 -C 6 Alkyl, C 1 -C 6 Alkoxy C 1 -C 6 Alkyl, phenyl which is unsubstituted or substituted by 1 to 5 substituents, 5 to 7 membered alicyclic ring containing 1 to 4 hetero atoms, 5 to 7 membered aromatic heterocyclic ring containing 1 to 4 hetero atoms, 5 to 7 membered alicyclic heterocyclic ring C containing 1 to 4 hetero atoms 1 -C 6 Alkyl or 5-to 7-membered aromatic heterocyclic C containing 1-4 hetero atoms 1 -C 6 Alkyl, the substituents are selected from nitro, halogen and C 1 -C 6 Alkyl, C 1 -C 6 Haloalkyl, C 1 -C 6 Alkoxy, C 1 -C 6 Haloalkoxy, C 3 -C 6 Cycloalkyl or C 3 -C 6 A cycloalkoxy group;
X 3 selected from hydrogen, cyano, halogen, C 1 -C 3 Alkylsulfonyl, C 1 -C 3 Alkylsulfinyl, C 1 -C 3 Alkylthio, C 1 -C 3 Haloalkylthio, C 1 -C 3 Alkyl, C 1 -C 3 Haloalkyl, C 1 -C 3 Alkoxy, C 1 -C 3 Alkoxy C 1 -C 3 Alkyl, C 1 -C 3 Alkoxy C 1 -C 3 Alkoxy, C 1 -C 3 Alkoxy C 1 -C 3 Alkoxy C 1 -C 3 Alkyl, C 3 -C 6 Cycloalkyl or C 3 -C 6 Cycloalkyl oxy;
when X is 1 Selected from chlorine, X 3 X is selected from methylsulfonyl 2 Is not thiazolyl;
Z 1 selected from C 1 -C 6 Alkyl, C 3 -C 6 Cycloalkyl, C 3 -C 6 Alkenyl, C 3 -C 6 Alkynyl or phenyl;
Z 2 selected from H, C 1 -C 6 Alkyl, C 1 -C 6 Haloalkyl, phenyl or phenyl substituted with one or more substituents selected from the group consisting of: halogen, cyano, nitro, C 1 -C 6 Alkyl, C 3 -C 6 Cycloalkyl or C 1 -C 6 A haloalkyl group;
R 1 to R 5 Independently selected from hydrogen, hydroxy, cyano, nitro, halogen, phenyl, C 1 -C 6 Alkyl, C 2 -C 6 Alkenyl, C 2 -C 6 Alkynyl, C 1 -C 6 Alkoxy or benzyloxy; wherein the method comprises the steps of
R 1 And R is R 2 Benzene rings or 5-7 membered alicyclic heterocyclic rings of 1-3 hetero atoms which may be constituted together with the carbon atoms on the benzene ring to which they are attached;
R 2 and R is R 3 Benzene rings or 5-7 membered alicyclic heterocyclic rings of 1-3 hetero atoms which may be constituted together with the carbon atoms on the benzene ring to which they are attached;
stereoisomers of the compounds of formula I described above.
In a further preferred said compound, formula I:
X 1 selected from hydrogen, cyano, nitro, halogen, C 1 -C 3 Alkylsulfonyl, C 1 -C 3 Alkyl, C 1 -C 3 A haloalkyl group;
w is selected from N or CX 2 ；
X 2 Selected from hydrogen, halogen, C 1 -C 3 Alkyl, C 1 -C 3 Haloalkyl, C 3 -C 6 Cycloalkyl, C 3 -C 6 Cycloalkyl C 1 -C 3 Alkyl, C 3 -C 6 Halogenated cycloalkyl C 1 -C 3 Alkyl, Y 1 Oxy, Y 1 Thio, Y 1 Y 2 Amino, Y 1 Sulfonyl, Y 1 Oxy C 1 -C 3 Alkyl, Y 1 Thio C 1 -C 3 Alkyl, Y 1 Y 2 Amino C 1 -C 3 Alkyl, Y 1 Sulfonyl C 1 -C 3 Alkyl, COY 1 、COOY 1 、OCOOY 1 、NY 1 COOY 2 、C(O)N Y 1 Y 2 、NY 1 C(O)N Y 1 Y 2 、NY 1 SO 2 Y 2 、NY 1 COY 2 、OSO 2 Y 1 、CH＝NOY 1 、C 1 -C 6 Alkyl-ch= NOY 1 Phenyl which is unsubstituted or substituted by 1 to 5 substituents, 5 to 7 membered alicyclic ring containing 1 to 4 hetero atoms, 5 to 7 membered aromatic heterocyclic ring containing 1 to 4 hetero atoms, 5 to 7 membered alicyclic heterocyclic ring C containing 1 to 4 hetero atoms 1 -C 3 Alkyl or 5-to 7-membered aromatic heterocyclic C containing 1-4 hetero atoms 1 -C 3 Alkyl, the substituents are selected from nitro, halogen and C 1 -C 3 Alkyl, C 1 -C 3 Haloalkyl, C 1 -C 3 Alkoxy, C 3 -C 6 Cycloalkyl or C 3 -C 6 A cycloalkoxy group;
Y 1 、Y 2 independently selected from C 1 -C 6 Alkyl, C 1 -C 6 Haloalkyl, C 3 -C 6 Cycloalkyl, C 3 -C 6 Cycloalkyl C 1 -C 6 Alkyl, C 1 -C 6 Alkoxy C 1 -C 6 Alkyl, phenyl which is unsubstituted or substituted by 1 to 5 substituents, 5 to 7 membered alicyclic ring containing 1 to 4 hetero atoms, 5 to 7 membered aromatic heterocyclic ring containing 1 to 4 hetero atoms, 5 to 7 membered alicyclic heterocyclic ring C containing 1 to 4 hetero atoms 1 -C 6 Alkyl or 5-to 7-membered aromatic heterocyclic C containing 1-4 hetero atoms 1 -C 6 Alkyl, the substituents are selected from nitro, halogen and C 1 -C 6 Alkyl, C 1 -C 6 Haloalkyl, C 1 -C 6 Alkoxy, C 1 -C 6 Haloalkoxy, C 3 -C 6 Cycloalkyl or C 3 -C 6 A cycloalkoxy group;
X 3 selected from hydrogen, cyano, halogen, C 1 -C 3 Alkylsulfonyl, C 1 -C 3 Alkyl, C 1 -C 3 A haloalkyl group;
when X is 1 Selected from chlorine, X 3 X is selected from methylsulfonyl 2 Is not thiazolyl;
Z 1 selected from C 1 -C 3 Alkyl or phenyl;
Z 2 selected from H, C 1 -C 3 Alkyl, C 1 -C 3 Haloalkyl or C 3 -C 6 Cycloalkyl;
R 1 to R 5 Each independently selected from hydrogen, hydroxy, cyano, nitro, halogen, phenyl, methyl, ethyl, propyl, ethenyl, propenyl, ethynyl, propynyl, methoxy, ethoxy, benzyloxy, trifluoromethyl or trifluoromethoxy;
R 1 and R is R 2 A benzene ring selected from the group consisting of carbon atoms on the benzene ring to which they are attached;
R 2 and R is R 3 Selected from benzene rings, 1, 3-dioxane rings or 1, 4-dioxane rings which are formed together with carbon atoms on the benzene rings to which they are attached;
the trans stereoisomer of the compound of formula I.
In the definition of compounds of the general formula I given above, the terms used in the collection are defined as follows:
alkyl refers to 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 groups in the form of cyclic chains such as cyclopropyl, methylcyclopropyl, cyclopropylcyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and the like. Alkenyl refers to straight or branched alkenyl groups such as vinyl, 1-propenyl, 2-propenyl, butenyl, pentenyl, hexenyl and the like. Alkynyl refers to straight or branched chain alkynyl groups such as 1-propynyl, 2-propynyl, butynyl, pentynyl, hexynyl and the like. Alkoxy refers to a group having an oxygen atom attached to the end of the alkyl group, such as methoxy, ethoxy, n-propoxy, isopropoxy, tert-butoxy, and the like. By 5-7 membered alicyclic ring containing 1-4 hetero atoms is meant a 5-7 membered heterocyclic ring containing 1-4 hetero atoms without aromatic character, such as ethylene oxide, tetrahydrofuran, imidazolidinone, caprolactam, 1, 3-dioxane ring, 1, 4-dioxane ring, etc. The 5-7 membered aromatic heterocycle having 1 to 4 hetero atoms means a 5-7 membered heterocyclic compound having 1 to 4 hetero atoms and having an aromatic character, such as furan, thiophene, pyrazole, pyridine, etc. Stereoisomers are those in which the hydrogen atom on the carbon-carbon double bond B is on the same side (cis) or on both sides (trans) of the B bond in the general formula I.
The compounds of formula I of the present invention can be prepared by the following method:
the compound of the general formula II and the compound of the general formula III are 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 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 a suitable base is advantageous for 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 referred to: modern pesticides, 10 (5), 16-20,23; 2011.
The preparation method of the compound of the general formula II comprises the following steps:
in the general formula IV, the compound of the general formula II is prepared by reacting 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. 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, etc. Suitable catalysts are selected from sodium carbonate, potassium carbonate, acetone cyanohydrin, azide, quaternary ammonium azide, metal cyanide, DMAP, and the like.
The preparation method of the compound of the general formula IV comprises the following steps:
the compounds of formula V are reacted with compounds of formula VI (prepared by methods described in commercial or reference EP 0240001) in a suitable solvent at a temperature of-10℃to the boiling point of the suitable solvent for 0.5 to 24 hours to give compounds 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 a suitable base is advantageous for 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 corresponding starting carboxylic acid (commercially available) of the compound of formula V is reacted with an acyl halide reagent in a suitable solvent at a temperature of-10℃to the boiling point of the suitable solvent for 0.5 to 48 hours to produce the compound of formula V. The acyl halogenating agent is selected from oxalyl chloride, sulfoxide chloride, phosphorus oxychloride, phosphorus trichloride or phosphorus pentachloride. Suitable solvents are selected from dichloromethane, 1, 2-dichloroethane, hexane, benzene, toluene, acetonitrile, acetic acid, dioxane or liquid acyl halogenating agents and the like.
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 have herbicidal activity and can be used for controlling various weeds in agriculture.
The invention also comprises a weeding composition taking the compound of the general formula I, a stereoisomer thereof or an agriculturally acceptable salt of the compound of 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 composition of the present invention can be applied in the form of various formulations. The compounds of the present invention are typically formulated in a formulation dissolved or dispersed in a carrier for easier dispersion when used as herbicides. For example: these chemicals can be formulated as wettable powders or emulsifiable concentrates and the like. Thus, in these compositions, at least one liquid or solid carrier is added, and it is often necessary to add an appropriate surfactant.
The present invention also provides a method of effecting weed control 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 are growing or to the surface of the growth medium thereof. Preferably, the effective dosage is 1 g to 1000 g per hectare, preferably 10 g to 500 g per hectare. For certain applications, one or more other herbicides may be added to the herbicidal compositions of the present invention, thereby producing additional advantages and effects.
The compounds of the present invention may be used alone or in combination with other known pesticides, fungicides, plant growth regulators or fertilizers.
Compared with the prior art, the cinnamate compound has excellent herbicidal activity and is safe to crops.
It should be understood that various changes and modifications can be made within the scope of the invention as defined in the appended claims.
Detailed Description
The following examples and green test results are provided to further illustrate the invention and are not meant to limit the invention.
Synthesis example
Example 1 synthesis of compound 1-1:
(1) Synthesis of 2-methanesulfonyl-4-trifluoromethylbenzoyl chloride
2-methanesulfonyl-4-trifluoromethylbenzoic acid (30 g, 112 mmol) and toluene (200 ml) were added to the flask, thionyl chloride (53 g, 447 mmol) was slowly added, the mixture was heated to reflux for 4 hours, and the solvent was distilled off under reduced pressure to give 32 g of yellow solid which was directly taken to the next step.
(2) Synthesis of (1, 3-dimethylpyrazol-5-yl) 2-methanesulfonyl-4-trifluoromethylbenzoate
To the reaction flask were added 1, 3-dimethyl-5-hydroxypyrazole (13 g, 112 mmol), 1, 2-dichloroethane (200 ml), triethylamine (34 g, 336 mmol), and a1, 2-dichloroethane solution of step 2-methanesulfonyl-4-trifluoromethylbenzoyl chloride (100 ml) was added dropwise. Stirring at room temperature for 1 hour, evaporating the solvent under reduced pressure, adding ethyl acetate (1000 ml) to the residue, extracting with water (500 ml) in a liquid-separated manner, washing the organic phase with saturated brine (500 ml) in turn, drying over anhydrous magnesium sulfate, evaporating the solvent under reduced pressure, separating the residue by column chromatography to obtain 28 g of yellow solid, yield: 68%.
(3) Synthesis of 1, 3-dimethyl-4- (2-methanesulfonyl-4-trifluoromethylbenzoyl) -5-hydroxypyrazole
2-methanesulfonyl-4-trifluoromethylbenzoic acid (1, 3-dimethylpyrazole-5-yl) ester (6 g, 16.6 mmol), 1, 2-dichloroethane (50 ml), triethylamine (15 g, 148 mmol), acetone cyanohydrin (1 ml) were added to the reaction flask, the mixture was allowed to react at 60℃for 6 hours, cooled to room temperature, water (100 ml) was added to the reaction solution, the layers were separated by shaking sufficiently, the pH of the aqueous phase was adjusted to between 2 and 3 with 20% hydrochloric acid, the aqueous phase was extracted twice with ethyl acetate (100 ml), the organic phase was washed with saturated brine (50 ml) in this order, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure to give 5.4 g of a red oil, yield: 90%.
(4) Synthesis of cinnamoyl chloride
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 slowly added, the mixture was stirred at room temperature for 1 hour, the solvent was distilled off under reduced pressure, toluene (15 ml) was added to the residue, stirred for 3 minutes, and the solvent was distilled off under reduced pressure to give 0.18 g as a pale yellow solid, which was directly used in the next step.
(5) Synthesis of Compound 1-1
To the reaction flask was added 1, 3-dimethyl-4- (2-methanesulfonyl-4-trifluoromethylbenzoyl) -5-hydroxypyrazole (0.4 g, 1.1 mmol), dichloromethane (20 ml), triethylamine (0.22 g, 2.2 mmol), and a dichloromethane solution of cinnamoyl chloride (15 ml) was added dropwise. After stirring at room temperature for 1 hour, the solvent was distilled off under reduced pressure, ethyl acetate (100 ml) was added to the residue, water (50 ml) was extracted by liquid-separation, the organic phase was washed with saturated brine (50 ml) in this order, dried over anhydrous magnesium sulfate, the solvent was distilled off 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: 64%.
Example 2 Synthesis of Compounds 1-7:
(1) Synthesis of 3,4- (methylenedioxy) cinnamoyl chloride
3,4- (methylenedioxy) cinnamic acid (0.21 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 slowly added, the mixture was stirred at room temperature for 1 hour, the solvent was distilled off under reduced pressure, toluene (15 ml) was added to the residue, stirred for 3 minutes, and then the solvent was distilled off under reduced pressure to give a pale yellow solid, 0.23 g, which was directly used in the next step.
(2) Synthesis of Compounds 1-7
To the reaction flask was added 1, 3-dimethyl-4- (2-methanesulfonyl-4-trifluoromethylbenzoyl) -5-hydroxypyrazole (0.4 g, 1.1 mmol, see example 1 step 3), dichloromethane (20 ml), triethylamine (0.22 g, 2.2 mmol), and a dichloromethane solution (15 ml) of 3,4- (methylenedioxy) cinnamoyl chloride was added dropwise. After stirring at room temperature for 1 hour, the solvent was distilled off under reduced pressure, ethyl acetate (100 ml) was added to the residue, water (50 ml) was extracted by liquid-separation, the organic phase was washed with saturated brine (50 ml) in this order, dried over anhydrous magnesium sulfate, the solvent was distilled off 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%.
Example 3 synthesis of compounds 1-16:
(1) Synthesis of 2-chloro-3-methoxymethyl-4-methanesulfonyl benzoyl chloride
To the reaction flask was added 2-methanesulfonyl-4-trifluoromethylbenzoic acid (4 g, 14.35 mmol), dichloromethane (30 ml) and DMF as one drop, oxalyl chloride (9.11 g, 71.8 mmol) was slowly added, the mixture was stirred at room temperature for 40 minutes, the solvent was distilled off under reduced pressure, toluene (15 ml) was added to the residue, stirred for 3 minutes, and the solvent was distilled off under reduced pressure to give 4.26 g as a yellow solid, which was directly taken to the next step.
(2) Synthesis of (1, 3-dimethylpyrazol-5-yl) 2-chloro-3-methoxymethyl-4-methylsulfonylbenzoate
To the reaction flask was added 1, 3-dimethyl-5-hydroxypyrazole (1.77 g, 15.79 mmol), dichloromethane (100 ml), triethylamine (2.9 g, 28.7 mmol), followed by dropwise addition of a dichloromethane solution of step 2-chloro-3-methoxymethyl-4-methanesulfonyl benzoyl chloride (30 ml). Stirring at room temperature for 1 hour, evaporating the solvent under reduced pressure, adding ethyl acetate (100 ml) to the residue, extracting with water (100 ml) in a liquid-separated manner, washing the organic phase with saturated brine (100 ml) in turn, drying over anhydrous magnesium sulfate, evaporating the solvent under reduced pressure, separating the residue by column chromatography to obtain 3.4 g of off-white solid, yield: 63.5%.
(3) Synthesis of 1, 3-dimethyl-4- (2-chloro-3-methoxymethyl-4-methylsulfonyl benzoyl) -5-hydroxypyrazole
2-chloro-3-methoxymethyl-4-methylsulfonylbenzoic acid (1, 3-dimethylpyrazol-5-yl) ester (3.4 g, 9.12 mmol), methylene chloride (100 ml), triethylamine (1.38 g, 13.68 mmol), acetone cyanohydrin (1 ml) were added to the reaction flask and reacted at room temperature for 12 hours, water extraction (50 ml. Times.3) was added to the reaction mixture, the aqueous phase was collected and then pH was adjusted to between 2 and 3 with 20% hydrochloric acid, ethyl acetate (100 ml) was extracted for two times, the organic phase was washed with saturated brine (50 ml) in this order, dried over anhydrous magnesium sulfate and the solvent was distilled off under reduced pressure to obtain 3.26 g of yellow solid, yield: 96%.
(5) Synthesis of Compounds 1-16
To the reaction flask was added 1, 3-dimethyl-4- (2-chloro-3-methoxymethyl-4-methylsulfonylbenzoyl) -5-hydroxypyrazole (0.4 g, 1.07 mmol), dichloromethane (20 ml), triethylamine (0.22 g, 2.15 mmol) and a solution of cinnamoyl chloride in dichloromethane (15 ml, for preparation see example 1, step 4) was added dropwise. After stirring at room temperature for 1 hour, the solvent was distilled off under reduced pressure, ethyl acetate (100 ml) was added to the residue, water (50 ml) was extracted by liquid-separation, the organic phase was washed with saturated brine (50 ml) in this order, dried over anhydrous magnesium sulfate, the solvent was distilled off 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%.
Other compounds of the general formula I, the partial compounds of which are shown in Table 1 and Table 2, can be obtained by replacing the starting materials according to the above-described method; wherein, in Table 1, W is selected from CX 2 And the three-dimensional configuration is trans; table 2 shows that W is selected from N, and the three-dimensional configuration is trans.
Compounds of the general formula I, wherein W is CX 2 And the three-dimensional configuration is trans.
TABLE 1 Structure and physical Properties of part of the Compounds of formula I
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Of part of the compounds 1 The H NMR data are as follows:
compounds 1-1 (600 MHz, 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 (600 MHz, 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 (600 MHz, 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 to 18 (600 MHz, 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)。
Compounds 1 to 20 (600 MHz, 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 (600 MHz, 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 to 22 (600 MHz, 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 (600 MHz, 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)。
Compounds 1 to 37 (600 MHz, 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)。
Compounds 1 to 76 (600 MHz, 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)。
Compounds 1-223 (600 MHz, 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)。
Compounds 1 to 226 (600 MHz, 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)。
Compounds 1 to 229 (600 MHz, 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)。
Compounds 1 to 232 (600 MHz, 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)。
Compounds 1-235 (600 MHz, 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 to 238 (600 MHz, 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)。
Compounds 1-259 (600 MHz, 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 (600 MHz, 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 (600 MHz, 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.
TABLE 2 Structure and physical Properties of part of the Compounds of formula I
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Biological measurement example
Example 4 determination of herbicidal Activity
Sowing broadleaf weeds (zinnia, abutilon) or grassy weeds (green bristlegrass and barnyard grass) seeds into paper cups with 7cm diameter and containing nutrient soil, covering 1cm after sowing, compacting, watering, culturing in a greenhouse according to a conventional method, and carrying out stem and leaf spraying treatment after 2-3 leaf periods of weeds.
After the raw material is dissolved in 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 requirement. Spraying treatment (spraying pressure 1.95 kg/cm) on crawler-type crop spraying machine (manufactured by UK Engineer Research Ltd.) according to the experimental design dose 2 The spraying amount of the spray liquid is 500L/hm 2 Track speed 1.48 km/h). The test was repeated 3 times. After the test materials are treated, the test materials are placed in an operation hall, after the liquid medicine is naturally dried in the shade, the test materials are placed in a greenhouse for management according to a conventional method, the reaction condition of weeds to the chemical agents is observed and recorded, after the test materials are treated, the control effect of the test materials to the weeds is visually detected at regular intervals, the test materials are expressed by 0-100%, and 0 represents no control effect and 100 represents complete killing.
The test results show that the compound of the general formula I has high prevention effect on various weeds. Of the compounds tested, as compound 1-1 was administered at a dose of 600g a.i./hm 2 Has better control effect on the zinnia, the abutilon, the green bristlegrass or the barnyard grass, and the control effect is more than or equal to 90 percent.
The compounds of the general formula are safe for 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 (5)

1. A cinnamate compound, which is characterized in that: the compound is shown in a general formula I:
wherein:
X 1 selected from C 1 -C 3 An alkylsulfonyl group;
w is selected from CX 2 ；
X 2 Selected from hydrogen;
X 3 selected from C 1 -C 3 A haloalkyl group;
Z 1 selected from C 1 -C 6 An alkyl group;
Z 2 selected from C 1 -C 6 An alkyl group;
R 1 to R 5 Each independently selected from hydrogen;
the hydrogen atoms on the carbon-carbon double bonds B of the compounds of the general formula I are on both sides of the bond B.
2. A compound according to claim 1, selected from the group consisting of:
。
3. use of a compound of the general formula I according to claim 1, characterized in that: the use of the compounds of formula I or of agriculturally acceptable salts of the compounds of formula I for controlling weeds.
4. A herbicidal composition characterized in that: the weeding composition is an active substance and an agriculturally acceptable carrier, and the active component is an agriculturally acceptable salt containing the compound of the general formula I or the compound of the general formula I as defined in claim 1; the weight percentage of the active components in the composition is 1-99%.
5. A method of controlling weeds with the composition of claim 4, wherein: a herbicidal composition according to claim 4 in a herbicidally effective amount applied to weeds or to a growth medium or locus of weeds.
CN201910950256.1A 2019-10-08 2019-10-08 Cinnamate compound and application thereof Active CN112624974B (en)

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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

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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

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