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CN110878086A - Five-membered ring substituted pyridazinol compound and derivative, preparation method, herbicidal composition and application thereof - Google Patents

Five-membered ring substituted pyridazinol compound and derivative, preparation method, herbicidal composition and application thereof Download PDF

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Publication number
CN110878086A
CN110878086A CN201811035457.0A CN201811035457A CN110878086A CN 110878086 A CN110878086 A CN 110878086A CN 201811035457 A CN201811035457 A CN 201811035457A CN 110878086 A CN110878086 A CN 110878086A
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radical
alkyl
group
substituted
cycloalkyl
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CN110878086B (en
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连磊
征玉荣
华荣保
王建峰
彭学岗
崔琦
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Qingdao Kingagroot Chemical Compound Co Ltd
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Qingdao Kingagroot Chemical Compound Co Ltd
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Priority to PCT/CN2018/105408 priority patent/WO2019148851A1/en
Priority to US16/966,704 priority patent/US12024500B2/en
Priority to BR112020015620-5A priority patent/BR112020015620B1/en
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    • C07D403/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • 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
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    • 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
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    • 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
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    • A01N43/82—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with three ring hetero atoms
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/84—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms six-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,4
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N55/00—Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur
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    • 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
    • C07D401/14—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 three or more hetero rings
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    • 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
    • C07D405/04—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 directly linked by a ring-member-to-ring-member bond
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    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
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    • C07—ORGANIC CHEMISTRY
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    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
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    • C07D413/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
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    • C07D417/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
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    • C07F7/0803—Compounds with Si-C or Si-Si linkages
    • C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
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    • C07F7/0814—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring said ring is substituted at a C ring atom by Si

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
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  • Plant Pathology (AREA)
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  • Engineering & Computer Science (AREA)
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  • Wood Science & Technology (AREA)
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  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Plural Heterocyclic Compounds (AREA)

Abstract

The invention belongs to the technical field of pesticides, and particularly relates to a five-membered ring substituted pyridazinol compound, a derivative, a preparation method, a weeding composition and application thereof. The compound is shown as a general formula I:
Figure DDA0001790744420000011
wherein X represents halogen, cyano, alkyl, haloalkyl, alkoxy, haloalkoxy, R1R2N‑(C＝O)‑、R1R2N-, etc.; ar represents
Figure DDA0001790744420000012
Het is selected from five-membered unsaturated rings containing, as part of the ring, in addition to the C atom in position 1, from 0 to 4 of the following atoms or groups: o, NRbOr S; raOne or more groups selected from the following groups: hydrogen, halogen, R-O- (CH)2)n‑，R1R2R3SiO-, etc.; m is 0 or 1, n and q respectively represent an integer between 0 and 8, and p represents an integer between 1 and 8; r represents hydrogen, alkyl, alkenyl, etc., with or without halogen; rb、R1、R2、R3Each independently represents hydrogen, nitro, hydroxy, amino, or the like. The compound, the derivative and the composition thereof have very high herbicidal activity, are safe to crops and have good selectivity.

Description

Five-membered ring substituted pyridazinol compound and derivative, preparation method, herbicidal composition and application thereof
Technical Field
The invention belongs to the technical field of pesticides, and particularly relates to a five-membered ring substituted pyridazinol compound, a derivative, a preparation method, a weeding composition and application thereof.
Background
The weed control is a crucial link in the process of realizing high-efficiency agriculture, and the current herbicides in the market are various, such as the pyridazine herbicide pyridate
Figure BDA0001790744410000011
Pyridazinol
Figure BDA0001790744410000012
And the like, which belong to photosystem II inhibitor herbicides, inhibit the progress of photosynthesis by blocking electron transfer and the transfer of light energy.
Due to the ever-expanding market, the problems of weed resistance, the life span of the drugs and the economic efficiency of the drugs, and the increasing attention of people to the environment, scientists are required to continuously research and develop new herbicide varieties with high efficiency, safety, economy and different action modes.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a five-membered ring substituted pyridazinol compound and derivatives thereof, a preparation method, a weeding composition and application thereof.
The technical scheme adopted by the invention is as follows:
a five-membered ring substituted pyridazinol compound and its derivatives are shown in formula I:
Figure BDA0001790744410000013
wherein X represents halogen, cyano, alkyl, haloalkyl, alkoxy, haloalkoxy, R1R2N-(C＝O)-、R1R2N-, hydroxy, unsubstituted or substituted aryl;
ar represents
Figure BDA0001790744410000014
Het is selected from five-membered unsaturated rings containing, as part of the ring, in addition to the C atom in position 1, from 0 to 4 of the following atoms or groups: o, NRbOr S;
Raone or more groups selected from the following groups: hydrogen, halogen, cyano, nitro, azido, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkylalkyl, unsubstituted or substituted aryl, arylalkyl, heteroaryl, heteroarylalkyl, with or without halogen, R-O- (CH)2)n-，R-O-(CH2)p-O-(CH2)q-，R-O-(CH2)p-S-(CH2)q-，R-S-(CH2)n-，R-S-(CH2)p-O-(CH2)q-，R-S-(CH2)p-S-(CH2)q-，R-O-(CH2)n-(C＝O)-(CH2)q-(O)m-，R-S-(CH2)n-(C＝S)-(CH2)q-(S)m-，R-O-(CH2)n-(C＝O)-(CH2)q-(S)m-，R-O-(CH2)n-(C＝S)-(CH2)q-(O)m-，R-S-(CH2)n-(C＝O)-(CH2)q-(O)m-，R-O-(CH2)n-(C＝S)-(CH2)q-(S)m-，R-S-(CH2)n-(C＝O)-(CH2)q-(S)m-，R-S-(CH2)n-(C＝S)-(CH2)q-(O)m-，R-(C＝O)-(CH2)n-，R-(C＝S)-(CH2)n-，R-(C＝O)-(CH2)n-O-(CH2)q-，R-(C＝S)-(CH2)n-S-(CH2)q-，R-(C＝O)-(CH2)n-S-(CH2)q-，R-(C＝S)-(CH2)n-O-(CH2)q-，R-SO-(CH2)n-(O)m-，R-SO-(CH2)n-(S)m-，R-SO-(CH2)n-(NR3)m-，R-SO2-(CH2)n-(O)m-，R-SO2-(CH2)n-(S)m-，R-SO2-(CH2)n-(NR3)m-，R1R2N-(CH2)n-，R1R2N-(CH2)n-O-(CH2)q-(O)m-，R1R2N-(CH2)n-O-(CH2)q-(S)m-，R1R2N-(CH2)n-O-(CH2)q-(NR3)m-，R1R2N-(CH2)n-(C＝O)-(CH2)q-(O)m-，R1R2N-(CH2)n-(C＝O)-(CH2)q-(S)m-，R1R2N-(CH2)n-(C＝O)-(CH2)q-(NR3)m-，R1R2N-(CH2)n-SO2-(CH2)q-(O)m-，R1R2N-(CH2)n-SO2-(CH2)q-(S)m-，R1R2N-(CH2)n-SO2-(CH2)q-(NR3)m-，R1R2PO3-(O)m-(CH2)q-，R1R2R3SiO-(CH2)q-，R1R2R3Si-(CH＝CH)m-(CH2)q-，R1R2C＝N-(O)m-(CH2)n-，R1R2C＝N-NH-(CH2)n-; or two adjacent RaTogether form-OCH2O-、-CH2CH2O-、-OCH2CH2O-、-OCH(CH3)O-、-OC(CH3)2O-、-OCF2O-、-CF2CF2O-、-OCF2CF2O-or-CH-;
m is 0 or 1, n and q respectively represent an integer between 0 and 8, and p represents an integer between 1 and 8; wherein each m, n, q, p in the above groups independently takes a value, and the value is such that each R takes a valueaThe groups are different from each other;
r represents hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkylalkyl, with or without halogen, and unsubstituted or substituted aryl, arylalkyl, heteroaryl, heteroarylalkyl;
Rb、R1、R2、R3each independently represents hydrogen, nitro, hydroxyl, amino, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkylalkyl, alkoxy, alkenyloxy, alkynyloxy, cycloalkyloxy, alkoxyalkyl, alkoxycarbonyl, alkylthiocarbonyl, alkylsulfonyl, alkylsulfonylalkyl, alkylcarbonyl, alkylcarbonylalkyl, alkanoyloxy, alkylamino, alkylaminocarbonyl, alkoxyaminocarbonyl, alkoxycarbonylalkyl, alkylaminocarbonylalkyl, trialkylsilyl, dialkylphosphono, and unsubstituted or substituted six-membered heterocyclic groups, aryl, arylalkyl, aryloxy, arylalkyloxy, arylalkyloxyalkyl, arylcarbonyl, arylsulfonyl, heteroaryl, heteroarylalkyl, heteroaryloxy, heteroarylalkyloxy, heteroaryloxyalkyl, heteroarylalkyloxyalkyl, heteroarylalkylcarbonyl, heteroarylcarbonyl, alkoxy, alkoxycarbonyl, alkoxyalkylcarbonyl, alkoxyalkylcarbonylalkyl, alkoxycarbonylalkyl, alkoxy, A heteroaryl sulfonyl group; or R1R2N-represents a six-membered heterocyclic group; or adjacent RaAnd RbTogether form-CH2CH2NR3CH2-。
Preferably, X represents halogen, cyano, C1～8Alkyl, halo C1～8Alkyl radical, C1～8Alkoxy, halo C1～8Alkoxy radical, R1R2N-(C＝O)-、R1R2N-, hydroxyl, unsubstituted or 1-5 substituents independently selected from halogen, cyano, nitro, hydroxyl, carboxyl, mercapto, amino and C with or without halogen1～8Alkyl radical, C3～8Cycloalkyl radical, C3～8Cycloalkyl radical C1～8Alkyl radical, C2～8Alkenyl radical, C2～8Alkynyl, C1～8Alkoxy radical, C1～8Alkylcarbonyl group, C1～8Alkoxycarbonyl group, C1～8Alkylsulfonyl radical, C1～8Alkylamino or C1～8Aryl substituted with a group selected from the group consisting of an alkanoyloxy group;
ar represents
Figure BDA0001790744410000031
Het is selected from the group consisting of five-membered unsaturated heterocycles containing 1 to 4 of the following atoms or groups as ring members in addition to the C atom in position 1: o, NRbOr S;
Raone or more groups selected from the following groups: hydrogen, halogen, cyano, nitro, azido, C with or without halogen1～8Alkyl radical, C2～8Alkenyl radical, C2～8Alkynyl, C3～8Cycloalkyl radical, C5～8Cycloalkenyl radical, C3～8Cycloalkyl radical C1～8Alkyl, unsubstituted or substituted by 1 to 5 groups independently selected from halogen, cyano, nitro, hydroxy, carboxy, mercapto, amino and C with or without halogen1～8Alkyl radical, C3～8Cycloalkyl radical, C3～8Cycloalkyl radical C1～8Alkyl radical, C2～8Alkenyl radical, C2～8Alkynyl, C1～8Alkoxy radical, C1～8Alkylcarbonyl group, C1～8Alkoxycarbonyl group, C1～8Alkylsulfonyl radical, C1～8Alkylamino or C1～8Aryl, aryl C substituted by radicals in alkanoyloxy1～8Alkyl, heteroaryl C1～8Alkyl, R-O- (CH)2)n-，R-O-(CH2)p-O-(CH2)q-，R-O-(CH2)p-S-(CH2)q-，R-S-(CH2)n-，R-S-(CH2)p-O-(CH2)q-，R-S-(CH2)p-S-(CH2)q-，R-O-(CH2)n-(C＝O)-(CH2)q-，R-S-(CH2)n-(C＝S)-(CH2)q-，R-O-(CH2)n-(C＝S)-(CH2)q-，R-S-(CH2)n-(C＝O)-(CH2)q-，R-O-(C＝O)-(CH2)q-(O)m-，R-S-(C＝S)-(CH2)q-(S)m-，R-O-(C＝O)-(CH2)q-(S)m-，R-O-(C＝S)-(CH2)q-(O)m-，R-S-(C＝O)-(CH2)q-(O)m-，R-O-(C＝S)-(CH2)q-(S)m-，R-S-(C＝O)-(CH2)q-(S)m-，R-S-(C＝S)-(CH2)q-(O)m-，R-O-(CH2)n-(C＝O)-(O)m-，R-S-(CH2)n-(C＝S)-(S)m-，R-O-(CH2)n-(C＝O)-(S)m-，R-O-(CH2)n-(C＝S)-(O)m-，R-S-(CH2)n-(C＝O)-(O)m-，R-O-(CH2)n-(C＝S)-(S)m-，R-S-(CH2)n-(C＝O)-(S)m-，R-S-(CH2)n-(C＝S)-(O)m-，R-(C＝O)-，R-(C＝S)-，R-(C＝O)-(CH2)n-O-，R-(C＝S)-(CH2)n-S-，R-(C＝O)-(CH2)n-S-，R-(C＝S)-(CH2)n-O-，R-(C＝O)-O-(CH2)q-，R-(C＝S)-S-(CH2)q-，R-(C＝O)-S-(CH2)q-，R-(C＝S)-O-(CH2)q-，R-SO-(O)m-，R-SO-(S)m-，R-SO-(NR3)m-，R-SO2-(O)m-，R-SO2-(S)m-，R-SO2-(NR3)m-，R-SO-(CH2)n-，R-SO2-(CH2)n-，R1R2N-，R1R2N-(CH2)n-O-(CH2)q-，R1R2N-(CH2)n-(C＝O)-(CH2)q-，R1R2N-(CH2)n-SO2-(CH2)q-，R1R2N-(CH2)n-(C＝O)-(O)m-，R1R2N-(CH2)n-(C＝O)-(S)m-，R1R2N-(CH2)n-(C＝O)-(NR3)m-，R1R2N-(CH2)n-SO2-(O)m-，R1R2N-(CH2)n-SO2-(S)m-，R1R2N-(CH2)n-SO2-(NR3)m-，R1R2N-(C＝O)-(CH2)n-(O)m-，R1R2N-(C＝O)-(CH2)n-(S)m-，R1R2N-(C＝O)-(CH2)n-(NR3)m-，R1R2N-SO2-(CH2)q-(O)m-，R1R2N-SO2-(CH2)q-(S)m-，R1R2N-SO2-(CH2)q-(NR3)m-，R1R2N-(CH2)n-O-，R1R2N-O-(CH2)q-，R1R2PO3-(O)m-，R1R2R3SiO-，R1R2R3Si-(CH＝CH)m-，R1R2C＝N-(O)m-，R1R2C ═ N-NH-; or two adjacent RaAre formed together-OCH2O-、-CH2CH2O-、-OCH2CH2O-、-OCH(CH3)O-、-OC(CH3)2O-、-OCF2O-、-CF2CF2O-、-OCF2CF2O-or-CH-;
m is 0 or 1, n and q respectively represent an integer between 0 and 6, and p represents an integer between 1 and 6; wherein each m, n, q, p in the above groups independently takes a value, and the value is such that each R takes a valueaThe groups are different from each other;
r represents hydrogen, C with or without halogen1～8Alkyl radical, C2～8Alkenyl radical, C2～8Alkynyl, C3～8Cycloalkyl radical, C5～8Cycloalkenyl radical, C3～8Cycloalkyl radical C1～8Alkyl, unsubstituted or substituted by 1 to 5 substituents independently selected from halogen, cyano, nitro, hydroxy, carboxy, mercapto, amino and C with or without halogen1～8Alkyl radical, C3～8Cycloalkyl radical, C3～8Cycloalkyl radical C1～8Alkyl radical, C2～8Alkenyl radical, C2～8Alkynyl, C1～8Alkoxy radical, C1～8Alkylcarbonyl group, C1～8Alkoxycarbonyl group, C1～8Alkylsulfonyl radical, C1～8Alkylamino or C1～8Aryl, aryl C substituted by radicals in alkanoyloxy1～8Alkyl, heteroaryl C1～8An alkyl group;
Rb、R1、R2、R3each independently represents hydrogen, nitro, hydroxy, amino, C with or without halogen1～8Alkyl radical, C2～8Alkenyl radical, C2～8Alkynyl, C3～8Cycloalkyl radical, C5～8Cycloalkenyl radical, C3～8Cycloalkyl radical C1～8Alkyl radical, C1～8Alkoxy radical, C2～8Alkenyloxy radical, C2～8Alkynyloxy, C3～8Cycloalkyl oxy, C1～8Alkoxy radical C1～8Alkyl radical, C1～8Alkoxycarbonyl group, C1～8Alkyl carbonyl radical C1～8Alkyl radical, C1～8Alkylthio carbonyl group, C1～8Alkylsulfonyl radical, C1～8Alkylsulfonyl radical C1～8Alkyl radical, C1～8Alkylcarbonyl group, C1～8Alkyl acyloxy, C1～8Alkylamino radical, C1～8Alkylaminocarbonyl radical, C1～8Alkoxyaminocarbonyl group, C1～8Alkoxycarbonyl radical C1～8Alkyl radical, C1～8Alkylamino carbonyl group C1～8Alkyl, tri-C1～8Alkylsilyl, di-C1～8Alkylphosphono and unsubstituted or substituted by 1 to 5 substituents independently selected from halogen, cyano, nitro, hydroxy, carboxy, mercapto, amino and C with or without halogen1～8Alkyl radical, C3～8Cycloalkyl radical, C3～8Cycloalkyl radical C1～8Alkyl radical, C2～8Alkenyl radical, C2～8Alkynyl, C1～8Alkoxy radical, C1～8Alkylcarbonyl group, C1～8Alkoxycarbonyl group, C1～8Alkylsulfonyl radical, C1～8Alkylamino or C1～8Six-membered heterocyclic radical, aryl radical C substituted by radicals in alkyl acyloxy1～8Alkyl, aryloxy, aryl C1～8Alkyloxy, aryloxy C1～8Alkyl, arylcarbonyl, arylsulfonyl, heteroaryl C1～8Alkyl, heteroaryloxy, heteroaryl C1～8Alkyloxy, heteroaryloxy C1～8Alkyl, heteroarylcarbonyl, heteroarylsulfonyl; or R1R2N-represents a six-membered heterocyclic group which may or may not contain other hetero atoms in the ring; or adjacent RaAnd RbTogether form-CH2CH2NR3CH2-。
More preferably, X represents fluorine, chlorine, bromine, iodine, cyano, C1～6Alkyl, halo C1～6Alkyl radical, C1～6Alkoxy, halo C1～6Alkoxy radical, R1R2N-(C＝O)-、R1R2N-, hydroxyl, unsubstituted or 1-5 substituents independently selected from halogen, cyano, nitro, hydroxyl, carboxyl, mercapto, amino and C with or without halogen1～6Alkyl radical, C3～6Cycloalkyl radical, C3～6CycloalkanesRadical C1～6Alkyl radical, C2～6Alkenyl radical, C2～6Alkynyl, C1～6Alkoxy radical, C1～6Alkylcarbonyl group, C1～6Alkoxycarbonyl group, C1～6Alkylsulfonyl radical, C1～6Alkylamino or C1～6Phenyl substituted with a group selected from the group consisting of alkyl acyloxy;
ar represents
Figure BDA0001790744410000041
Het is selected from the group consisting of five-membered unsaturated heterocycles containing as ring members, in addition to the C atom in position 1,2, 3 or 4 of the following atoms or groups: o, NRbOr S;
Raone or more groups selected from the following groups: hydrogen, fluorine, chlorine, bromine, cyano, nitro, azido, C with or without fluorine, chlorine, bromine1～6Alkyl radical, C2～6Alkenyl radical, C2～6Alkynyl, C3～6Cycloalkyl radical, C5～6Cycloalkenyl radical, C3～6Cycloalkyl radical C1～6Alkyl, unsubstituted or substituted by 1 to 3 groups independently selected from fluorine, chlorine, bromine, cyano, nitro, hydroxy, carboxy, mercapto, amino and C with or without fluorine, chlorine, bromine1～6Alkyl radical, C3～6Cycloalkyl radical, C3～6Cycloalkyl radical C1～6Alkyl radical, C2～6Alkenyl radical, C2～6Alkynyl, C1～6Alkoxy radical, C1～6Alkylcarbonyl group, C1～6Alkoxycarbonyl group, C1～6Alkylsulfonyl radical, C1～6Alkylamino or C1～6Aryl, aryl C substituted by radicals in alkanoyloxy1～6Alkyl, heteroaryl C1～6Alkyl, R-O-, R-O- (CH)2)p-O-，R-O-(CH2)p-S-，R-S-，R-S-(CH2)p-O-，R-S-(CH2)p-S-，R-O-(C＝O)-(O)m-，R-S-(C＝S)-(S)m-，R-O-(C＝O)-(S)m-，R-O-(C＝S)-(O)m-，R-S-(C＝O)-(O)m-，R-O-(C＝S)-(S)m-，R-S-(C＝O)-(S)m-，R-S-(C＝S)-(O)m-，R-O-(C＝O)-(CH2)q-，R-S-(C＝S)-(CH2)q-，R-O-(C＝S)-(CH2)q-，R-S-(C＝O)-(CH2)q-，R-O-(CH2)n-(C＝O)-，R-S-(CH2)n-(C＝S)-，R-O-(CH2)n-(C＝S)-，R-S-(CH2)n-(C＝O)-，R-(C＝O)-，R-(C＝S)-，R-(C＝O)-O-，R-(C＝S)-S-，R-(C＝O)-S-，R-(C＝S)-O-，R-SO-，R-SO2-，R1R2N-，R1R2N-O-，R1R2N-(C＝O)-(CH2)p-，R1R2N-(C＝O)-(O)m-，R1R2N-(C＝O)-(S)m-，R1R2N-(C＝O)-(NR3)m-，R1R2N-SO2-(CH2)p-，R1R2N-SO2-，R1R2N-(CH2)p-(C＝O)-，R1R2N-(CH2)p-SO2-，R1R2N-(CH2)p-O-，R1R2N-O-(CH2)p-，R1R2PO3-，R1R2R3SiO-，R1R2R3Si-，R1R2R3Si-CH＝CH-，R1R2C＝N-，R1R2C＝N-O-，R1R2C ═ N-NH-; or two adjacent RaTogether form-CH ═ CH-;
m is 0 or 1, n and q respectively represent 0, 1,2, 3 or 4, and p represents 1,2, 3 or 4; wherein each m, n, q, p in the above groups independently takes a value, and the value is such that each R takes a valueaThe groups are different from each other;
r represents hydrogen, C with or without fluorine, chlorine or bromine1～6Alkyl radical, C2～6Alkenyl radical, C2～6Alkynyl, C3～6Cycloalkyl radical, C5～6Cycloalkenyl radical, C3～6Cycloalkyl radical C1～6Alkyl, unsubstituted or substituted by 1 to 3 groups independently selected from fluorine, chlorine, bromine, cyano, nitro, hydroxy, carboxy, mercapto, amino and C with or without fluorine, chlorine or bromine1～6Alkyl radical, C3～6Cycloalkyl radical, C3～6Cycloalkyl radical C1～6Alkyl radical, C2～6Alkenyl radical, C2～6Alkynyl, C1～6Alkoxy radical, C1～6Alkylcarbonyl group, C1～6Alkoxycarbonyl group, C1～6Alkylsulfonyl radical, C1～6Alkylamino or C1～6Aryl, aryl C substituted by radicals in alkanoyloxy1～6Alkyl, heteroaryl C1～6An alkyl group;
Rb、R1、R2、R3each independently represents hydrogen, nitro, hydroxyl, amino, C with or without fluorine, chlorine or bromine1～6Alkyl radical, C2～6Alkenyl radical, C2～6Alkynyl, C3～6Cycloalkyl radical, C5～6Cycloalkenyl radical, C3～6Cycloalkyl radical C1～6Alkyl radical, C1～6Alkoxy radical, C2～6Alkenyloxy radical, C2～6Alkynyloxy, C3～6Cycloalkyl oxy, C1～6Alkoxy radical C1～6Alkyl radical, C1～6Alkoxycarbonyl group, C1～6Alkylthio carbonyl group, C1～6Alkylsulfonyl radical, C1～6Alkylsulfonyl radical C1～6Alkyl radical, C1～6Alkylcarbonyl group, C1～6Alkyl carbonyl radical C1～6Alkyl radical, C1～6Alkyl acyloxy, C1～6Alkylamino radical, C1～6Alkylaminocarbonyl radical, C1～6Alkoxyaminocarbonyl group, C1～6Alkoxycarbonyl radical C1～6Alkyl radical, C1～6Alkylamino carbonyl group C1～6Alkyl, tri-C1～6Alkylsilyl, di-C1～6Alkylphosphono and unsubstituted or substituted 1-3 of C independently selected from fluorine, chlorine, bromine, cyano, nitro, hydroxyl, carboxyl, mercapto, amino and optionally fluorine, chlorine and bromine1～6Alkyl radical, C3～6Cycloalkyl radical, C3～6Cycloalkyl radical C1～6Alkyl radical, C2～6Alkenyl radical, C2～6Alkynyl, C1～6Alkoxy radical, C1～6Alkylcarbonyl group, C1～6Alkoxycarbonyl group, C1～6Alkylsulfonyl radical, C1～6Alkylamino or C1～6Substituted by radicals in the group of alkanoyloxy
Figure BDA0001790744410000061
Aryl, aryl C1～6Alkyl, aryloxy, aryl C1～6Alkyloxy, aryloxy C1～6Alkyl, arylcarbonyl, arylsulfonyl, heteroaryl C1～6Alkyl, heteroaryloxy, heteroaryl C1～6Alkyloxy, heteroaryloxy C1～6Alkyl, heteroarylcarbonyl, heteroarylsulfonyl; or R1R2N-represents
Figure BDA0001790744410000062
Or adjacent RaAnd RbTogether form-CH2CH2N(Boc)CH2-；
Said aryl is
Figure BDA0001790744410000063
Figure BDA0001790744410000064
Heteroaryl is selected from
Figure BDA0001790744410000065
Figure BDA0001790744410000066
Figure BDA0001790744410000067
R' represents hydrogen, nitro, hydroxyl, amino, C with or without fluorine, chlorine or bromine1～6Alkyl radical, C2～6Alkenyl radical, C2～6Alkynyl, C3～6Cycloalkyl radical, C5～6Cycloalkenyl radical, C3～6Cycloalkyl radical C1～6Alkyl radical, C1～6Alkoxy radicalBase, C2～6Alkenyloxy radical, C2～6Alkynyloxy, C3～6Cycloalkyl oxy, C1～6Alkoxy radical C1～6Alkyl radical, C1～6Alkoxycarbonyl group, C1～6Alkylthio carbonyl group, C1～6Alkylsulfonyl radical, C1～6Alkylsulfonyl radical C1～6Alkyl radical, C1～6Alkylcarbonyl group, C1～6Alkyl carbonyl radical C1～6Alkyl radical, C1～6Alkyl acyloxy, C1～6Alkylamino radical, C1～6Alkylaminocarbonyl radical, C1～6Alkoxyaminocarbonyl group, C1～6Alkoxycarbonyl radical C1～6Alkyl radical, C1～6Alkylamino carbonyl group C1～6Alkyl, tri-C1～6Alkylsilyl, di-C1～6Alkylphosphono and unsubstituted or substituted 1-3 of C independently selected from fluorine, chlorine, bromine, cyano, nitro, hydroxyl, carboxyl, mercapto, amino and optionally fluorine, chlorine and bromine1～6Alkyl radical, C3～6Cycloalkyl radical, C3～6Cycloalkyl radical C1～6Alkyl radical, C2～6Alkenyl radical, C2～6Alkynyl, C1～6Alkoxy radical, C1～6Alkylcarbonyl group, C1～6Alkoxycarbonyl group, C1～6Alkylsulfonyl radical, C1～6Alkylamino or C1～6Substituted by radicals in the group of alkanoyloxy
Figure BDA0001790744410000071
Aryl, aryl C1～6Alkyl, aryloxy, aryl C1～6Alkyloxy, aryloxy C1～6Alkyl, arylcarbonyl, arylsulfonyl, heteroaryl C1～6Alkyl, heteroaryloxy, heteroaryl C1～6Alkyloxy, heteroaryloxy C1～6Alkyl, heteroarylcarbonyl, heteroarylsulfonyl.
Further preferably, X represents fluorine, chlorine, bromine, iodine, cyano, methyl, ethyl, trifluoromethyl, pentafluoroethyl, difluoromethyl, monofluoromethyl, methoxy, ethoxy, trifluoromethoxy, pentafluoroethoxy;
het represents
Figure BDA0001790744410000072
Figure BDA0001790744410000073
RaOne or more groups selected from the following groups: hydrogen, methyl, ethyl, cyano, cyclopropyl, phenyl, fluoro, chloro, bromo, iodo, cyano, nitro, difluoromethyl, 2,2, 2-trifluoroethyl, trifluoromethyl, methoxy, ethoxy, benzyloxy, -COOEt, amino, methylamino, dimethylamino, acetylamino, trifluoromethyl,
Figure BDA0001790744410000074
Figure BDA0001790744410000075
or Ar represents
Figure BDA0001790744410000076
RbRepresents hydrogen, methyl, ethyl, n-propyl, isopropyl, difluoromethyl, 2,2, 2-trifluoroethyl, acetyl, phenyl, benzyl, methyl, ethyl, isopropyl, trifluoromethyl,
Figure BDA0001790744410000081
Triphenylmethyl group.
The derivatives of the invention
Figure BDA0001790744410000082
The derivative refers to agriculturally acceptable hydroxyl derivatives at the 4-position of the pyridazine ring in the general formula I, and comprises salt, ester, oxime, hydroxylamine, ether and other derivatives.
The salt derivative is a salt used in a general agricultural chemical, and for example, it can be made into an alkali metal salt, an alkaline earth metal salt, or an amine salt, or, when a basic moiety is present in the molecule, it can be made into a salt such as a sulfate, a hydrochloride, a nitrate, or a phosphate. These salts are also included in the present invention if they are used as herbicides for agriculture and horticulture. In the present invention, the "alkali metal salt" may be, for example, a sodium salt, a potassium salt or a lithium salt, and is preferably a sodium salt or a potassium salt. In the present invention, the "alkaline earth metal salt" may be, for example, a calcium salt or a magnesium salt, and is preferably a calcium salt. In the present invention, the "amine salt" may be, for example, an alkyl secondary amine salt, an alkyl tertiary amine salt, or an alkyl quaternary amine salt; primary, secondary, tertiary or quaternary alkanolamine alkoxides; primary, secondary, tertiary or quaternary alkyl alkanol amine salts; or a primary, secondary, tertiary or quaternary alkoxy alkanol amine salt, preferably wherein the alkyl, alkanol and alkoxy groups are independently saturated and independently contain C1-C4 carbon atoms, more preferably a monoethanolamine, dimethylethanolamine, triethanolamine, dimethylamine, triethylamine, isopropylamine, choline or diglycolamine salt.
Solvates of the compounds of the invention are also encompassed by the invention.
The compound of the present invention also includes a compound having an asymmetric carbon atom, and in this case, the present invention also includes a mixture of one optically active substance and a plurality of optically active substances in an arbitrary ratio.
The ester derivative is a compound in which an acyl group (including a carbonyl group, a thiocarbonyl group, a sulfoxide group, a sulfonyl group, a phosphoryl group, a thiophosphoryl group, etc.) is bonded to an oxygen atom of a hydroxyl group at the 4-position of a pyridazine ring, and examples thereof include a methanesulfonyl acyl group or a C1 to C18 alk (thio) carbonyl group which may be substituted [ the substituent is a halogen atom, an amino group, a C3 to C8 cycloalkyl group, a C1 to C8 alkoxy group, a C1 to C8 alkylthio group, a C1 to C8 alkoxycarbonyl group, a C1 to C8 alkylcarbonyloxy group, a C1 to C8 alkylcarbonyl group, a C2 to C8 alkenyloxycarbonyl group which may be substituted { the substituent is a C3 to C8 cycloalkyl group, a cyano group, and a benzoyl group which may be substituted (the substituent is the same or different from 3 to 3 substituents selected from the halogen atom, the C1 to C8 alkyl group, the C1 to C8 haloalkyl group, the C8 alkoxycarbonyl group, the nitro group, and the C8 to C8 alkylsulfonyl group), A hydroxymethylphosphinyl group, an optionally substituted C3-C8 cycloalkenyloxycarbonyl group { the substituentIs an identical or different 1-2 substituents selected from oxo and optionally substituted benzoyl (the substituents are identical or different 1-3 substituents selected from halogen atom, C1-C8 alkyl, C1-C8 haloalkyl, C1-C8 alkoxycarbonyl, nitro and C1-C8 alkylsulfonyl), or optionally substituted 5-or 6-membered heterocyclyloxycarbonyl { the ring of the heterocycle contains 1 nitrogen atom, oxygen atom or sulfur atom, and may further contain 1-2 nitrogen atoms. The substituent is selected from halogen atom, C1-C8 alkyl, optionally substituted phenoxy (the substituent is 1-3 same or different substituents selected from halogen atom, C1-C8 alkyl, C1-C8 haloalkyl, C3-C8 cycloalkyl and C1-C8 alkoxycarbonyl), 2, 3-dihydro-1H-indenyloxy and optionally substituted benzoyl (the substituent is 1-3 same or different substituents selected from halogen atom, C1-C8 alkyl, C1-C8 haloalkyl, C1-C8 alkoxycarbonyl, nitro and C1-C8 alkylsulfonyl), optionally substituted phenyl, phenoxy, benzyloxy, phenylthio and benzylthio (the substituent is 1-3 same or different substituents selected from halogen atom, C1-C8 alkyl, C1-C8 alkoxy, C8-C8 haloalkyl and C5872 alkoxycarbonyl), And 1 or more same or different substituents selected from C1 to C8 alkylthio]C3-C8 Cycloalkane (thio) carbonyl, adamantyl (thio) carbonyl, optionally substituted C2-C8 alkenylthio (thio) carbonyl { the substituent is a halogen atom, C1-C8 alkoxy, and 1 or more identical or different substituents selected from 1 to 3 substituents selected from a halogen atom, C1-C8 alkyl, C1-C8 alkoxy, C1-C8 haloalkyl, and C1-C8 alkoxycarbonyl }, C2-C8 alkynyl (thio) carbonyl, optionally substituted benzoyl (thio) acyl, or naphthoyl (thio) acyl [ the substituent is a halogen atom, optionally substituted C1-C8 alkyl (the substituent is 1 or more identical or different substituents selected from a halogen atom and phenyl), cyano, hydroxy, C1-C585 alkylcarbonyl, C4623-C1 alkoxycarbonyl, optionally substituted C2-C8 alkenylthio (thio) carbonyl { the substituent is 1 or more identical or different substituents selected from a halogen atom and phenyl }, and (C4684-C355823 alkoxy) carbonyl, C1-C8 alkylcarbonyloxy group, C1-C8 alkylcarbonylamino group, amino group which may be substituted(s) (C)The substituent is 1 to 3 identical or different substituents selected from C1 to C8 alkyl, C1 to C8 alkoxy, C1 to C8 alkylcarbonyl, halogenated C1 to C8 alkyl and phenyl), and optionally substituted C2 to C8 alkenyloxycarbonyl { the substituent is 1 to 3 identical or different substituents selected from C8 cycloalkyl, cyano and optionally substituted benzoyl (the substituents are 1 to 3 identical or different substituents selected from halogen atom, C8 to C8 alkyl, C8 to C8 haloalkyl, C8 to C8 alkoxycarbonyl, nitro and C8 to C8 alkylsulfonyl), or optionally substituted C8 to C8 cycloalkoxycarbonyl { the substituent is one or more identical or different substituents selected from oxo and optionally substituted benzoyl (the substituents are 1 to 3 identical or different substituents selected from halogen atom, C8 to C8 alkyl, C72 to C8 haloalkyl, C8 to C8 alkoxycarbonyl, and optionally substituted C8 to C8 alkylsulfonyl) 1 to 2 substituents of (a), phenyl group, nitro group, optionally substituted C1 to C8 alkoxy group (the substituents may be the same or different 1 to 3 substituents selected from halogen atom and phenyl group), phenoxy group, optionally substituted 5-or 6-membered heterocyclyloxycarbonyl group { the ring of the heterocycle contains 1 nitrogen atom, oxygen atom or sulfur atom, and may further contain 1 to 2 nitrogen atoms. The substituent is selected from a halogen atom, a C1-C8 alkyl group, a phenoxy group which may be substituted (the substituent is 1-3 same or different substituents selected from a halogen atom, a C1-C8 alkyl group, a C1-C8 haloalkyl group, a C3-C8 cycloalkyl group and a C1-C8 alkoxycarbonyl group), a 2, 3-dihydro-1H-indenyloxy group, a benzoyl group which may be substituted (the substituent is 1-3 same or different substituents selected from a halogen atom, a C1-C8 alkyl group, a C1-C8 haloalkyl group, a C1-C8 alkoxycarbonyl group, a nitro group and a C1-C8 alkylsulfonyl group), and a 5-or 6-membered heterocyclic oxysulfonyl group which may be substituted { the ring of the heterocyclic ring contains 1 nitrogen atom, an oxygen atom or a sulfur atom, and may further contain 1-2 nitrogen atoms. The substituent is selected from halogen atom, C1-C8 alkyl, optionally substituted phenoxy (the substituent is selected from halogen atom, C1-C8 alkyl, C1-C8 halogenated alkyl, C3-C8 cycloalkyl and C1-C8 alkoxycarbonyl, which are the same or different 1-3 substituents), 2,3-dihydro-1H-indoxyl and optionally substituted benzoyl (the substituent is the same or different 1-3 substituents selected from halogen atom, C1-C8 alkyl, C1-C8 haloalkyl, C1-C8 alkoxycarbonyl, nitro and C1-C8 alkylsulfonyl) }]Halogen-substituted mercaptoformyl group, and optionally substituted 3-to 8-membered heterocyclic (thio) carbonyl group { the heterocyclic ring contains 1 nitrogen atom, oxygen atom or sulfur atom, may further contain 1 to 2 nitrogen atoms, and may form a 5-to 6-membered spiro ring containing 1 to 2 oxygen atoms on an arbitrary carbon atom in the heterocyclic ring. The substituent is selected from halogen atom, C1-C8 alkyl group (the substituent is selected from halogen atom and phenyl group 1 or more same or different substituents), C1-C8 alkyl carbonyl, C1-C8 alkoxy carbonyl, phenyl group (the substituent is selected from same or different 1-3 halogen atoms), nitro, hydroxy, C1-C8 alkoxy, phenoxy, C1-C8 alkylthio, C2-C8 alkenyl thio and phenylthio) which may be substituted 1-3 substituents, 5-14 member condensed bi-or tri-cyclic heterocyclic (thio) carbonyl (the heterocyclic ring contains 1 nitrogen atom, oxygen atom or sulfur atom, and may further contain 1-2 nitrogen atoms or oxygen atoms), the substituent is selected from halogen atom and C1-C8 alkyl group 1-3 same or different substituents, A 5-or 6-membered heterocyclic (thio) carbonyl (containing 1 nitrogen atom, oxygen atom or sulfur atom in the ring of the heterocyclic ring, and optionally 1 to 2 nitrogen atoms), a C1-C18 alkoxy (thio) carbonyl or C1-C18 alkylthio (thio) carbonyl (the substituent may be 1 or more of the same or different substituents selected from a halogen atom, a C1-C8 alkoxy group and a phenyl group), a C2-C8 alkenyloxy (thio) carbonyl, a C2-C8 alkenylthio (thio) carbonyl, a C2-C8 alkynyloxy (thio) carbonyl, a C2-C8 alkynylthio (thio) carbonyl, a C3-C8 cycloalkyloxy (thio) carbonyl, a C3-C8 cycloalkylthio (thio) carbonyl, a substituted phenoxy (thio) carbonyl, a phenylthio (thio) carbonyl, a benzene C1-C5 alkyloxy (thio) carbonyl or a benzene C8 alkylcarbonyl group substituted with 1 to 2 nitrogen atoms, C1-C8 alkyl, cyanoA group consisting of C1-C8 alkylcarbonyl, C1-C8 alkoxycarbonyl, nitro and C1-C8 alkoxy, which may be the same or different, 1-3 substituents), condensed polycyclic hydrocarbyloxy (thio) carbonyl, condensed polycyclic hydrocarbylthio (thio) carbonyl, optionally substituted 5-or 6-membered heterocyclic oxy (thio) carbonyl or 5-or 6-membered heterocyclic thio (thio) carbonyl { the ring of the heterocycle contains 1 nitrogen atom, oxygen atom or sulfur atom, and may further contain 1-2 nitrogen atoms. The substituent is a halogen atom, a C1-C8 alkyl group, a phenoxy group which may be substituted (the substituent is 1 to 3 identical or different substituents selected from a halogen atom, a C1-C8 alkyl group, a C1-C8 haloalkyl group, a C3-C8 cycloalkyl group and a C1-C8 alkoxycarbonyl group), a 2, 3-dihydro-1H-indenyloxy group and a benzoyl group which may be substituted (the substituent is 1 to 3 identical or different substituents selected from a halogen atom, a C1-C8 alkyl group, a C1-C8 haloalkyl group, a C1-C8 alkoxycarbonyl group, a nitro group and a C1-C42 alkylsulfonyl group), a aminomethyl (thio) acyl group which may be substituted { the substituent is a plurality of identical or different substituents selected from a C1-C8 alkyl group which may be substituted (the substituent is 1 to 3 identical or different substituents selected from a halogen atom, a C5956 alkoxycarbonyl group, a cyano group, a phenyl group and a C1-C8 alkoxycarbonyl group), 1 to 3 substituents selected from C2 to C8 alkenyl, phenyl, C1 to C8 alkylcarbonyl, C1 to C8 alkoxycarbonyl and C1 to C8 alkoxy, which may be the same or different,
Figure BDA0001790744410000111
(Het is a 5-6 membered heterocyclic ring containing, in addition to the C and N atoms in position 1, 0-3 or fewer atoms or groups as ring members O, NRb、C＝O，RaAnd RbIndependently represents hydrogen, C1-C8 alkyl), optionally substituted C1-C8 alkylsulfoxide, C1-C8 alkylsulfonyl, C2-C8 alkenylsulfonyl or C3-C8 cycloalkylsulfonyl (the substituent is 1 or more same or different substituents selected from halogen atom, C1-C8 alkylsulfonyl), optionally substituted phenylsulfonyl, benzylsulfonyl or naphthylsulfonyl [ the substituent is selected from halogen atom, C1-C8 alkyl, halogenated C1-C8 alkyl, cyano, C1-C8 alkylcarbonyl, C1-C8 alkyl)Alkoxycarbonyl, nitro, C1 to C8 alkoxy, halogenated C1 to C8 alkoxy, C1 to C8 alkylsulfonyl, optionally substituted aminoacyl (the substituent is C1 to C8 alkyl), optionally substituted phenoxy (the substituent is 1 to 3 substituents selected from a halogen atom, C1 to C8 alkyl, C8 to C8 haloalkyl, C8 to C8 cycloalkyl and C8 to C8 alkoxycarbonyl), optionally substituted C8 to C8 alkenyloxysulfonyl { the substituent is C8 to C8 cycloalkyl, cyano and optionally substituted benzoyl (the substituent is 1 to 3 substituents selected from a halogen atom, C8 to C8 alkyl, C8 to C8 haloalkyl, C8 to C8 alkoxycarbonyl, nitro and C8 alkylsulfonyl) and optionally substituted C3 } substituents are the same or different C3 substituents selected from a halogen atom, C8 to C8 alkyl, C8 alkoxy, nitro and C8 to C8 alkylsulfonyl { the substituent is optionally substituted C8 to C8 oxo } sulfonyl { the substituent is optionally substituted phenyl } substituted phenyl { the group The substituent is 1 to 2 identical or different substituents selected from 1 to 3 identical or different substituents selected from a halogen atom, a C1 to C8 alkyl group, a C1 to C8 haloalkyl group, a C1 to C8 alkoxycarbonyl group, a nitro group and a C1 to C8 alkylsulfonyl group), and a 5-or 6-membered heterocyclyloxysulfonyl group which may be substituted { the heterocycle has 1 nitrogen atom, oxygen atom or sulfur atom in the ring, and may further have 1 to 2 nitrogen atoms. The substituent is 1 to 3 identical or different substituents selected from a halogen atom, a C1 to C8 alkyl group, a phenoxy group which may be substituted (the substituent is 1 to 3 identical or different substituents selected from a halogen atom, a C1 to C8 alkyl group, a C1 to C8 haloalkyl group, a C3 to C8 cycloalkyl group and a C1 to C8 alkoxycarbonyl group), a 2, 3-dihydro-1H-indenyloxy group and a benzoyl group which may be substituted (the substituent is 1 to 3 identical or different substituents selected from a halogen atom, a C1 to C8 alkyl group, a C1 to C8 haloalkyl group, a C1 to C8 alkoxycarbonyl group, a nitro group and a C1 to C8 alkylsulfonyl group)]5-to 10-membered heterocyclylsulfonyl or 5-to 10-membered heterocyclyloxysulfonyl which may be substituted { the heterocycle contains 1 nitrogen atom, oxygen atom or sulfur atom in the ring, and may further contain 1 to 2 nitrogen atoms. The substituent is selected from halogen atom, C1-C8 alkyl, and optionally substituted phenoxy (the substituent is selected from halogen atom, C1-C8)Alkyl, C1-C8 haloalkyl, C3-C8 cycloalkyl and C1-C8 alkoxycarbonyl, 1 to 3 substituents which are the same or different and which are selected from the group consisting of halogen atoms, C1-C8 alkyl, C1-C8 haloalkyl, C1-C8 alkoxycarbonyl, nitro and C1-C8 alkylsulfonyl, 2, 3-dihydro-1H-indoxyl and benzoyl which may be substituted, which is the same or different and which is 1 to 3 substituents which are the same or different and which are selected from the group consisting of halogen atoms, C1-C8 alkylsulfonyl, C1-C8 alkylaminosulfonyl which may be substituted, which is 1 or more substituents which are the same or different and which are selected from the group consisting of halogen atoms,
Figure BDA0001790744410000121
(Het is a 5-6 membered heterocyclic ring containing, in addition to the C and N atoms in position 1, 0-3 or fewer atoms or groups as ring members O, NRb、C＝O，RaAnd RbIndependently represents a compound bonded with hydrogen, C1-C8 alkyl, di (C1-C8 alkyl) phosphoryl and di (C1-C8 alkyl) thiophosphoryl.
Preferably, the substituent may be a C1 to C10 alk (thio) carbonyl group { which may be substituted by 1 or more identical or different substituents selected from fluorine, chlorine, bromine, C3 to C6 cycloalkyl, C1 to C6 alkoxy, C1 to C6 alkylthio, C1 to C6 alkoxycarbonyl, C1 to C6 alkylcarbonyl, C1 to C6 alkylcarbonyloxy, phenyl, phenylthio, phenoxy or benzyloxy which may be substituted (which may be selected from fluorine, chlorine, bromine, C1 to C6 alkyl, and 1 to 3 same or different substituents selected from fluorine, chlorine, bromine, C6 alkyl, and C6 alkoxy), a C6 to C6 cycloalkyl (thio) carbonyl group { which may be substituted by 1 to 3 same or different substituents selected from fluorine, chlorine, bromine, C6 alkoxy, phenyl, phenylthio, or phenoxy (which may be substituted by fluorine, chlorine, bromine, C1 to C6 alkyl, and 6 alkoxy } or a plurality of same or different substituents selected from fluorine, chlorine, bromine, C1 to C6 alkoxy } and 6 alkoxy } may be substituted by one or more same or different substituents selected from one, A benzoyl (thio) acyl group or a naphthoyl (thio) acyl group which may be substituted { the substituent is a C1-C6 alkyl group or a C1-C6 alkoxy group which may be substituted (the substituent is the same or selected from the group consisting of fluorine, chlorine, bromine and phenyl group1 to 3 different substituents), cyano, hydroxy, C1 to C6 alkylcarbonyl, C1 to C6 alkoxycarbonyl, C1 to C6 alkylcarbonyloxy, C1 to C6 alkylcarbonylamino, 1 to 3 identical or different substituents selected from C1 to C6 alkyl, C1 to C6 alkoxy, C1 to C6 alkylcarbonyl, halogenated C1 to C6 alkyl and phenyl, nitro, phenoxy, 1 to 3 identical or different substituents selected from 3 to 8-membered heterocyclic (thio) carbonyl { the heterocyclic ring is a heterocyclic ring having 1 to 3 substituents) which may be substituted
Figure BDA0001790744410000122
Figure BDA0001790744410000123
The substituent is selected from fluorine, chlorine, bromine, C1-C6 alkyl which may be substituted (the substituent is 1 or more same or different substituents selected from fluorine, chlorine, bromine and phenyl), C1-C6 alkylcarbonyl, C1-C6 alkoxycarbonyl, phenyl which may be substituted (the substituent is 1-3 same or different substituents selected from fluorine, chlorine and bromine), nitro, hydroxyl, C1-C6 alkoxy, phenoxy, C1-C6 alkylthio, C2-C6 alkenylthio and phenylthio), 5-14 membered condensed bicyclic or tricyclic heterocyclic (thio) carbonyl which may be substituted (the heterocyclic is 1-3 same or different substituents selected from fluorine, chlorine, bromine and phenyl)
Figure BDA0001790744410000124
Figure BDA0001790744410000125
Figure BDA0001790744410000131
Figure BDA0001790744410000132
The substituents are 1 to 3 same or different substituents selected from fluorine, chlorine, bromine and C1 to C6 alkyl), C1 to C10 alkoxy (thio) carbonyl or C1 to C10 alkylthio (thio) carbonyl which may be substituted (the substituents are 1 or more selected from fluorine, chlorine, bromine, C1 to C6 alkoxy and phenyl)Identical or different substituents), C3-C6 cycloalkyloxy (thio) carbonyl, C3-C6 cycloalkylthio (thio) carbonyl, optionally substituted phenoxy (thio) carbonyl, phenylthio (thio) carbonyl, benzene C1-C6 alkyloxy (thio) carbonyl or benzene C1-C6 alkylthio (thio) carbonyl (the substituents being identical or different 1-3 substituents selected from fluorine, chlorine, bromine, C1-C6 alkyl, cyano, C1-C6 alkylcarbonyl, C1-C6 alkoxycarbonyl, nitro and C1-C6 alkoxy), optionally substituted aminomethyl (thio) acyl { the substituents being optionally substituted C1-C6 alkyl (the substituents being 1 or more identical or different substituents selected from fluorine, chlorine, bromine), C2-C6 alkenyl, phenyl, C1-C6 alkylcarbonyl, C72-C6 alkoxycarbonyl and optionally substituted C6-C6 alkoxycarbonyl }, and,
Figure BDA0001790744410000133
(Het is
Figure BDA0001790744410000134
Figure BDA0001790744410000135
RaAnd RbIndependently represents hydrogen, C-C alkyl), a C-C alkylsulfoxide group which may be substituted, a C-C alkylsulfonyl group, a C-C alkenylsulfonyl group or a C-C cycloalkylsulfonyl group (the substituent may be 1 or more of the same or different substituents selected from fluorine, chlorine, bromine and C-C alkylsulfonyl), a phenylsulfonyl group, a benzylsulfonyl group or a naphthylsulfonyl group which may be substituted { the substituent may be a same substituent selected from fluorine, chlorine, bromine, C-C alkyl, a halogenated C-C alkyl group, a cyano group, a C-C alkylcarbonyl group, a C-C alkoxycarbonyl group, a nitro group, a C-C alkoxy group, a halogenated C-C alkoxy group, a C-C alkylsulfonyl group, an aminoacyl group which may be substituted (the substituent may be a C-C alkyl group), a phenoxy group which may be substituted (the substituent may be the same or different 1 to 3 substituents selected from fluorine, chlorine, bromine, a C-C alkyl group, a C-C haloalkyl group, a C-C cycloalkyl group and a C-C alkoxycarbonyl group) Or 1 to 3 different substituents }, a 5-to 10-membered heteroarylsulfonyl group which may be substituted{ the heterocycle is
Figure BDA0001790744410000136
Figure BDA0001790744410000137
Figure BDA0001790744410000141
The substituent is 1 to 3 same or different substituents selected from fluorine, chlorine, bromine, C1 to C6 alkyl, optionally substituted phenoxy (1 to 3 same or different substituents selected from fluorine, chlorine, bromine, C1 to C6 alkyl, C1 to C6 haloalkyl, C3 to C6 cycloalkyl and C1 to C6 alkoxycarbonyl), optionally substituted C1 to C6 alkylaminosulfonyl (1 or more same or different substituents selected from fluorine, chlorine and bromine), or optionally substituted,
Figure BDA0001790744410000142
(Het is
Figure BDA0001790744410000143
RaAnd RbIndependently represents a compound bonded with hydrogen, C1-C6 alkyl, di (C1-C6 alkyl) phosphoryl and di (C1-C6 alkyl) thiophosphoryl.
The oxime derivative is a compound containing an oxime group bonded to an oxygen atom of a hydroxyl group at the 4-position of the pyridazine ring
Figure BDA0001790744410000144
The compound of (1) can be, for example, R11、R22Each independently represents hydrogen, an optionally substituted C1-C18 alkyl group or C2-C18 alkenyl group (the substituent is 1 or more identical or different substituents selected from a halogen atom, a C1-C8 alkoxy group, a C1-C8 alkylthio group, and a C1-C8 alkylamino group), an optionally substituted phenyl group, a phenylacyl group, or a 5-6-membered heterocyclic aromatic group (the substituent is a halogen atom, a C1-C8 alkyl group, a C2-C8 alkenyl group, a C2-C8 alkynyl group, a C3-C8 cycloalkyl group, a C1-C8 haloalkyl group, a C1-C8 alkylcarbonyl group, a C1-C8 alkoxy group, a C1-C8 alkoxycarbonyl groupC1-C8 alkylamino, hydroxy, carboxy, mercapto, amino, cyano, nitro and C1-C8 alkylsulfonyl, wherein the arylheterocyclyl contains at least one heteroatom such as oxygen, sulfur, nitrogen), or R11、R22Form a 5, 6-membered saturated carbocyclic ring or a 5, 6-membered heterocyclic ring (containing at least one heteroatom such as oxygen, sulfur, nitrogen, etc.).
Preferably, R may be11、R22Each independently represents hydrogen, an optionally substituted C1-C10 alkyl group or C2-C10 alkenyl group (the substituent is 1 or more same or different substituents selected from fluorine, chlorine, bromine, C1-C6 alkoxy, C1-C6 alkylthio group, and C1-C6 alkylamino group), an optionally substituted phenyl group, a phenylacyl group, or a 5-6 membered aromatic heterocyclic group (the aromatic heterocyclic group is an optionally substituted phenyl group, a phenylacyl group, or a 5-6 membered aromatic heterocyclic group
Figure BDA0001790744410000145
Figure BDA0001790744410000146
The substituent is 1 to 3 identical or different substituents selected from fluorine, chlorine, bromine, C1 to C6 alkyl, C3 to C6 cycloalkyl, C1 to C6 haloalkyl, C1 to C6 alkylcarbonyl, C1 to C6 alkoxy, C1 to C6 alkoxycarbonyl, C1 to C6 alkylamino, hydroxyl, carboxyl, mercapto, amino, cyano, nitro and C1 to C6 alkylsulfonyl), or R11、R22Form a 5, 6-membered saturated carbocyclic ring or a 5, 6-membered heterocyclic ring (containing at least one heteroatom such as oxygen, sulfur, nitrogen, etc.).
The hydroxylamine derivative is a hydroxylamine-containing group bonded to the oxygen atom of the hydroxyl group at the 4-position of the pyridazine ring
Figure BDA0001790744410000147
The compound of (1) can be, for example, R11’、R22' independently represent hydrogen, a C1-C18 alkyl group or a C2-C18 alkenyl group which may be substituted (the substituent is 1 or more same or different substituents selected from a halogen atom, a C1-C8 alkoxy group, a C1-C8 alkylthio group, a C1-C8 alkylamino group), a phenyl group which may be substituted (the substituent is selected from a halogen atom, a C1EC8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, C1-C8 haloalkyl, C1-C8 alkylcarbonyl, C1-C8 alkoxy, C1-C8 alkoxycarbonyl, C1-C8 alkylamino, hydroxyl, carboxyl, mercapto, amino, cyano, nitro and 1-3 substituents selected from C1-C8 alkylsulfonyl, C1-C18 alkoxycarbonyl, optionally substituted benzoyl [ the substituent is a halogen atom, optionally substituted C1-C1 alkyl, C1-C1 alkenyl, C1-C1 alkynyl or C1-C1 cycloalkyl (the substituent is a 1-3 substituents selected from halogen atom and phenyl), cyano, C1-C1 alkylcarbonyl, C1-C1 alkoxycarbonyl, C3972-C1 alkylsulfonyl, optionally substituted cyano { 1-C1 alkoxycarbonyl and { 1 substituent is a halogen atom { 1-C1 substituent, C1-C8 alkyl, C1-C8 haloalkyl, C1-C8 alkoxycarbonyl, nitro and 1-3 identical or different substituents selected from C1-C8 alkylsulfonyl), C3-C8 cycloalkoxycarbonyl which may be substituted (the substituent is 1-2 identical or different substituents selected from oxo and optionally substituted benzoyl (the substituent is 1-3 identical or different substituents selected from halogen atom, C1-C8 alkyl, C1-C8 haloalkyl, C1-C8 alkoxycarbonyl, nitro and C1-C8 alkylsulfonyl), hydroxy, carboxy, mercapto, amino, phenyl, nitro, optionally substituted C1-C8 alkoxy, C1-C8 alkylamino or C1-C8 alkylamino (the substituents are 3 identical or different substituents selected from alkylthio) and phenyl), Phenoxy group, optionally substituted 5-or 6-membered heterocyclyloxycarbonyl group { the ring of the heterocycle contains 1 nitrogen atom, oxygen atom or sulfur atom, and may further contain 1 to 2 nitrogen atoms. The substituent is selected from halogen atom, C1-C8 alkyl, optionally substituted phenoxy (the substituent is selected from 1-3 identical or different substituents selected from halogen atom, C1-C8 alkyl, C1-C8 haloalkyl, C3-C8 cycloalkyl and C1-C8 alkoxycarbonyl), 2, 3-dihydro-1H-indenoxy and optionally substituted benzoyl (the substituent is selected from halogen atom, C1-C8 alkyl, C1-C8 haloalkaneA group consisting of C1-C8 alkoxycarbonyl group, nitro group and C1-C8 alkylsulfonyl group, which may be the same or different, which may be 1-3 substituents) and optionally substituted 5-or 6-membered heterocyclyloxysulfonyl group { the heterocycle may contain 1 nitrogen atom, oxygen atom or sulfur atom in the ring, and may further contain 1-2 nitrogen atoms. The substituent is 1 to 3 identical or different substituents selected from a halogen atom, a C1 to C8 alkyl group, a phenoxy group which may be substituted (the substituent is 1 to 3 identical or different substituents selected from a halogen atom, a C1 to C8 alkyl group, a C1 to C8 haloalkyl group, a C3 to C8 cycloalkyl group and a C1 to C8 alkoxycarbonyl group), a 2, 3-dihydro-1H-indenyloxy group and a benzoyl group which may be substituted (the substituent is 1 to 3 identical or different substituents selected from a halogen atom, a C1 to C8 alkyl group, a C1 to C8 haloalkyl group, a C1 to C8 alkoxycarbonyl group, a nitro group and a C1 to C8 alkylsulfonyl group)]。
Preferably, R may be11’、R22' independently represent hydrogen, a C1-C10 alkyl group or a C2-C10 alkenyl group which may be substituted (the substituent is 1 or more same or different substituents selected from fluorine, chlorine and bromine), a C1-C10 alkoxycarbonyl group, a phenyl group or a benzoyl group which may be substituted (the substituent is 1 or more same or different substituents selected from fluorine, chlorine, bromine, a C1-C6 alkyl group, a C2-C6 alkenyl group, a C2-C6 alkynyl group, a C3-C6 cycloalkyl group, a C1-C6 haloalkyl group, a C1-C6 alkylcarbonyl group, a C1-C6 alkoxy group, a C1-C6 alkoxycarbonyl group, a C1-C6 alkylamino group, a hydroxyl group, a carboxyl group, a mercapto group, an amino group, a cyano group, a nitro group and a C1-C6 alkylsulfonyl group).
The ether derivative is a compound in which the following group is bonded to an oxygen atom of a hydroxyl group at the 4-position of the pyridazine ring, and may be, for example, a C1-C18 alkyl group or a C2-C18 alkenyl group which may be substituted (the substituent is 1 or more same or different substituents selected from a halogen atom, a C1-C8 alkoxy group, a C1-C8 alkylthio group, a C1-C8 alkylamino group, a di-C1-C8 alkylamino group, a C1-C8 alkoxycarbonyl group, and a C1-C8 alkoxycarbonyloxy group), a phenyl group, a benzyl group or a benzoyl group which may be substituted [ the substituted C1-C8 alkyl group ]The group is selected from a halogen atom, a C1-C8 alkyl group which may be substituted, a C2-C8 alkenyl group, a C2-C8 alkynyl group, a C3-C8 cycloalkyl group (the substituents are 1 to 3 same or different substituents selected from a halogen atom and a phenyl group), a cyano group, a C1-C8 alkylcarbonyl group, a C1-C8 alkoxycarbonyl group, a C1-C8 alkylsulfonyl group, a C2-C8 alkenyloxycarbonyl group which may be substituted { the substituents are 1 to 3 same or different substituents selected from a C3-C8 cycloalkyl group, a cyano group and a benzoyl group which may be substituted (the substituents are 1 to 3 same or different substituents selected from a halogen atom, a C1-C8 alkyl group, a C1-C8 haloalkyl group, a C1-C8 alkoxycarbonyl group, a nitro group and a C1-C8 alkylsulfonyl group) } the substituents are 1 to 3 same or different substituents selected from a halogen atom, a C3-C8 alkoxycarbonyl group which may be substituted { the substituents are an oxo group, C1-C8 alkyl, C1-C8 haloalkyl, C1-C8 alkoxycarbonyl, nitro and C1-C8 alkylsulfonyl) 1-2 identical or different substituents selected from 1-3 identical or different substituents }, hydroxyl, carboxyl, mercapto, amino, phenyl, nitro, optionally substituted C1-C8 alkoxy, C1-C8 alkylamino or C1-C8 alkylthio (the substituents are 1-3 identical or different substituents selected from halogen atoms and phenyl), phenoxy, optionally substituted 5-or 6-membered heterocyclyloxycarbonyl { the ring of which contains 1 nitrogen atom, oxygen atom or sulfur atom, and may further contain 1-2 nitrogen atoms. The substituent is selected from a halogen atom, a C1-C8 alkyl group, a phenoxy group which may be substituted (the substituent is 1-3 same or different substituents selected from a halogen atom, a C1-C8 alkyl group, a C1-C8 haloalkyl group, a C3-C8 cycloalkyl group and a C1-C8 alkoxycarbonyl group), a 2, 3-dihydro-1H-indenyloxy group, a benzoyl group which may be substituted (the substituent is 1-3 same or different substituents selected from a halogen atom, a C1-C8 alkyl group, a C1-C8 haloalkyl group, a C1-C8 alkoxycarbonyl group, a nitro group and a C1-C8 alkylsulfonyl group), and a 5-or 6-membered heterocyclic oxysulfonyl group which may be substituted { the ring of the heterocyclic ring contains 1 nitrogen atom, an oxygen atom or a sulfur atom, and may further contain 1-2 nitrogen atoms. The substituent is selected from halogen atom, C1-C8 alkylA phenoxy group which may be substituted (the substituent is 1 to 3 identical or different substituents selected from a halogen atom, a C1-C8 alkyl group, a C1-C8 haloalkyl group, a C3-C8 cycloalkyl group and a C1-C8 alkoxycarbonyl group), a 2, 3-dihydro-1H-indoxyl group and 1 to 3 identical or different substituents selected from a benzoyl group which may be substituted (the substituent is 1 to 3 identical or different substituents selected from a halogen atom, a C1-C8 alkyl group, a C1-C8 haloalkyl group, a C1-C8 alkoxycarbonyl group, a nitro group and a C1-C8 alkylsulfonyl group)]. Wherein, when X represents cyano in the general formula I-1, Ar represents
Figure BDA0001790744410000171
When the above group M is not a methyl group.
Preferably, the substituted alkyl group may be a C8 to C18 alkyl group, a C8 to C18 alkenyl group, a substituted C1 to C10 alkyl group, a C2 to C10 alkenyl group (the substituent may be 1 or more same or different substituents selected from fluorine, chlorine, bromine, C1 to C6 alkoxy groups, C1 to C6 alkylthio groups, C1 to C6 alkylamino groups, C1 to C6 alkoxycarbonyl groups, and C1 to C6 alkoxycarbonyloxy groups), a substituted phenyl group, benzyl group, or benzoyl C1 to C6 alkyl group (the substituent may be one or more same or different substituents selected from fluorine, chlorine, bromine, C6 to C6 alkyl groups, C6 to C6 alkenyl groups, C6 to C6 alkynyl groups, C6 to C6 cycloalkyl groups, C6 to C6 haloalkyl groups, C6 to C6 alkylcarbonyl groups, C6 to C6 alkoxy groups, C6 to C6 alkoxycarbonyl groups, C6 alkyl groups, C6 to C6, C6 to C6 alkylamino groups, and nitro sulfonyl groups).
A preparation method of the five-membered ring substituted pyridazinol compound comprises the following steps:
(1) carrying out Suzuki reaction on a compound II and a compound III to prepare a compound shown as a general formula IV;
(2) carrying out halogenation reaction on the compound shown in the general formula IV to prepare a compound shown in the general formula V;
(3) preparing a compound shown as a general formula I by hydrolyzing a compound shown as a general formula V;
the chemical reaction equation is as follows:
Figure BDA0001790744410000172
L1and L2Each independently represents halogen, preferably chlorine, bromine, iodine.
The reaction temperature is within the range of 20-150 ℃, and preferably 50-130 ℃.
The step (1) is carried out in the presence of a catalyst, a base and a solvent, wherein the catalyst is Pd (dppf) Cl2CH2Cl2、Pd(dba)2、Pd2(dba)3、Pd(PPh3)4、PdCl2、Pd(OAc)2、Pd(dppf)Cl2、Pd(PPh3)2Cl2Or Ni (dppf) Cl2The base is selected from Et3N、NaHCO3、KOAc、K2CO3、K3PO4、Na2CO3、CsF、Cs2CO3One or more than two of t-BuONa, EtONa, KOH and NaOH, wherein the solvent is THF/water, toluene/water, DMF/water, 1, 4-dioxane/water, toluene/ethanol/water or acetonitrile/water, THF, toluene, 1, 4-dioxane, acetonitrile and DMF system; the step (2) is carried out in the presence of a halogenating reagent, a catalyst and a solvent, wherein the halogenating reagent is N-chlorosuccinimide, N-bromosuccinimide or N-iodosuccinimide, the catalyst is benzoyl peroxide, and the solvent is acetonitrile; the step (3) is carried out in the presence of a base and a solvent, or in the presence of boron tribromide, hydrobromic acid acetic acid solution, hydrochloric acid methanol solution and hydrochloric acid ethyl acetate solution, wherein the base is preferably NaOH, KOH, potassium acetate and sodium acetate, and the solvent is preferably water and DMSO.
The chemical reaction equation for preparing the ester and ether derivatives is as follows:
Figure BDA0001790744410000181
wherein, Y1Halogen, preferably chlorine, bromine;
the chemical reaction equation for preparing oxime and hydroxylamine derivatives is as follows:
Figure BDA0001790744410000182
wherein, Y2Halogen, preferably chlorine and fluorine.
The reaction for preparing the ester and ether derivatives and the second reaction for preparing the oxime and hydroxylamine derivatives are carried out in the presence of alkali and solvent, wherein the alkali is one or more than two of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, cesium carbonate, triethylamine and diisopropylethylamine; the solvent is THF, 1, 4-dioxane, toluene, 1, 2-dichloroethane, ethyl acetate, acetonitrile, DMF, acetone, dichloromethane or chloroform; the first step of the reaction for preparing the oxime and hydroxylamine derivatives thereof is carried out in the presence of a halogenating agent, Phenofluor/cesium fluoride or POCl, and a solvent3The solvent is one or more than two of toluene, 1, 2-dichloroethane and DMF; the reaction temperature is selected from the range of 0-120 ℃, and preferably 20-80 ℃.
The compounds to which the present invention relates may exist in the form of one or more stereoisomers. The various isomers include enantiomers, diastereomers, geometric isomers. It is within the scope of the present invention for these isomers to include mixtures of these isomers.
A herbicide composition comprises (I) a five-membered ring substituted pyridazinol compound shown as a general formula I and a derivative thereof.
Preferably, it further comprises (ii) one or more additional herbicides and/or safeners.
More preferably, (iii) an agrochemically acceptable formulation auxiliary.
The additional herbicide is selected from one of HPPD inhibitors, hormones, PDS inhibitors; preferably, the HPPD inhibitor is sulcotrione, mesotrione, topramezone, tembotrione, fluroxypyr, mesotrione, benzobicyclon, lancotrione, topramezone, triazophone, topramezone, pyrazox, pyrazotoconazole, pyraflutole, tralkoxydim, tolpyralate, fenquinotrione, isoxaflutole; the hormones are fluroxypyr, quinclorac, 2-methyl-4-chlorophenoxypropionic acid, MCPB, 2,4-D, 2, 4-dichlorpropionic acid, 2,4-DB, dicamba, picloram, triclopyr, clopyralid, triclopyr and derivatives thereof, and the PDS inhibitor is flurtamone, diflufenican, flurbiprofen, beflubutamid, flurfenpyr, and fluridone.
Among them, fluroxypyr derivatives include, but are not limited to: fluroxypyr meptyl ester; 2-methyl-4-chloro-phenoxy-2-methyl-4-chlorophenoxypropionic acid, MCPB derivatives include but are not limited to: sodium salt, potassium salt, dimethylammonium salt, isopropylamine salt, etc., and methyl ester, ethyl ester, isooctyl ester, ethyl thioester, etc.; 2,4-D, 2, 4-Dipropionic acid, 2,4-DB derivatives include but are not limited to: salts such as sodium, potassium, dimethylammonium, triethanolammonium, isopropylamine, choline and the like, and esters such as methyl, ethyl, butyl, isooctyl and the like.
A method for controlling noxious plants, which comprises applying a herbicidally effective amount of at least one of the five-membered ring-substituted pyridazinol compounds and derivatives thereof or the herbicidal composition to plants or a noxious plant area.
The application of at least one of the five-membered ring substituted pyridazinol compounds and derivatives thereof or the herbicide composition in controlling harmful plants.
Preferably, the five-membered ring substituted pyridazinol compound and at least one of the derivatives thereof or the herbicidal composition is used for controlling harmful plants in crops of useful plants.
More preferably, the useful crop is a transgenic crop or a crop treated with genome editing techniques.
The compounds of the formula I according to the invention have outstanding herbicidal activity against a large number of economically important monocotyledonous and dicotyledonous harmful plants. The active substances according to the invention are also effective against perennial weeds which grow from rhizomes, or other perennial organs and are difficult to control. In this connection, it is generally immaterial whether the substance is used before sowing, before germination or after germination. Mention is made in particular of representative examples of the monocotyledonous and dicotyledonous weed groups which the compounds of the invention can control, without being restricted to a defined species. Examples of weed species for which the active substance acts effectively include monocotyledons: annual avena, rye, grass, alopecurus, farris, barnyard grass, digitaria, setaria and sedge, and perennial agropyron, bermudagrass, cogongrass and sorghum, and perennial sedge.
With regard to dicotyledonous weed species, the action can be extended to species such as the annual cleavers, viola, veronica, picea, chickweed, amaranthus, sinapis, ipomoea, sida, matricaria and abutilon species, and the perennial weeds cyclocarya, thistle, sorrel and artemisia. The active substances according to the invention are effective in controlling harmful plants, such as barnyard grass, sagittaria, alisma, eleocharis, saccharum and cyperus, in this particular condition of sowing of rice. If the compounds of the present invention are applied to the soil surface before germination, seedlings of weeds can be completely prevented before the weeds grow out, or the weeds stop growing when they grow out of cotyledons and finally die completely after three to four weeks. The compounds of the invention are particularly active against plants such as, for example, alpinia, sesamum indicum, polygonum convolvulus, chickweed, veronica vinifera, veronica albo, viola tricolor and amaranth, cleavers and kochia.
Although the compounds of the invention have excellent herbicidal activity against monocotyledonous and dicotyledonous weeds, they are not at all harmful or only insignificantly harmful to the important economic crop plants, such as wheat, barley, rye, rice, maize, sugar beet, cotton and soybean. Especially good compatibility with cereal crops such as wheat, barley and maize, especially wheat. The compounds according to the invention are therefore very suitable for selectively controlling unwanted vegetation in agricultural crops or ornamental plants.
Due to their herbicidal properties, these active substances can be used for controlling harmful plants in the cultivation of genetically engineered plants which are known or are to occur. Transgenic plants often have advantageous traits, such as resistance to specific insecticides, particularly to specific herbicides, resistance to plant diseases or to microorganisms pathogenic to plant diseases, such as specific insects or microorganisms of fungi, bacteria or viruses. Other specific traits are related to the conditions of the product, such as quantity, quality, storage stability, composition and specific ingredients. Thus, it is known that the resulting transgenic plant products have an increased starch content or an improved starch quality or a different fatty acid composition.
The compounds of the formula I according to the invention or their salts are preferably used for economically important transgenic crops and ornamentals, for example cereals, such as wheat, barley, rye, oats, millet, rice, cassava and maize, or for the cultivation of sugar beet, cotton, soybean, rapeseed, potato, tomato, pea and other vegetable plants. The compounds of the formula I are preferably used as herbicides for cultivating useful plants which are resistant to the action of the herbicide or which are resistant to the toxic action of the herbicide by genetic engineering.
Conventional methods for breeding plants having improved shape over known plants include, for example, conventional mating methods and mutant breeding. In other words, new plants with improved traits may be obtained by means of methods of genetic engineering (see, for example, EP-0221044A, EP-0131624A). For example, several methods have been described:
to improve starch synthesis in plants, crop plants are modified by genetic engineering (e.g. WO 92/11376, WO92/14827, WO 91/19806);
transgenic crop plants which are resistant to particular herbicides, to glufosinate herbicides (e.g. EP-0242236A, EP-0242246A) or to glyphosate-type herbicides (WO 92/00377), or to sulfonylurea-type herbicides (EP-0257993A, US-5013659A);
transgenic crop plants, such as cotton, which produce Bacillus thuringiensis toxins (Bt toxins) which protect against attack on plants by specific pests (EP-0142924A, EP-0193259A);
-transgenic crop plants with improved fatty acid composition (WO 91/13972).
A number of molecular biotechnologies are known which enable the production of transgenic plants with improved traits (see, for example, Sambrook et al, 1989, molecular amplification, second edition of the laboratory Manual, Cold spring harbor laboratory publications in USA, Cold spring harbor, New York; or Winnacker "Gene und Klone" [ genes and clones ], VCH Weinheim, second edition 1996 or Christou, "trends in plant science" 1(1996)423- "431)). In order to carry out the manipulation of genetic engineering, it is possible to introduce nucleic acid molecules into plasmids, which undergo mutations or sequence changes by recombination of DNA sequences. Using standard methods as described above, it is possible, for example, to exchange substrates, remove partial sequences or add natural or synthetic sequences. In order to ligate the DNA fragments to each other, it is possible to attach a binder or a linker to the fragments.
Plant cells of reduced activity gene products can be prepared, for example, by expressing at least one suitable antisense-RNA, sense-RNA to achieve a cosuppression effect, or by expressing at least one suitably configured ribozyme which specifically cleaves transcripts of the gene products.
For this purpose, it is possible to use DNA molecules which contain the entire coding sequence of the gene product, including any flanking sequences which may be present, and to use DNA molecules which contain only a part of the coding sequence which has to be long enough to achieve an antisense effect in the cell. Sequences that are highly homologous but not identical to the coding sequence of the gene product may also be used.
When expressing the nucleic acid molecule in a plant, the synthetic protein can be localized in any desired plant cell compartment. However, for localization in a specific chamber, it is possible, for example, to link the coding region to a DNA sequence in order to ensure localization in a specific location. These sequences are known to those skilled in the art (see, for example, Braun et al, EMBO J.11(1992) 3219-3227; Wolter et al, Proc. Natl. Acad. Sci. USA 85(1988), 846-850; Sonnewald et al Plant J.1(1991), 95-106).
Transgenic plant cells can be recombined into whole plants using known techniques. The transgenic plant may be of any desired plant variety, i.e., monocotyledonous and dicotyledonous plants. In this way, it is possible to obtain transgenic plants with improved traits by overexpressing, inhibiting or suppressing homologous (═ natural) genes or gene sequences, or by expressing heterologous (═ external) genes or gene sequences.
When the active substances according to the invention are used on transgenic crops, in addition to the harmful-plant-inhibiting effects observed on other crops, special effects are often observed on the corresponding transgenic crops, for example an improved or enlarged spectrum of weed control, improved application rates in the application, preferably a good combination of resistance of the transgenic crop and herbicide performance, and an influence on the growth and yield of the transgenic crop plants. The invention therefore also provides for the use of the compounds as herbicides for controlling harmful plants in transgenic crop plants.
In addition, the compound of the invention can obviously regulate the growth of crop plants. These compounds are used to target the control of plant components and to promote harvesting, such as desiccation and stunting of plants, by regulating the metabolism of plants involved. They are also suitable for regulating and inhibiting undesirable vegetation without destroying the growth of the crop plants. Inhibiting plant growth plays a very important role in many monocotyledonous and dicotyledonous crop plants, since this reduces or completely prevents lodging.
The compounds of the present invention may be applied using a general formulation, wettable powders, concentrated emulsions, sprayable solutions, powders or granules may be used, so the present invention also provides herbicidal compositions comprising compounds of formula I. depending on the general biological and/or chemical physical parameters, the compounds of formula I may be formulated in a variety of ways. examples of suitable formulation choices are Wettable Powders (WP), water Soluble Powders (SP), water soluble concentrates, concentrated Emulsions (EC), emulsions such as oil dispersed in water and water dispersed in oil (EW), sprayable solutions, Suspension Concentrates (SC), dispersible oil suspensions (OD), suspensions with oil or water as diluents, miscible oil solutions, powders (DP), Capsule Suspensions (CS), core encapsulated (casing) compositions, granules for broadcasting and soil application, Spray granules, coated granules and absorbent granules, water dispersible granules (WG), water Soluble Granules (SG), water soluble granules (formula), microcapsules and wax preparations, these individual formulations are known in the literature, published as "mineral, published under" market, 9, published ", published by" company.
The necessary formulation auxiliaries, such as inerts, surfactants, solvents and other additives, are likewise known and are described in the documents mentioned below, for example in Watkins, "handbook of powdered diluents pesticides and carriers", second edition, Darland book Caldwell n.j.; h.v.01phen, "entry to clay colloid chemistry," second edition, j.wiley and Sons, n.y.; marsden, second edition "solvent guide", Interscience, n.y.1963; "annual report of detergents and emulsifiers" by McCutcheon, MC issues, Ridgewood n.j.; sisley and Wood, "surfactant encyclopedia", chemical publishing company, n.y.1964;
Figure BDA0001790744410000221
is/are as follows
Figure BDA0001790744410000222
[ ethylene oxide adduct surfactant]"Chemische Technologie" of Wiss.Verlagagesell.Stuttgart 1976, Winnacker-K ü chler [ chemical Process]Volume 7, c.hauser Verlag Munich, 4 th edition 1986.
Wettable powders can be uniformly dispersed in water and, in addition to the active substance, include diluents or inert substances, ionic and nonionic surfactants (wetting agents, dispersants), such as polyethoxylated alkylphenols, polyethoxylated fatty alcohols, polyoxyethylated fatty amines, fatty alcohol polyglycol ether sulfates, alkylsulfonates, alkylphenylsulfonates, sodium lignosulfonates, sodium 2,2 '-dinaphthylmethane-6, 6' -disulfonate, sodium dibutylnaphthalenesulfonate or sodium oleoylmethyltaurate. To prepare wettable powders, the active substances of the herbicides are finely ground, for example using customary instruments, such as hammer mills, fan mills and jet mills, with simultaneous or sequential incorporation of the adjuvants.
Emulsions are prepared by dissolving the active substance in an organic solvent, such as butanol, cyclohexanone, dimethylformamide, xylene or higher boiling aromatics or hydrocarbons or mixtures of solvents, and adding one or more ionic and/or nonionic surfactants (emulsifiers). Examples of emulsifiers which may be used are calcium alkylarylsulfonates, for example calcium dodecylbenzenesulfonate, or nonionic emulsifiers, for example polyglycol esters of fatty acids, alkylarylpolyglycol ethers, fatty alcohol polyglycol ethers, propylene oxide-ethylene oxide condensation products, alkyl polyethers, sorbitan esters, for example sorbitan fatty acid esters, or polyoxyethylene sorbitan esters, for example polyoxyethylene sorbitan fatty acid esters.
The active substance and finely divided solid substances, for example talc, natural clays such as kaolin, bentonite and pyrophyllite, or diatomaceous earth, are ground to give a powder. Water or oil based suspensions may be prepared, for example, by wet milling using a commercially available bead mill, with or without the addition of a surfactant of the other formulation type described above.
For preparing emulsions, for example oil-in-water Emulsions (EW), it is possible to use aqueous organic solvents, using stirrers, colloid mills and/or static mixers, and, if desired, to add surfactants of another formulation type as described above.
Granules are prepared by spraying the active substance onto the adsorbate, granulating with inert material, or concentrating the active substance onto the surface of a carrier, for example sand, kaolinite, and granulating the inert material with a binder, for example polyvinyl alcohol, sodium polyacrylate or mineral oil. Suitable active substances can be granulated by the process for preparing fertilizer granules, if desired mixed with fertilizers. The preparation of water-suspendable granules is carried out by customary methods, for example spray-drying, fluidized-bed granulation, millstone granulation, mixing using high-speed mixers and extrusion without solid inert materials.
For the preparation of granules using a millstone, a fluidized bed, an extruder and Spray coating, see the following processes, for example "Spray Drying handbook", third edition 1979, g.goodwin ltd, london; browning, "Agglomeration", chemical and engineering 1967, page 147 ff; "Perry's handbook of Engineers of chemistry", fifth edition, McGraw-Hill, New York 1973, pages 8-57. If preparations for crop protection products are to be known, see, for example, G.C. Klingman, "Weed Control as a Science", John Wiley and Sons, New York, pages 196181-96 and J.D. Freyer, S.A. Evans "Weed Control Manual", fifth edition, Blackwell scientific rules, Oxford university 1968, page 101-.
Agrochemical formulations generally comprise from 0.1 to 99%, in particular from 0.1 to 95% by weight of active substance of formula I. The concentration of active substance in wettable powders is, for example, from about 10 to 99% by weight, with usual formulation components making up the remainder to 100% by weight. The concentration of the active substance in the emulsion concentrate may be about 1 to 90%, preferably 5 to 80% by weight. Powder formulations contain from 1 to 30% by weight of active, usually preferably from 5 to 20% by weight of active, whereas sprayable solutions contain from about 0.05 to 80%, preferably from 2 to 50% by weight of active. The content of active substance in the aqueous suspension granules depends primarily on whether the active substance is liquid or solid, and the auxiliaries, fillers and the like used in granulation. The content of active substance in the water-suspendable granule formulation is, for example, between 1 and 95% by weight, preferably between 10 and 80% by weight.
The active substance formulations mentioned may additionally comprise tackifiers, wetting agents, dispersants, emulsifiers, penetrants, preservatives, antifreezes, solvents, fillers, carriers, colorants, antifoams, evaporation inhibitors and generally customary pH and viscosity regulators in all cases.
On the basis of these formulations, it is also possible to mix them with other insecticide active substances, such as insecticides, acaricides, herbicides and fungicides, and also with safeners, fertilizers and/or plant growth regulators, either premixed or mixed in containers.
When used, the commercially available formulations are diluted in the usual manner, if desired, for example in wettable powders, concentrated emulsions, suspensions and granules suspended in water, using water. Powders, granules for soil application or solutions for spreading and spraying generally do not require further dilution with inert substances before use. The required amount of the compound of formula I to be used varies with the external conditions, such as temperature, humidity, the nature of the herbicide used, etc. It may vary widely, for example between 0.001 and 1.0kg/ha, or more of active substance, but preferably between 0.005 and 750g/ha, in particular between 0.005 and 250 g/ha.
Detailed Description
The following examples are intended to illustrate the invention and should not be construed as limiting it in any way. The scope of the invention is indicated by the appended claims.
In view of the economic and diversity of the compounds, we prefer to synthesize some of the compounds, selected from the compounds synthesized in tables 1 and 2 below. Specific compound structures and corresponding compound information are shown in tables 1 and 2. The compounds in tables 1 and 2 are only for better illustrating the present invention, but do not limit the present invention, and it should not be understood to limit the scope of the above-mentioned subject matter of the present invention to the following compounds for those skilled in the art.
Table 1 Structure of Compound I and methods of making the same1HNMR data
Figure BDA0001790744410000241
Figure BDA0001790744410000242
Figure BDA0001790744410000251
Figure BDA0001790744410000261
Figure BDA0001790744410000271
Figure BDA0001790744410000281
Figure BDA0001790744410000291
Figure BDA0001790744410000301
Figure BDA0001790744410000311
Figure BDA0001790744410000321
Figure BDA0001790744410000331
Figure BDA0001790744410000341
Figure BDA0001790744410000351
Figure BDA0001790744410000361
Figure BDA0001790744410000371
Figure BDA0001790744410000381
Figure BDA0001790744410000391
Figure BDA0001790744410000401
Figure BDA0001790744410000411
Figure BDA0001790744410000421
Figure BDA0001790744410000431
Figure BDA0001790744410000441
Figure BDA0001790744410000451
Figure BDA0001790744410000461
Figure BDA0001790744410000471
Figure BDA0001790744410000481
Figure BDA0001790744410000491
Figure BDA0001790744410000501
TABLE 2 Structure of group M in derivative Compound I-1
Figure BDA0001790744410000502
Figure BDA0001790744410000503
Figure BDA0001790744410000511
Figure BDA0001790744410000521
Figure BDA0001790744410000531
Figure BDA0001790744410000541
Figure BDA0001790744410000551
Figure BDA0001790744410000561
Figure BDA0001790744410000571
Figure BDA0001790744410000581
Figure BDA0001790744410000591
Figure BDA0001790744410000601
Figure BDA0001790744410000611
Figure BDA0001790744410000621
Figure BDA0001790744410000631
TABLE 3 Structure of derivative Compound I-1 and related compounds1HNMR data
Figure BDA0001790744410000632
Figure BDA0001790744410000633
Figure BDA0001790744410000641
Figure BDA0001790744410000651
Figure BDA0001790744410000661
Figure BDA0001790744410000671
Several methods for preparing the compounds of the present invention are illustrated in the schemes and examples below. The starting materials are commercially available or can be prepared by methods known in the literature or as shown in detail. It will be appreciated by those skilled in the art that other synthetic routes may also be utilized to synthesize the compounds of the present invention. Although specific starting materials and conditions for the synthetic route are described below, they can be readily substituted with other similar starting materials and conditions, and variations or modifications of the preparation process of the present invention, such as various isomers of the compounds, are included in the scope of the present invention. In addition, the preparation methods described below may be further modified in accordance with the present disclosure using conventional chemical methods well known to those skilled in the art. For example, protecting the appropriate groups during the reaction, and the like.
The following process examples are provided to facilitate a further understanding of the methods of preparation of the invention, and the particular materials, species and conditions used are intended to be further illustrative of the invention and are not intended to limit the reasonable scope thereof. The reagents used in the synthesis of the compounds indicated in the following table are either commercially available or can be readily prepared by one of ordinary skill in the art.
Examples of representative compounds are as follows:
1. synthesis of Compound 1
Figure BDA0001790744410000672
(1) Placing compound 1-a (10g, 67mmol), compound 1-b (14.9g,67mmol) and potassium carbonate (27.8g,201mmol) in a round-bottom three-neck flask, adding 1, 4-dioxane (100 mL)/water (20mL), replacing nitrogen three times, and rapidly adding Pd (dppf) Cl under nitrogen protection2CH2Cl2(0.2g) and then replaced with nitrogen three times, the reaction mixture was replaced with nitrogen again three times, and the reaction mixture was reacted at 100 ℃ for 16 hours, and after completion of the detection by high performance liquid chromatography, the reaction system was concentrated and separated by column chromatography to obtain 10g (48mmol, yield 71%) of compound 1-c (gray solid).
(2) Compound 1-c (10g, 48mmol), N-chlorosuccinimide (6.4g, 48mmol), benzoyl peroxide (0.5g, catalytic amount), acetonitrile (100mL) were placed in a round-bottom three-necked flask and reacted at 80 ℃ for 16 hours, and a small amount of the starting material was detected by HPLC to remain, followed by concentration and column chromatography to give 5g (21mmol, yield 42%) of Compound 1-d (white solid).
(3) Placing compound 1-d (1g, 4mmol), potassium acetate (2g, 20mmol) and 10mL DMSO in a round bottom three-neck flask, reacting at 120 ℃ for 2 hours, cooling the reaction liquid to 25 ℃ after the reaction is detected by high performance liquid chromatography, dropwise adding 1M HCl into the reaction liquid until the pH of the solution is about 5, controlling the temperature (not higher than 25 ℃), separating out solids, carrying out suction filtration on the separated solids, washing with a large amount of water, pulping and purifying the solids by using methyl tert-butyl ether (20mL) and a small amount of methanol (1mL), and drying after suction filtration to obtain 300mg (1.3mmol, yield 32%) of compound 1 (white-like solid).
2. Synthesis of Compound 1-1
Figure BDA0001790744410000681
The compound 1(1 equivalent), potassium carbonate (3 equivalents) and acetonitrile (10V) were added to a 50mL single-neck eggplant-shaped bottle at room temperature, and the mixture was added dropwise thereto at room temperature
Figure BDA0001790744410000682
(1.2 eq.) after completion of the dropwise addition, the mixture was stirred at room temperature for 30 minutes. The reaction was completed by TLC, the acetonitrile was removed from the reaction system by distillation under reduced pressure, dissolved in water (5V), extracted with ethyl acetate (5V × 3), removed by distillation under reduced pressure, and the residue was separated by column chromatography on silica gel (100 mesh to 200 mesh) to give the product in 72% yield.
3. Synthesis of Compounds 1-5
Figure BDA0001790744410000683
Compound 1(1 equivalent), triethylamine (2 equivalents) and dichloromethane (5V) were added in a 50mL single-neck eggplant-shaped bottle under ice-bath, and dropwise added under ice-bath
Figure BDA0001790744410000684
(1.2 eq) and then stirred at room temperature for 30 minutes. The reaction was completed by TLC, the reaction was extracted with dichloromethane (5V) with water (5V), dichloromethane was distilled off under reduced pressure, and the residue was separated by column chromatography on silica gel (100 mesh to 200 mesh) to give the product in 73% yield.
4. Synthesis of Compounds 1-6
Figure BDA0001790744410000685
Adding 1(1 equivalent) of compound into a 50mL single-mouth eggplant-shaped bottle at room temperature,
Figure BDA0001790744410000686
(1.2 equiv.), potassium carbonate (3 equiv.) and acetonitrile (10V), warmed to 80 ℃ and stirred for 12 h. The reaction was completed by TLC, the reaction system was distilled under reduced pressure to remove acetonitrile, dissolved in water (5V), extracted with ethyl acetate (5V × 3), distilled under reduced pressure to remove ethyl acetate, and the residue was separated by column chromatography on silica gel (100 mesh to 200 mesh) to give the product in 79% yield.
5. Synthesis of Compounds 1-8
Figure BDA0001790744410000691
The compound 1(1 equivalent), potassium carbonate (3 equivalents) and acetonitrile (3V) were added to a 50mL single-neck eggplant-shaped bottle at room temperature, and the mixture was added dropwise thereto at room temperature
Figure BDA0001790744410000692
(1.2 eq.) after completion of the dropwise addition, the mixture was stirred at room temperature for 30 minutes. The reaction was completed by TLC, the acetonitrile was removed from the reaction system by distillation under reduced pressure, dissolved in water (5V), extracted with ethyl acetate (5V × 3), removed by distillation under reduced pressure, and the residue was separated by column chromatography on silica gel (100 mesh to 200 mesh) to give the product in 72% yield.
6. Synthesis of Compounds 1-9
Figure BDA0001790744410000693
Adding 1(1 equivalent) of compound into a 50mL single-mouth eggplant-shaped bottle at room temperature,
Figure BDA0001790744410000694
(1.2 equiv.), potassium carbonate (3 equiv.) and acetonitrile (10V), warmed to 80 ℃ and stirred for 12 h. The reaction was completed by TLC, the reaction system was distilled under reduced pressure to remove acetonitrile, dissolved in water (5V), extracted with ethyl acetate (5V × 3), distilled under reduced pressure to remove ethyl acetate, and the residue was separated by column chromatography on silica gel (100 mesh to 200 mesh) to give the product in 85% yield.
7. Synthesis of Compounds 1-25
Figure BDA0001790744410000695
Referring to the synthesis method of the compound 1, the compound 9 is prepared, and then the compound 9(1 equivalent), triethylamine (3 equivalents) and dichloromethane (10V) are added into a 50mL single-neck eggplant-shaped bottle in ice bath, and dropwise added in ice bath
Figure BDA0001790744410000696
(1.2 eq) and then stirred at room temperature for 30 minutes. The reaction was completed by TLC, the reaction was extracted with dichloromethane (5V) with water (5V), dichloromethane was distilled off under reduced pressure, and the residue was separated by column chromatography on silica gel (100 mesh to 200 mesh) to give the product in 81% yield.
8. Synthesis of Compounds 1-36
Figure BDA0001790744410000701
Referring to the synthesis method of the compound 1, the compound 22 is prepared, and then the compound 22(1 equivalent), Phenofluor (1.5 equivalents), cesium fluoride (three equivalents), toluene (10V) are added into a 50mL single-neck eggplant-shaped bottle at room temperature, heated to 80 ℃, and stirred for 18 h. TLC detection reaction is completed, and intermediate compound 1-36-a is post-processed. In another 50mL single-neck eggplant-shaped bottle, Compound 1-36-a (1) was added at room temperatureEquivalent weight)
Figure BDA0001790744410000702
(1.2 equiv.), potassium carbonate (3 equiv.) and acetonitrile (10V), warmed to 80 ℃ and stirred for 18 h. The reaction was completed by TLC, the acetonitrile was removed from the reaction system by distillation under reduced pressure, dissolved in water (5V), extracted with ethyl acetate (5V x 3), removed by distillation under reduced pressure, and the residue was separated by column chromatography on silica gel (100 mesh to 200 mesh) to give the product in 65% yield.
9. Synthesis of Compounds 1-47
Figure BDA0001790744410000703
With reference to the above synthesis method of Compound 1, Compound 48 was prepared, and Compound 48(1 equivalent), POCl was added to a 50mL single-neck eggplant-shaped bottle at room temperature3(1.5 equiv.), 1, 2-dichloroethane (10V) and 5% N, N-dimethylformamide, the temperature is raised to 80 ℃, and the mixture is stirred for 6 hours. TLC detection reaction is completed, water (5V) is added for dissolution, 1, 2-dichloroethane is used for extraction (5V 3), and reduced pressure distillation is carried out to remove 1, 2-dichloroethane, thus obtaining the compound 1-47-a. Adding 1-47-a (1 equivalent) of compound into another 50mL single-mouth eggplant-shaped bottle at room temperature,
Figure BDA0001790744410000704
(1.2 equiv.), potassium hydroxide (3 equiv.) and N, N-dimethylformamide (10V), heated to 100 ℃ and stirred for 18 h. The reaction was completed by TLC, dissolved in water (5V), extracted with ethyl acetate (5V x 3), distilled under reduced pressure to remove ethyl acetate, and the residue was separated by column chromatography on silica gel (100 mesh to 200 mesh) to give the product in 48% yield.
Evaluation of biological Activity:
the activity level criteria for harmful plant destruction (i.e. growth control rate) are as follows:
10 level: death is complete;
and 9, stage: the growth control rate is more than 90%;
and 8, stage: the growth control rate is more than 80 percent;
and 7, stage: the growth control rate is more than 70%;
and 6, level: the growth control rate is more than 60 percent;
and 5, stage: the growth control rate is more than 50%;
4, level: the growth control rate is more than 40%;
and 3, level: the growth control rate is more than 30 percent;
and 2, stage: the growth control rate is more than 20 percent;
level 1: the growth control rate is lower than 20%;
level 0: no effect is produced.
The growth control rate is the fresh weight control rate.
Post-emergence test experiments: placing monocotyledonous and dicotyledonous weed seeds and main crop seeds (wheat, corn, rice, soybean, cotton, rape, millet and sorghum) in a plastic pot filled with soil, then covering the plastic pot with 0.5-2 cm of soil to make the plastic pot grow in a good greenhouse environment, treating test plants in a 4-5 leaf period after sowing for 2-3 weeks, respectively dissolving the compound of the invention to be tested by acetone, then adding Tween 80, diluting the solution into a solution with certain water to a certain concentration, and spraying the solution onto the plants by a spray tower. The weeds were cultured in the greenhouse for 3 weeks after application, and the experimental effects of the weeds after 3 weeks are shown in tables 3 and 4.
TABLE 3 post-emergence weed test of Compound I
Figure BDA0001790744410000711
Figure BDA0001790744410000721
TABLE 4 post emergent weed test (2000 g/ha) for derivative compound I-1
Number of Compounds Amaranthus retroflexus (lour.) Merr Chenopodium quinoa (L.) Merr Herb of common Setaria Herb of veronica
1-1 10 10 10 10
1-2 10 10 10 10
1-3 10 10 10 10
1-4 10 10 10 10
1-5 10 10 10 10
1-6 10 10 10 10
1-7 10 10 10 10
1-8 10 10 10 10
1-9 10 10 10 10
1-10 10 10 10 10
1-11 10 10 10 10
Comparative experiment:
the post-emergence test conditions were as above, and the experimental results are shown in table 5.
Control compound a:
Figure BDA0001790744410000722
control compound B:
Figure BDA0001790744410000723
TABLE 5 comparative experimental results
Number of Compounds Barnyard grass Herb of common Setaria Tang style food Indian rorippa herb Herb of veronica Metering
1 8 10 7 10 10 300 g/hectare
29 8 10 6 10 9 300 g/hectare
33 N N N 10 10 300 g/hectare
1-1 8 10 8 10 10 300 g/hectare
1-2 8 10 10 10 10 300 g/hectare
1-3 9 10 9 10 10 300 g/hectare
1-11 9 9 7 10 10 300 g/hectare
Control Compound A 0 2 0 2 5 300 g/hectare
Control Compound B 0 2 0 3 5 300 g/hectare
Note: and N is no data.
As can be seen from the above table, the compounds of the present invention have better herbicidal activity than the control compounds A and B.
Pre-emergence test experiment:
placing the monocotyledon and dicotyledon weed seeds and main crop seeds (wheat, corn, rice, soybean, cotton, rape, millet and sorghum) in a plastic pot filled with soil, then covering the plastic pot with 0.5-2 cm of soil, respectively dissolving the compound of the invention to be tested by acetone, then adding Tween 80, diluting the solution into solution with a certain concentration by using a certain amount of water, and immediately spraying the solution after sowing. After the application, the mixture is cultured in a greenhouse for 4 weeks, and after 3 weeks, experimental results are observed, so that the medicament has a superior effect under the measurement of 250 g/hectare, particularly on weeds such as cockspur grass, kukukuh, piemarker and the like, and a plurality of compounds have good selectivity on corn, wheat, rice, soybean and rape.
Experiments show that the compound generally has good weed control effect, particularly has good effect on weeds widely occurring in corn fields, paddy fields and wheat fields, and has good commercial value. In particular we have noted extremely high activity against ALS inhibitor resistant broadleaf weeds.
Evaluating the safety of transplanted rice and the weed control effect of paddy field:
after the paddy field soil was filled in a tank of 1/1,000,000 hectare, seeds of barnyard grass, japanese iris, bidens tripartita and edible tulip were sown, and soil was lightly covered thereon. Standing in a state of water storage depth of 0.5-1 cm in a greenhouse, and implanting tuber of Pseudobulbus Cremastrae seu pleiones in the next or 2 days. Thereafter, the water storage depth was maintained at 3 to 4 cm, and an aqueous dilution of a wettable powder or a suspension, which was prepared by a usual formulation method, was dropped uniformly by a pipette at a time point when barnyard grass, japanese iris, or burley reached 0.5 leaf and the bulb reached the primary leaf stage to obtain a predetermined amount of active ingredient.
In addition, after filling the 1/1,000,000 hectare pot with paddy field soil, leveling is carried out to ensure that the water storage depth is 3-4 cm, and the rice (japonica rice) at the 3-leaf stage is transplanted with the transplanting depth of 3 cm on the next day. The compound of the present invention was treated on the 5 th day after transplantation in the same manner as described above.
The growth states of barnyard grass, Chinese iris, bidens tripartita and edible tulip on the 14 th day after the treatment with the medicament and the growth states of rice on the 21 th day after the treatment with the medicament are respectively observed by naked eyes, the weeding effect is evaluated according to the activity standard level of 1-10, and tests show that a plurality of compounds of the invention have excellent activity and selectivity, particularly for the edible tulip and the barnyard grass.
Note: the seeds of barnyard grass, Chinese iris, edible tulip and bidens tripartita are all collected from Heilongjiang in China, and are detected to have drug resistance to pyrazosulfuron-ethyl with conventional dosage.
Meanwhile, a plurality of tests show that the compound and the composition thereof have good selectivity on gramineous lawns such as zoysia japonica, bermuda grass, festuca arundinacea, bluegrass, ryegrass, seashore paspalum and the like, and can prevent and kill a plurality of key gramineous weeds and broadleaf weeds. Tests on wheat, corn, rice, sugarcane, soybean, cotton, sunflower, potato, fruit trees, vegetables and the like under different application modes also show excellent selectivity and commercial value.

Claims (10)

1. A five-membered ring substituted pyridazinol compound and its derivatives are shown in formula I:
Figure FDA0001790744400000011
wherein X represents halogen, cyano, alkyl, haloalkyl, alkoxy, haloalkoxy, R1R2N-(C＝O)-、R1R2N-, hydroxy, unsubstituted or substituted aryl;
ar represents
Figure FDA0001790744400000012
Het is selected from five-membered unsaturated rings containing, as part of the ring, in addition to the C atom in position 1, from 0 to 4 of the following atoms or groups: o, NRbOr S;
Raone or more groups selected from the following groups: hydrogen, halogen, cyano, nitro, azido, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkylalkyl, unsubstituted or substituted aryl, arylalkyl, heteroaryl, heteroarylalkyl, with or without halogen, R-O- (CH)2)n-，R-O-(CH2)p-O-(CH2)q-，R-O-(CH2)p-S-(CH2)q-，R-S-(CH2)n-，
R-S-(CH2)p-O-(CH2)q-，R-S-(CH2)p-S-(CH2)q-，R-O-(CH2)n-(C＝O)-(CH2)q-(O)m-，
R-S-(CH2)n-(C＝S)-(CH2)q-(S)m-，R-O-(CH2)n-(C＝O)-(CH2)q-(S)m-，
R-O-(CH2)n-(C＝S)-(CH2)q-(O)m-，R-S-(CH2)n-(C＝O)-(CH2)q-(O)m-，
R-O-(CH2)n-(C＝S)-(CH2)q-(S)m-，R-S-(CH2)n-(C＝O)-(CH2)q-(S)m-，
R-S-(CH2)n-(C＝S)-(CH2)q-(O)m-，R-(C＝O)-(CH2)n-，R-(C＝S)-(CH2)n-，R-(C＝O)-(CH2)n-O-(CH2)q-，
R-(C＝S)-(CH2)n-S-(CH2)q-，R-(C＝O)-(CH2)n-S-(CH2)q-，R-(C＝S)-(CH2)n-O-(CH2)q-，
R-SO-(CH2)n-(O)m-，R-SO-(CH2)n-(S)m-，R-SO-(CH2)n-(NR3)m-，R-SO2-(CH2)n-(O)m-，
R-SO2-(CH2)n-(S)m-，R-SO2-(CH2)n-(NR3)m-，R1R2N-(CH2)n-，R1R2N-(CH2)n-O-(CH2)q-(O)m-，
R1R2N-(CH2)n-O-(CH2)q-(S)m-，R1R2N-(CH2)n-O-(CH2)q-(NR3)m-，
R1R2N-(CH2)n-(C＝O)-(CH2)q-(O)m-，R1R2N-(CH2)n-(C＝O)-(CH2)q-(S)m-，
R1R2N-(CH2)n-(C＝O)-(CH2)q-(NR3)m-，R1R2N-(CH2)n-SO2-(CH2)q-(O)m-，
R1R2N-(CH2)n-SO2-(CH2)q-(S)m-，R1R2N-(CH2)n-SO2-(CH2)q-(NR3)m-，R1R2PO3-(O)m-(CH2)q-，
R1R2R3SiO-(CH2)q-，R1R2R3Si-(CH＝CH)m-(CH2)q-，R1R2C＝N-(O)m-(CH2)n-，
R1R2C＝N-NH-(CH2)n-; or two adjacent RaTogether form-OCH2O-、-CH2CH2O-、-OCH2CH2O-、-OCH(CH3)O-、-OC(CH3)2O-、-OCF2O-、-CF2CF2O-、-OCF2CF2O-or-CH-;
m is 0 or 1, n and q respectively represent an integer between 0 and 8, and p represents an integer between 1 and 8;
r represents hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkylalkyl, with or without halogen, and unsubstituted or substituted aryl, arylalkyl, heteroaryl, heteroarylalkyl;
Rb、R1、R2、R3each independently represents hydrogen, nitro, hydroxy,amino, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkylalkyl, alkoxy, alkenyloxy, alkynyloxy, cycloalkyloxy, alkoxyalkyl, alkoxycarbonyl, alkylthiocarbonyl, alkylsulfonyl, alkylsulfonylalkyl, alkylcarbonyl, alkylcarbonylalkyl, alkanoyloxy, alkylamino, alkylaminocarbonyl, alkoxyaminocarbonyl, alkoxycarbonylalkyl, alkylaminocarbonylalkyl, trialkylsilyl, dialkylphosphono, and unsubstituted or substituted six-membered heterocyclic groups, aryl, arylalkyl, aryloxy, arylalkyloxy, aryloxyalkyl, arylcarbonyl, arylsulfonyl, heteroaryl, heteroarylalkyl, heteroaryloxy, heteroarylalkyloxy, heteroaryloxyalkyl, heteroaryloxycarbonyl, heteroarylsulfonyl, with or without halogen; or R1R2N-represents a six-membered heterocyclic group; or adjacent RaAnd RbTogether form-CH2CH2NR3CH2-。
2. The five-membered ring substituted pyridazinol compound and the derivatives thereof according to claim 1,
x represents halogen, cyano, C1～8Alkyl, halo C1～8Alkyl radical, C1～8Alkoxy, halo C1～8Alkoxy radical, R1R2N-(C＝O)-、R1R2N-, hydroxyl, unsubstituted or 1-5 substituents independently selected from halogen, cyano, nitro, hydroxyl, carboxyl, mercapto, amino and C with or without halogen1～8Alkyl radical, C3～8Cycloalkyl radical, C3～8Cycloalkyl radical C1～8Alkyl radical, C2～8Alkenyl radical, C2～8Alkynyl, C1～8Alkoxy radical, C1～8Alkylcarbonyl group, C1～8Alkoxycarbonyl group, C1～8Alkylsulfonyl radical, C1～8Alkylamino or C1～8Aryl substituted with a group selected from the group consisting of an alkanoyloxy group;
ar represents
Figure FDA0001790744400000021
Het is selected from the group consisting of five-membered unsaturated heterocycles containing 1 to 4 of the following atoms or groups as ring members in addition to the C atom in position 1: o, NRbOr S;
Raone or more groups selected from the following groups: hydrogen, halogen, cyano, nitro, azido, C with or without halogen1～8Alkyl radical, C2～8Alkenyl radical, C2～8Alkynyl, C3～8Cycloalkyl radical, C5～8Cycloalkenyl radical, C3～8Cycloalkyl radical C1～8Alkyl, unsubstituted or substituted by 1 to 5 groups independently selected from halogen, cyano, nitro, hydroxy, carboxy, mercapto, amino and C with or without halogen1～8Alkyl radical, C3～8Cycloalkyl radical, C3～8Cycloalkyl radical C1～8Alkyl radical, C2～8Alkenyl radical, C2～8Alkynyl, C1～8Alkoxy radical, C1～8Alkylcarbonyl group, C1～8Alkoxycarbonyl group, C1～8Alkylsulfonyl radical, C1～8Alkylamino or C1～8Aryl, aryl C substituted by radicals in alkanoyloxy1～8Alkyl, heteroaryl C1～8Alkyl, R-O- (CH)2)n-，R-O-(CH2)p-O-(CH2)q-，
R-O-(CH2)p-S-(CH2)q-，R-S-(CH2)n-，R-S-(CH2)p-O-(CH2)q-，R-S-(CH2)p-S-(CH2)q-，
R-O-(CH2)n-(C＝O)-(CH2)q-，R-S-(CH2)n-(C＝S)-(CH2)q-，R-O-(CH2)n-(C＝S)-(CH2)q-，
R-S-(CH2)n-(C＝O)-(CH2)q-，R-O-(C＝O)-(CH2)q-(O)m-，R-S-(C＝S)-(CH2)q-(S)m-，
R-O-(C＝O)-(CH2)q-(S)m-，R-O-(C＝S)-(CH2)q-(O)m-，R-S-(C＝O)-(CH2)q-(O)m-，
R-O-(C＝S)-(CH2)q-(S)m-，R-S-(C＝O)-(CH2)q-(S)m-，R-S-(C＝S)-(CH2)q-(O)m-，
R-O-(CH2)n-(C＝O)-(O)m-，R-S-(CH2)n-(C＝S)-(S)m-，R-O-(CH2)n-(C＝O)-(S)m-，
R-O-(CH2)n-(C＝S)-(O)m-，R-S-(CH2)n-(C＝O)-(O)m-，R-O-(CH2)n-(C＝S)-(S)m-，
R-S-(CH2)n-(C＝O)-(S)m-，R-S-(CH2)n-(C＝S)-(O)m-，R-(C＝O)-，R-(C＝S)-，R-(C＝O)-(CH2)n-O-，
R-(C＝S)-(CH2)n-S-，R-(C＝O)-(CH2)n-S-，R-(C＝S)-(CH2)n-O-，R-(C＝O)-O-(CH2)q-，
R-(C＝S)-S-(CH2)q-，R-(C＝O)-S-(CH2)q-，R-(C＝S)-O-(CH2)q-，R-SO-(O)m-，R-SO-(S)m-，
R-SO-(NR3)m-，R-SO2-(O)m-，R-SO2-(S)m-，R-SO2-(NR3)m-，R-SO-(CH2)n-，R-SO2-(CH2)n-，
R1R2N-，R1R2N-(CH2)n-O-(CH2)q-，R1R2N-(CH2)n-(C＝O)-(CH2)q-，R1R2N-(CH2)n-SO2-(CH2)q-，
R1R2N-(CH2)n-(C＝O)-(O)m-，R1R2N-(CH2)n-(C＝O)-(S)m-，R1R2N-(CH2)n-(C＝O)-(NR3)m-，
R1R2N-(CH2)n-SO2-(O)m-，R1R2N-(CH2)n-SO2-(S)m-，R1R2N-(CH2)n-SO2-(NR3)m-，
R1R2N-(C＝O)-(CH2)n-(O)m-，R1R2N-(C＝O)-(CH2)n-(S)m-，R1R2N-(C＝O)-(CH2)n-(NR3)m-，
R1R2N-SO2-(CH2)q-(O)m-，R1R2N-SO2-(CH2)q-(S)m-，R1R2N-SO2-(CH2)q-(NR3)m-，
R1R2N-(CH2)n-O-，R1R2N-O-(CH2)q-，R1R2PO3-(O)m-，R1R2R3SiO-，R1R2R3Si-(CH＝CH)m-，
R1R2C＝N-(O)m-，R1R2C ═ N-NH-; or two adjacent RaTogether form-OCH2O-、-CH2CH2O-、-OCH2CH2O-、-OCH(CH3)O-、-OC(CH3)2O-、-OCF2O-、-CF2CF2O-、-OCF2CF2O-or-CH-;
m is 0 or 1, n and q respectively represent an integer between 0 and 6, and p represents an integer between 1 and 6;
r represents hydrogen, C with or without halogen1～8Alkyl radical, C2～8Alkenyl radical, C2～8Alkynyl, C3～8Cycloalkyl radical, C5～8Cycloalkenyl radical, C3～8Cycloalkyl radical C1～8Alkyl, unsubstituted or substituted by 1 to 5 substituents independently selected from halogen, cyano, nitro, hydroxy, carboxy, mercapto, amino and C with or without halogen1～8Alkyl radical, C3～8Cycloalkyl radical, C3～8Cycloalkyl radical C1～8Alkyl radical, C2～8Alkenyl radical, C2～8Alkynyl, C1～8Alkoxy radical, C1～8Alkylcarbonyl group, C1～8Alkoxycarbonyl group, C1～8Alkylsulfonyl radical, C1～8Alkylamino or C1～8Aryl, aryl C substituted by radicals in alkanoyloxy1～8Alkyl, heteroaryl C1～8An alkyl group;
Rb、R1、R2、R3each independently represents hydrogen, nitro, hydroxy, amino, C with or without halogen1～8Alkyl radical, C2～8Alkenyl radical, C2～8Alkynyl, C3～8Cycloalkyl radical, C5～8Cycloalkenyl radical, C3～8Cycloalkyl radical C1～8Alkyl radical, C1～8Alkoxy radical, C2～8Alkenyloxy radical, C2～8Alkynyloxy, C3～8Cycloalkyl oxy, C1～8Alkoxy radical C1～8Alkyl radical, C1～8Alkoxycarbonyl group, C1～8Alkyl carbonyl radical C1～8Alkyl radical, C1～8Alkylthio carbonyl group, C1～8Alkylsulfonyl radical, C1～8Alkylsulfonyl radical C1～8Alkyl radical, C1～8Alkylcarbonyl group, C1～8Alkyl acyloxy, C1～8Alkylamino radical, C1～8Alkylaminocarbonyl radical, C1～8Alkoxyaminocarbonyl group, C1～8Alkoxycarbonyl radical C1～8Alkyl radical, C1～8Alkylamino carbonylsRadical C1～8Alkyl, tri-C1～8Alkylsilyl, di-C1～8Alkylphosphono and unsubstituted or substituted by 1 to 5 substituents independently selected from halogen, cyano, nitro, hydroxy, carboxy, mercapto, amino and C with or without halogen1～8Alkyl radical, C3～8Cycloalkyl radical, C3～8Cycloalkyl radical C1～8Alkyl radical, C2～8Alkenyl radical, C2～8Alkynyl, C1～8Alkoxy radical, C1～8Alkylcarbonyl group, C1～8Alkoxycarbonyl group, C1～8Alkylsulfonyl radical, C1～8Alkylamino or C1～8Six-membered heterocyclic radical, aryl radical C substituted by radicals in alkyl acyloxy1～8Alkyl, aryloxy, aryl C1～8Alkyloxy, aryloxy C1～8Alkyl, arylcarbonyl, arylsulfonyl, heteroaryl C1～8Alkyl, heteroaryloxy, heteroaryl C1～8Alkyloxy, heteroaryloxy C1～8Alkyl, heteroarylcarbonyl, heteroarylsulfonyl; or R1R2N-represents a six-membered heterocyclic group which may or may not contain other hetero atoms in the ring; or adjacent RaAnd RbTogether form-CH2CH2NR3CH2-；
The derivative refers to an agriculturally acceptable hydroxyl derivative at the 4-position of the pyridazine ring in the general formula I.
3. The five-membered ring substituted pyridazinol compound and the derivatives thereof according to claim 1 or 2,
x represents fluorine, chlorine, bromine, iodine, cyano, C1～6Alkyl, halo C1～6Alkyl radical, C1～6Alkoxy, halo C1～6Alkoxy radical, R1R2N-(C＝O)-、R1R2N-, hydroxyl, unsubstituted or 1-5 substituents independently selected from halogen, cyano, nitro, hydroxyl, carboxyl, mercapto, amino and C with or without halogen1～6Alkyl radical, C3～6Cycloalkyl radical, C3～6Cycloalkyl radical C1～6Alkyl radical, C2～6Alkenyl radical, C2～6Alkynyl, C1～6Alkoxy radical, C1～6Alkylcarbonyl group, C1～6Alkoxycarbonyl group, C1～6Alkylsulfonyl radical, C1～6Alkylamino or C1～6Phenyl substituted with a group selected from the group consisting of alkyl acyloxy;
ar represents
Figure FDA0001790744400000041
Het is selected from the group consisting of five-membered unsaturated heterocycles containing as ring members, in addition to the C atom in position 1,2, 3 or 4 of the following atoms or groups: o, NRbOr S;
Raone or more groups selected from the following groups: hydrogen, fluorine, chlorine, bromine, cyano, nitro, azido, C with or without fluorine, chlorine, bromine1～6Alkyl radical, C2～6Alkenyl radical, C2～6Alkynyl, C3～6Cycloalkyl radical, C5～6Cycloalkenyl radical, C3～6Cycloalkyl radical C1～6Alkyl, unsubstituted or substituted by 1 to 3 groups independently selected from fluorine, chlorine, bromine, cyano, nitro, hydroxy, carboxy, mercapto, amino and C with or without fluorine, chlorine, bromine1～6Alkyl radical, C3～6Cycloalkyl radical, C3～6Cycloalkyl radical C1～6Alkyl radical, C2～6Alkenyl radical, C2～6Alkynyl, C1～6Alkoxy radical, C1～6Alkylcarbonyl group, C1～6Alkoxycarbonyl group, C1～6Alkylsulfonyl radical, C1～6Alkylamino or C1～6Aryl, aryl C substituted by radicals in alkanoyloxy1～6Alkyl, heteroaryl C1～6Alkyl, R-O-, R-O- (CH)2)p-O-，R-O-(CH2)p-S-，R-S-，R-S-(CH2)p-O-，R-S-(CH2)p-S-，R-O-(C＝O)-(O)m-，R-S-(C＝S)-(S)m-，R-O-(C＝O)-(S)m-，R-O-(C＝S)-(O)m-，R-S-(C＝O)-(O)m-，R-O-(C＝S)-(S)m-，R-S-(C＝O)-(S)m-，R-S-(C＝S)-(O)m-，R-O-(C＝O)-(CH2)q-，R-S-(C＝S)-(CH2)q-，R-O-(C＝S)-(CH2)q-，R-S-(C＝O)-(CH2)q-，R-O-(CH2)n-(C＝O)-，R-S-(CH2)n-(C＝S)-，R-O-(CH2)n-(C＝S)-，R-S-(CH2)n-(C＝O)-，R-(C＝O)-，R-(C＝S)-，R-(C＝O)-O-，R-(C＝S)-S-，R-(C＝O)-S-，R-(C＝S)-O-，R-SO-，R-SO2-，R1R2N-，R1R2N-O-，R1R2N-(C＝O)-(CH2)p-，R1R2N-(C＝O)-(O)m-，R1R2N-(C＝O)-(S)m-，R1R2N-(C＝O)-(NR3)m-，R1R2N-SO2-(CH2)p-，R1R2N-SO2-，R1R2N-(CH2)p-(C＝O)-，R1R2N-(CH2)p-SO2-，R1R2N-(CH2)p-O-，R1R2N-O-(CH2)p-，R1R2PO3-，R1R2R3SiO-，R1R2R3Si-，R1R2R3Si-CH＝CH-，R1R2C＝N-，R1R2C＝N-O-，R1R2C ═ N-NH-; or two adjacent RaTogether form-CH ═ CH-;
m is 0 or 1, n and q respectively represent 0, 1,2, 3 or 4, and p represents 1,2, 3 or 4;
r represents hydrogen, C with or without fluorine, chlorine or bromine1～6Alkyl radical, C2～6Alkenyl radical, C2～6Alkynyl, C3～6Cycloalkyl radical, C5～6Cycloalkenyl radical, C3～6Cycloalkyl radical C1～6Alkyl, unsubstituted or substituted by 1 to 3 groups independently selected from fluorine, chlorine, bromine, cyano, nitro, hydroxy, carboxy, mercapto, amino, and with or without fluorineC of chlorine, bromine1～6Alkyl radical, C3～6Cycloalkyl radical, C3～6Cycloalkyl radical C1～6Alkyl radical, C2～6Alkenyl radical, C2～6Alkynyl, C1～6Alkoxy radical, C1～6Alkylcarbonyl group, C1～6Alkoxycarbonyl group, C1～6Alkylsulfonyl radical, C1～6Alkylamino or C1～6Aryl, aryl C substituted by radicals in alkanoyloxy1～6Alkyl, heteroaryl C1～6An alkyl group;
Rb、R1、R2、R3each independently represents hydrogen, nitro, hydroxyl, amino, C with or without fluorine, chlorine or bromine1～6Alkyl radical, C2～6Alkenyl radical, C2～6Alkynyl, C3～6Cycloalkyl radical, C5～6Cycloalkenyl radical, C3～6Cycloalkyl radical C1～6Alkyl radical, C1～6Alkoxy radical, C2～6Alkenyloxy radical, C2～6Alkynyloxy, C3～6Cycloalkyl oxy, C1～6Alkoxy radical C1～6Alkyl radical, C1～6Alkoxycarbonyl group, C1～6Alkylthio carbonyl group, C1～6Alkylsulfonyl radical, C1～6Alkylsulfonyl radical C1～6Alkyl radical, C1～6Alkylcarbonyl group, C1～6Alkyl carbonyl radical C1～6Alkyl radical, C1～6Alkyl acyloxy, C1～6Alkylamino radical, C1～6Alkylaminocarbonyl radical, C1～6Alkoxyaminocarbonyl group, C1～6Alkoxycarbonyl radical C1～6Alkyl radical, C1～6Alkylamino carbonyl group C1～6Alkyl, tri-C1～6Alkylsilyl, di-C1～6Alkylphosphono and unsubstituted or substituted 1-3 of C independently selected from fluorine, chlorine, bromine, cyano, nitro, hydroxyl, carboxyl, mercapto, amino and optionally fluorine, chlorine and bromine1～6Alkyl radical, C3～6Cycloalkyl radical, C3～6Cycloalkyl radical C1～6Alkyl radical, C2～6Alkenyl radical, C2～6Alkynyl, C1～6Alkoxy radical, C1～6Alkylcarbonyl group, C1～6Alkoxycarbonyl group, C1～6Alkylsulfonyl radical, C1～6Alkylamino or C1～6Substituted by radicals in the group of alkanoyloxy
Figure FDA0001790744400000051
Aryl, aryl C1～6Alkyl, aryloxy, aryl C1～6Alkyloxy, aryloxy C1～6Alkyl, arylcarbonyl, arylsulfonyl, heteroaryl C1～6Alkyl, heteroaryloxy, heteroaryl C1～6Alkyloxy, heteroaryloxy C1～6Alkyl, heteroarylcarbonyl, heteroarylsulfonyl; or R1R2N-represents
Figure FDA0001790744400000052
Or adjacent RaAnd RbTogether form-CH2CH2N(Boc)CH2-；
Said aryl is
Figure FDA0001790744400000053
Figure FDA0001790744400000054
Heteroaryl is selected from
Figure FDA0001790744400000055
Figure FDA0001790744400000056
Figure FDA0001790744400000061
Figure FDA0001790744400000062
R' represents hydrogen, nitro, hydroxyl, amino, C with or without fluorine, chlorine or bromine1～6Alkyl radical, C2～6Alkenyl radical, C2～6Alkynyl, C3～6A cycloalkyl group, a,C5～6Cycloalkenyl radical, C3～6Cycloalkyl radical C1～6Alkyl radical, C1～6Alkoxy radical, C2～6Alkenyloxy radical, C2～6Alkynyloxy, C3～6Cycloalkyl oxy, C1～6Alkoxy radical C1～6Alkyl radical, C1～6Alkoxycarbonyl group, C1～6Alkylthio carbonyl group, C1～6Alkylsulfonyl radical, C1～6Alkylsulfonyl radical C1～6Alkyl radical, C1～6Alkylcarbonyl group, C1～6Alkyl carbonyl radical C1～6Alkyl radical, C1～6Alkyl acyloxy, C1～6Alkylamino radical, C1～6Alkylaminocarbonyl radical, C1～6Alkoxyaminocarbonyl group, C1～6Alkoxycarbonyl radical C1～6Alkyl radical, C1～6Alkylamino carbonyl group C1～6Alkyl, tri-C1～6Alkylsilyl, di-C1～6Alkylphosphono and unsubstituted or substituted 1-3 of C independently selected from fluorine, chlorine, bromine, cyano, nitro, hydroxyl, carboxyl, mercapto, amino and optionally fluorine, chlorine and bromine1～6Alkyl radical, C3～6Cycloalkyl radical, C3～6Cycloalkyl radical C1～6Alkyl radical, C2～6Alkenyl radical, C2～6Alkynyl, C1～6Alkoxy radical, C1～6Alkylcarbonyl group, C1～6Alkoxycarbonyl group, C1～6Alkylsulfonyl radical, C1～6Alkylamino or C1～6Substituted by radicals in the group of alkanoyloxy
Figure FDA0001790744400000063
Aryl, aryl C1～6Alkyl, aryloxy, aryl C1～6Alkyloxy, aryloxy C1～6Alkyl, arylcarbonyl, arylsulfonyl, heteroaryl C1～6Alkyl, heteroaryloxy, heteroaryl C1～6Alkyloxy, heteroaryloxy C1～6Alkyl, heteroarylcarbonyl, heteroarylsulfonyl;
the derivative refers to agriculturally acceptable hydroxyl derivatives at the 4-position of the pyridazine ring in the general formula I, and comprises salt, ester, oxime, hydroxylamine and ether derivatives.
4. The five-membered ring substituted pyridazinol compound and the derivatives thereof according to claim 1 or 2,
x represents fluorine, chlorine, bromine, iodine, cyano, methyl, ethyl, trifluoromethyl, pentafluoroethyl, difluoromethyl, monofluoromethyl, methoxy, ethoxy, trifluoromethoxy, pentafluoroethoxy;
het represents
Figure FDA0001790744400000064
Figure FDA0001790744400000071
RaOne or more groups selected from the following groups: hydrogen, methyl, ethyl, cyano, cyclopropyl, phenyl, fluoro, chloro, bromo, iodo, cyano, nitro, difluoromethyl, 2,2, 2-trifluoroethyl, trifluoromethyl, methoxy, ethoxy, benzyloxy, -COOEt, amino, methylamino, dimethylamino, acetylamino, trifluoromethyl,
Figure FDA0001790744400000072
Figure FDA0001790744400000073
or Ar represents
Figure FDA0001790744400000074
RbRepresents hydrogen, methyl, ethyl, n-propyl, isopropyl, difluoromethyl, 2,2, 2-trifluoroethyl, acetyl, phenyl, benzyl, methyl, ethyl, isopropyl, trifluoromethyl,
Figure FDA0001790744400000075
A triphenylmethyl group;
the derivative refers to agriculturally acceptable hydroxyl derivatives at the 4-position of the pyridazine ring in the general formula I, and comprises salt, ester, oxime, hydroxylamine and ether derivatives.
5. A method for preparing the five-membered ring substituted pyridazinol compound and the derivatives thereof according to any one of claims 1 to 4, wherein the method for preparing the five-membered ring substituted pyridazinol compound comprises the steps of:
(1) carrying out Suzuki reaction on a compound II and a compound III to prepare a compound shown as a general formula IV;
(2) carrying out halogenation reaction on the compound shown in the general formula IV to prepare a compound shown in the general formula V;
(3) preparing a compound shown as a general formula I by hydrolyzing a compound shown as a general formula V;
the chemical reaction equation is as follows:
Figure FDA0001790744400000076
L1and L2Each independently represents halogen, preferably chlorine, bromine, iodine;
the chemical reaction equation for preparing the ester and ether derivatives is as follows:
Figure FDA0001790744400000081
wherein, Y1Halogen, preferably chlorine, bromine;
the chemical reaction equation for preparing oxime and hydroxylamine derivatives is as follows:
Figure FDA0001790744400000082
wherein, Y2Halogen, preferably chlorine and fluorine.
6. The method for preparing five-membered ring substituted pyridazinol compound and derivatives thereof according to claim 5, wherein the reaction temperature is 20-150 ℃In the enclosure, preferably 50-130 ℃; the step (1) is carried out in the presence of a catalyst, a base and a solvent, wherein the catalyst is Pd (dppf) Cl2CH2Cl2、Pd(dba)2、Pd2(dba)3、Pd(PPh3)4、PdCl2、Pd(OAc)2、Pd(dppf)Cl2、Pd(PPh3)2Cl2Or Ni (dppf) Cl2The base is selected from Et3N、NaHCO3、KOAc、K2CO3、K3PO4、Na2CO3、CsF、Cs2CO3One or more than two of t-BuONa, EtONa, KOH and NaOH, wherein the solvent is THF/water, toluene/water, DMF/water, 1, 4-dioxane/water, toluene/ethanol/water or acetonitrile/water, THF, toluene, 1, 4-dioxane, acetonitrile and DMF system; the step (2) is carried out in the presence of a halogenating reagent, a catalyst and a solvent, wherein the halogenating reagent is N-chlorosuccinimide, N-bromosuccinimide or N-iodosuccinimide, the catalyst is benzoyl peroxide, and the solvent is acetonitrile; the step (3) is carried out in the presence of a base and a solvent, or in the presence of boron tribromide, hydrobromic acid acetic acid solution, hydrochloric acid methanol solution and hydrochloric acid ethyl acetate solution, wherein the base is preferably NaOH, KOH, potassium acetate and sodium acetate, and the solvent is preferably water and DMSO; the reaction for preparing the ester and ether derivatives and the second reaction for preparing the oxime and hydroxylamine derivatives are carried out in the presence of alkali and solvent, wherein the alkali is one or more than two of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, cesium carbonate, triethylamine and diisopropylethylamine; the solvent is THF, 1, 4-dioxane, toluene, 1, 2-dichloroethane, ethyl acetate, acetonitrile, DMF, acetone, dichloromethane or chloroform; the first step of the reaction for preparing the oxime and hydroxylamine derivatives thereof is carried out in the presence of a halogenating agent, Phenofluor/cesium fluoride or POCl, and a solvent3The solvent is one or more than two of toluene, 1, 2-dichloroethane and DMF; the reaction temperature is selected from the range of 0-120 ℃, and preferably 20-80 ℃.
7. A herbicidal composition comprising (I) the five-membered ring-substituted pyridazinol compound represented by the general formula I according to any one of claims 1 to 4 and a derivative thereof; preferably, further comprising (ii) one or more additional herbicides and/or safeners; more preferably, (iii) an agrochemically acceptable formulation auxiliary.
8. A herbicide composition as claimed in claim 7, wherein said additional herbicide is selected from one of HPPD inhibitors, hormones, PDS inhibitors; preferably, the HPPD inhibitor is sulcotrione, mesotrione, topramezone, tembotrione, fluroxypyr, mesotrione, benzobicyclon, lancotrione, topramezone, triazophone, topramezone, pyrazox, pyrazotoconazole, pyraflutole, tralkoxydim, tolpyralate, fenquinotrione, isoxaflutole; the hormones are fluroxypyr, quinclorac, 2-methyl-4-chlorophenoxypropionic acid, MCPB, 2,4-D, 2, 4-dichlorpropionic acid, 2,4-DB, dicamba, picloram, triclopyr, clopyralid, triclopyr and derivatives thereof, and the PDS inhibitor is flurtamone, diflufenican, flurbiprofen, beflubutamid, flurfenpyr, and fluridone.
9. A method for controlling harmful plants, which comprises applying a herbicidally effective amount of at least one of the five-membered ring-substituted pyridazinol compounds and derivatives thereof according to any one of claims 1 to 4 or the herbicidal composition according to any one of claims 7 to 8 to plants or to the area of harmful plants.
10. Use of at least one of the five-membered ring substituted pyridazinol compounds and derivatives thereof according to any one of claims 1 to 4 or the herbicidal composition according to any one of claims 7 to 8 for controlling noxious plants, preferably for controlling noxious plants in crops of useful plants, which are transgenic or genome editing technology-treated crops.
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BR112020015620-5A BR112020015620B1 (en) 2018-02-02 2018-09-13 PYRIDAZINOLE COMPOUNDS WITH SUBSTITUTED FIVE-MEMBER RING OR DERIVATIVE THEREOF, METHODS FOR PREPARING THE SAME, HERBICIDAL COMPOSITION, USE THEREOF AND METHOD FOR CONTROLLING A WEED

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CN105121411A (en) * 2013-04-15 2015-12-02 杜邦公司 Fungicidal amides
CN105451558A (en) * 2013-08-05 2016-03-30 先正达参股股份有限公司 Pyrazolyl pyrrolinones and their use as herbicides
WO2017148787A1 (en) * 2016-03-04 2017-09-08 Galapagos Nv Novel compounds and pharmaceutical compositions thereof for the treatment of fibrosis

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5362708A (en) * 1990-04-05 1994-11-08 Agrolinz Agrarchemikalien Gmbh Herbicidal agent
CN103910672A (en) * 2013-01-08 2014-07-09 连云港润众制药有限公司 Preparation method for vismodegib
CN105121411A (en) * 2013-04-15 2015-12-02 杜邦公司 Fungicidal amides
CN105451558A (en) * 2013-08-05 2016-03-30 先正达参股股份有限公司 Pyrazolyl pyrrolinones and their use as herbicides
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