CN110878081B - Pyridinyl ring substituted pyridazinol compounds and derivatives thereof, preparation method, weeding composition and application - Google Patents

Pyridinyl ring substituted pyridazinol compounds and derivatives thereof, preparation method, weeding composition and application Download PDF

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CN110878081B
CN110878081B CN201811035345.5A CN201811035345A CN110878081B CN 110878081 B CN110878081 B CN 110878081B CN 201811035345 A CN201811035345 A CN 201811035345A CN 110878081 B CN110878081 B CN 110878081B
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substituted
alkyl
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pyridine ring
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CN110878081A (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/CN2018/105407 priority patent/WO2019148850A1/en
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Abstract

The invention belongs to the technical field of pesticides, and particularly relates to a pyridine ring substituted pyridazinol compound, a derivative thereof, a preparation method, a weeding composition and application. The compound is shown in a general formula I: Wherein X is selected from halogen, cyano, alkyl, haloalkyl, alkoxy, haloalkoxy, R 1R2N-(C＝O)-、R1R2 N-, hydroxy, unsubstituted or substituted aryl; y is independently selected from hydrogen, halogen, cyano, nitro, R-O- (CH 2)n-,R1R2R3 SiO-and the like, R is an integer between 0 and 4, m is 0 or 1, n and q are respectively selected from an integer between 0 and 8, p is selected from an integer between 1 and 8, R is selected from hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl and the like which contain or do not contain halogen, R 1、R2、R3 is independently selected from hydrogen, nitro, hydroxyl and the like.

Description

Pyridinyl ring substituted pyridazinol compounds and derivatives thereof, preparation method, weeding composition and application
Technical Field
The invention belongs to the technical field of pesticides, and particularly relates to a pyridine ring substituted pyridazinol compound, a derivative thereof, a preparation method, a weeding composition and application.
Background
The prevention and control of weeds are a vital link in the process of realizing efficient agriculture, and the herbicides on the market at present are various in variety, such as pyridazine herbicide pyridatePyridazinol/>And the like, which belong to the class of photosystem ii inhibitors, inhibit the progress of photosynthesis by blocking electron transfer and transfer of light energy.
Due to the continuous expansion of the market, the resistance of weeds, the service life of medicines, the economy of medicines and other problems and the increasing importance of people on 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 pyridine ring substituted pyridazinol compound and a derivative thereof, a preparation method, a weeding composition and application, wherein the compound and the derivative thereof have very high weeding activity, are safe to crops and have good selectivity.
The technical scheme adopted by the invention is as follows:
A pyridine ring substituted pyridazinol compound and its derivative shown in general formula I:
Wherein X is selected from halogen, cyano, alkyl, haloalkyl, alkoxy, haloalkoxy, R 1R2N-(C＝O)-、R1R2 N-, hydroxy, unsubstituted or substituted aryl;
y is independently selected from hydrogen, halogen, cyano, nitro, azido, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkylalkyl, optionally halogen, unsubstituted or substituted aryl, arylalkyl, heteroaryl, heteroarylalkyl ,R-O-(CH2)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 Y's together form -OCH2O-、-CH2CH2O-、-OCH2CH2O-、-OCH(CH3)O-、-OC(CH3)2O-、-OCF2O-、-CF2CF2O-、-OCF2CF2O- or-ch=ch-;
r is an integer between 0 and 4, m is 0 or 1, n and q are respectively selected from integers between 0 and 8, and p is selected from integers between 1 and 8; wherein each m, n, q, p of the above groups is independently valued, and the values are such that each Y group is different from each other;
r is selected from hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkylalkyl, with or without halogen, and unsubstituted or substituted aryl, arylalkyl, heteroaryl, heteroarylalkyl;
R 1、R2、R3 is independently selected from the group consisting of hydrogen, nitro, hydroxy, amino, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkylalkyl, alkoxy, alkenyloxy, alkynyloxy, cycloalkyloxy, alkoxyalkyl, alkoxycarbonyl, alkylthio carbonyl, alkylsulfonyl, alkylsulfonylalkyl, alkylcarbonyl, alkylcarbonyloxy, alkylamino, alkylaminocarbonyl, alkoxycarbonyl, alkoxycarbonylalkyl, alkylaminocarbonylalkyl, trialkylsilyl, dialkylphosphono, and unsubstituted or substituted aryl, arylalkyl, aryloxy, arylalkyloxy, aryloxyalkyl, arylcarbonyl, arylsulfonyl, heteroaryl, heteroarylalkyl, heteroaryloxy, heteroaryloxyalkyl, heteroarylcarbonyl, heteroarylsulfonyl; or R 1R2 N-is selected from unsubstituted or substituted six-membered heterocyclic groups.
Preferably, X is selected from halogen, cyano, C 1～8 alkyl, halo C 1～8 alkyl, C 1～8 alkoxy, halo C 1～8 alkoxy, R 1R2N-(C＝O)-、R1R2 N-, hydroxy, unsubstituted or aryl substituted with 1 to 5 groups independently selected from halogen, cyano, nitro, hydroxy, carboxy, mercapto, amino, and C 1～8 alkyl, C 3～8 cycloalkyl, C 3～8 cycloalkyl C 1～8 alkyl, C 2～8 alkenyl, C 2～8 alkynyl, C 1～8 alkoxy, C 1～8 alkylcarbonyl, C 1～8 alkoxycarbonyl, C 1～8 alkylsulfonyl, C 1～8 alkylamino, or C 1～8 alkanoyloxy, with or without halogen;
Y is independently selected from the group consisting of hydrogen, halogen, cyano, nitro, azido, C 1～8 alkyl, C 2～8 alkenyl, C 2～8 alkynyl, C 3～8 cycloalkyl, C 5～8 cycloalkenyl, C 3～8 cycloalkyl C 1～8 alkyl, aryl C 1～8 alkyl, heteroaryl C 1～8 alkyl ,R-O-(CH2)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-; substituted with 1 to 5 groups independently selected from the group consisting of halogen, cyano, nitro, hydroxy, carboxy, mercapto, amino, C 1～8 alkyl, C 3～8 cycloalkyl, C 3～8 cycloalkyl C 1～8 alkyl, C 2～8 alkenyl, C 2～8 alkynyl, C 1～8 alkoxy, C 1～8 alkylcarbonyl, C 1～8 alkoxycarbonyl, C 1～8 alkylsulfonyl, C 1～8 alkylamino or C 1～8 alkanoyloxy, or two adjacent Y groups together form -OCH2O-、-CH2CH2O-、-OCH2CH2O-、-OCH(CH3)O-、-OC(CH3)2O-、-OCF2O-、-CF2CF2O-、-OCF2CF2O- or-CH=CH-;
r is an integer between 0 and 4, m is 0 or 1, n and q are respectively selected from integers between 0 and 6, and p is selected from integers between 1 and 6; wherein each m, n, q, p of the above groups is independently valued, and the values are such that each Y group is different from each other;
R is selected from the group consisting of hydrogen, C 1～8 alkyl with or without halogen, C 2～8 alkenyl, C 2～8 alkynyl, C 3～8 cycloalkyl, C 5～8 cycloalkenyl, C 3～8 cycloalkyl C 1～8 alkyl, and aryl, aryl C 1～8 alkyl, heteroaryl C 1～8 alkyl that is unsubstituted or substituted with 1 to 5 groups independently selected from the group consisting of halogen, cyano, nitro, hydroxy, carboxyl, mercapto, amino, and C 1～8 alkyl with or without halogen, C 3～8 cycloalkyl, C 3～8 cycloalkyl C 1～8 alkyl, C 2～8 alkenyl, C 2～8 alkynyl, C 1～8 alkoxy, C 1～8 alkylcarbonyl, C 1～8 alkoxycarbonyl, C 1～8 alkylsulfonyl, C 1～8 alkylamino, or C 1～8 alkanoyloxy;
R 1、R2、R3 is independently selected from the group consisting of hydrogen, nitro, hydroxy, amino, C 1～8 alkyl, C 2～8 alkenyl, C 2～8 alkynyl, C 2～8 cycloalkyl, C 2～8 cycloalkenyl, C 2～8 cycloalkyl C 2～8 alkyl, C 2～8 alkoxy, C 2～8 alkenyloxy, C 2～8 alkynyloxy, C 2～8 cycloalkyloxy, C 2～8 alkoxy C 2～8 alkyl, C 2～8 alkoxycarbonyl, C 2～8 alkylcarbonyl C 2～8 alkyl, C 2～8 alkylthio carbonyl, C 2～8 alkylsulfonyl C 2～8 alkyl, C 2～8 alkylcarbonyl, C 2～8 alkanoyloxy, C 2～8 alkylamino, C 2～8 alkylaminocarbonyl, C 2～8 alkoxyaminocarbonyl, C 2～8 alkoxycarbonyl C 2～8 alkyl, C 2～8 alkylaminocarbonyl C 2～8 alkyl, tri C 2～8 alkylsilyl, di C 2～8 alkylphosphono, and C 2～8 alkyl, C 2～8 cycloalkyl C 2～8 alkyl, C 2～8 alkenyl, C 2～8 alkynyl, C 2～8 alkoxy, C 2～8 alkylcarbonyl, C 2～8 alkoxycarbonyl, C 2～8 cycloalkyl, C 2～8 alkyl, C 2～8 alkenyl, C 2～8 alkynyl, C 2～8 alkoxy, C 2～8 alkylcarbonyl, C 2～8 alkyl, optionally containing halogen, unsubstituted or substituted by 1 to 5 groups selected independently from halogen, cyano, nitro, hydroxy, carboxyl, mercapto, amino aryl substituted by C 2～8 alkylsulfonyl, C 2～8 alkylamino or C 2～8 alkanoyloxy, aryl C 2～8 alkyl, aryloxy, aryl C 2～8 alkyloxy, aryloxy C 2～8 alkyl, arylcarbonyl, arylsulfonyl, heteroaryl C 2～8 alkyl, heteroaryloxy, heteroarylc 1～8 -alkyloxy, heteroaryloxy C 1～8 -alkyl, heteroarylcarbonyl, heteroarylsulfonyl; or R 1R2 N-is selected from six-membered heterocyclyl with or without further heteroatoms on the ring, unsubstituted or substituted by a member selected from C 1～8 alkyl, halogenated C 1～8 alkyl, C 1～8 alkoxy, halogenated C 1～8 alkoxy, C 1～8 alkoxycarbonyl, halogen.
More preferably, X is selected from fluorine, chlorine, bromine, cyano, C 1～6 alkyl, halogenated C 1～6 alkyl, C 1～6 alkoxy, halogenated C 1～6 alkoxy, R 1R2N-(C＝O)-、R1R2 N-, hydroxy, phenyl unsubstituted or substituted with 1 to 3 groups independently selected from halogen, cyano, nitro, hydroxy, carboxy, mercapto, amino, C 1～6 alkyl with or without halogen, C 3～6 cycloalkyl, C 3～6 cycloalkyl C 1～6 alkyl, C 2～6 alkenyl, C 2～6 alkynyl, C 1～6 alkoxy, C 1～6 alkylcarbonyl, C 1～6 alkoxycarbonyl, C 1～6 alkylsulfonyl, C 1～6 alkylamino or C 1～6 alkanoyloxy;
Y is independently selected from hydrogen, fluorine, chlorine, bromine, cyano, nitro, azido, C 1～6 alkyl with or without fluorine, chlorine, bromine, C 2～6 alkenyl, C 2～6 alkynyl, C 3～6 cycloalkyl, C 5～6 cycloalkenyl, C 3～6 cycloalkyl C 1～6 alkyl, aryl C 1～6 alkyl, heteroaryl C 1～6 alkyl ,R-O-,R-O-(CH2)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 Y groups together form-CH=CH-;
r is 0, 1, 2, 3 or 4, m is 0 or 1, n, q are selected from 0, 1, 2, 3 or 4, respectively, p is selected from 1, 2, 3 or 4; wherein each m, n, q, p of the above groups is independently valued, and the values are such that each Y group is different from each other;
R is selected from hydrogen, C 1～6 alkyl with or without fluorine, chlorine, bromine, C 2～6 alkenyl, C 2～6 alkynyl, C 3～6 cycloalkyl, C 5～6 cycloalkenyl, C 3～6 cycloalkyl C 1～6 alkyl, and aryl, aryl C 1～6 alkyl, heteroaryl C 1～6 alkyl that are unsubstituted or substituted with 1 to 3 groups independently selected from fluorine, chlorine, bromine, cyano, nitro, hydroxyl, carboxyl, mercapto, amino, and C 1～6 alkyl with or without fluorine, chlorine, bromine, C 3～6 cycloalkyl, C 3～6 cycloalkyl C 1～6 alkyl, C 2～6 alkenyl, C 2～6 alkynyl, C 1～6 alkoxy, C 1～6 alkylcarbonyl, C 1～6 alkoxycarbonyl, C 1～6 alkylsulfonyl, C 1～6 alkylamino, or C 1～6 alkanoyloxy;
R 1、R2、R3 is each independently selected from the group consisting of hydrogen, nitro, hydroxy, amino, C 1～6 alkyl, C 2～6 alkenyl, C 2～6 alkynyl, C 3～6 cycloalkyl, C 5～6 cycloalkenyl, C 5～6 cycloalkyl C 5～6 alkyl, C 5～6 alkoxy, C 5～6 alkenyloxy, C 5～6 alkynyloxy, C 5～6 cycloalkyloxy, C 5～6 alkoxy C 5～6 alkyl, C 5～6 alkoxycarbonyl, C 5～6 alkylthio carbonyl, C 5～6 alkylsulfonyl C 5～6 alkyl, C 5～6 alkylcarbonyl C 5～6 alkyl, C 5～6 alkanoyloxy, C 5～6 alkylamino, C 5～6 alkylaminocarbonyl, C 5～6 alkoxyaminocarbonyl, C 5～6 alkoxycarbonyl C2 alkyl, C 5～6 alkylaminocarbonyl C 5～6 alkyl, tri C 5～6 alkylsilyl, di 5～6 alkylphosphono, and aryl, aryl C 5～6 alkyl, aryloxy, aryl C 5～6 alkyloxy, aryloxy C 5～6 alkyl, arylcarbonyl, arylsulfonyl, heteroaryl, unsubstituted or substituted with 1 to 3 groups independently selected from fluoro, chloro, bromo, cyano, nitro, hydroxy, carboxy, mercapto, amino, C 5～6 alkyl, C 5～6 cycloalkyl C 5～6 alkyl, C 5～6 alkenyl, C 5～6 alkynyl, C 5～6 alkoxy, C 5～6 alkylcarbonyl, C 5～6 alkoxycarbonyl, C 5～6 alkylsulfonyl, C 5～6 alkylamino, or C 5～6 alkanoyloxy, with or without fluoro, chloro, bromo, C 5～6 alkyl, C 5～6 cycloalkyl, C 5～6 alkoxycarbonyl, aryl sulfonyl, heteroaryl, aryl, heteroaryl, and the like, heteroaryl C 1～6 alkyl, heteroaryloxy, heteroaryl C 1～6 alkyloxy, heteroaryloxy C 1～6 alkyl, heteroarylcarbonyl, heteroarylsulfonyl; or R 1R2 N-is selected from
The aryl group is Heteroaryl is selected from/> R' represents hydrogen, nitro, hydroxy, amino, C 1～6 alkyl with or without fluorine, chlorine, bromine, C 2～6 alkenyl, C 2～6 alkynyl, C 3～6 cycloalkyl, C 5～6 cycloalkenyl, C 3～6 cycloalkyl C 1～6 alkyl, C 1～6 alkoxy, C 2～6 alkenyloxy, C 2～6 alkynyloxy, C 3～6 cycloalkyloxy, C 1～6 alkoxy C 1～6 alkyl, C 1～6 alkoxycarbonyl, C 1～6 alkylthio carbonyl, C 1～6 alkylsulfonyl C 1～6 alkyl, C 1～6 alkylcarbonyl, C 1～6 alkanoyloxy, C 1～6 alkylamino, C 1～6 alkylaminocarbonyl, C 1～6 alkoxyaminocarbonyl, C 1～6 alkoxycarbonyl C 1～6 alkyl, C 1～6 alkylaminocarbonyl C 1～6 alkyl, tri C 1～6 alkylsilyl, di C 1～6 alkylphosphono, and/>, unsubstituted or substituted with 1 to 3 groups independently selected from fluoro, chloro, bromo, cyano, nitro, hydroxy, carboxy, mercapto, amino, C 1～6 alkyl, C 1～6 cycloalkyl C 1～6 alkyl, C 1～6 alkenyl, C 1～6 alkynyl, C 1～6 alkoxy, C 1～6 alkylcarbonyl, C 1～6 alkoxycarbonyl, C 1～6 alkylsulfonyl, C 1～6 alkylamino, or C 1～6 alkanoyloxy groups, with or without fluoro, chloro, bromo, C 1～6 alkyl, C 1～6 cycloalkyl C 1～6 alkyl, C 1～6 alkenyl, C 1～6 alkynyl, C 1～6 alkoxycarbonyl, C 1～6 alkylsulfonyl, C 1～6 alkylamino, C 1～6 alkanoyloxy, andAryl, arylc 1～6 alkyl, aryloxy, arylc 1～6 alkyl oxy, aryloxy C 1～6 alkyl, arylcarbonyl, arylsulfonyl, heteroaryl, heteroarylc 1～6 alkyl, heteroaryloxy, heteroarylc 1～6 alkyl oxy, heteroaryloxy C 1～6 alkyl, heteroarylcarbonyl, heteroarylsulfonyl.
Further preferably, X is selected from the group consisting of chloro, cyano, methyl, ethyl, trifluoromethyl, pentafluoroethyl, difluoromethyl, monofluoromethyl, methoxy, ethoxy, trifluoromethoxy, pentafluoroethoxy,
R is 0,1, 2, 3 or 4;
Y is independently selected from the group consisting of hydrogen, methyl, ethyl, methoxy, ethoxy, fluoro, chloro, bromo, amino, cyano, trifluoromethyl,
Or alternativelyRepresentative/>
The derivatives of the inventionRefers to the agriculturally acceptable derivatives of the hydroxyl group at the 4-position of the pyridazine ring in the general formula I, and comprises salts, esters, oximes, hydroxylamine, ethers and the like.
The salt derivative is a salt used in a general agricultural chemical, and for example, an alkali metal salt, an alkaline earth metal salt or an amine salt, or when an alkaline moiety is present in a molecule, a salt such as a sulfate, a hydrochloride, a nitrate, a phosphate, or the like can be prepared. These salts are also included in the present invention as long as they are used as herbicides for agriculture and gardening. 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, 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 alkanolamines; primary, secondary, tertiary or quaternary alkyl alkanolamines; or a primary, secondary, tertiary or quaternary alkoxyalkanolamine salt, preferably wherein the alkyl, alkanol and alkoxy groups are independently saturated and independently contain C1-C4 carbon atoms, more preferably monoethanolamine, dimethylethanolamine, triethanolamine, dimethylamine, triethylamine, isopropylamine, choline or diglycolamine salts.
Solvates of the compounds of the present invention are also encompassed within the present invention.
The compounds of the present invention also include compounds having asymmetric carbon atoms, in which 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 the pyridazine ring, and may be, for example, a (thio) acyl group or a C1-C18 alkyl (thio) carbonyl group which may be substituted [ the substituent is the same or different 1-3 substituents selected from the group consisting of a halogen atom, an amino group, a C3-C8 cycloalkyl group, a C1-C8 alkoxy group, a C1-C8 alkylthio group, a C1-C8 alkoxycarbonyl group, a C1-C8 alkylcarbonyloxy group, a C1-C8 alkylcarbonyl group, a C2-C8 alkenyloxycarbonyl group which may be substituted { the substituent is the same or different 1-3 substituents selected from the group consisting of a C3-C8 cycloalkyl group, a cyano group and a benzoyl group which may be substituted }, the substituent is the same or different 1-3 substituents selected from the group consisting of 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, a hydroxy methyl phosphino group, a C3-C8 alkenyloxycarbonyl group which may be substituted { the substituent is the same or different 1-3 substituents selected from the group consisting of 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, a C1-C3 substituent which may be substituted { the same or different 1-C8 alkoxycarbonyl group, a C1-C8 alkoxycarbonyl group which may be substituted { the same or different 1-C8 alkenyloxycarbonyl group, a C1-C8 alkenyloxycarbonyl group which may be substituted { the C3-C8 alkenyloxycarbonyl group. The substituent is a halogen atom, a C1-C8 alkyl group, a optionally substituted phenoxy group (the substituent is 1-3 substituents selected from the group consisting of a halogen atom, a C1-C8 alkyl group, a C1-C8 haloalkyl group, a C3-C8 cycloalkyl group and a C1-C8 alkoxycarbonyl group, which may be the same or different), a 2, 3-dihydro-1H-indenyloxy group and an optionally substituted benzoyl group (the substituent is 1-3 substituents selected from the group consisting of 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, which may be the same or different), an optionally substituted phenyl group, phenoxy group, benzyloxy group, phenylthio group and benzylthio group (the substituent is an optionally substituted phenyl group selected from the group consisting of a halogen atom, a C1-C8 alkyl group, a phenylthio group and a benzylthio group) C1-C8 alkoxy, C1-C8 haloalkyl and C1-C8 alkoxycarbonyl, and 1 or more identical or different substituents selected from C1-C8 alkylthio ], C3-C8 cycloalkyl (thio) carbonyl, adamantyl (thio) carbonyl, optionally substituted C2-C8 alkenyl (thio) carbonyl { the substituent being one or more identical or different substituents selected from the group consisting of a halogen atom, C1-C8 alkoxy and optionally substituted phenyl, phenylthio or phenoxy (the substituent being one or more identical or different substituents selected from the group consisting of a halogen atom, C1-C8 alkyl, C1-C8 alkoxy, C1-C8 haloalkyl and C1-C8 alkoxycarbonyl }, C2-C8 alkynyl (thio) carbonyl }, phenylthio or phenylthio, A benzylthio group or a naphthylthio group which may be substituted [ the substituent being a halogen atom, a C1-C8 alkyl group which may be substituted (the substituent being 1 or more substituents which may be the same or different selected from the halogen atom and the phenyl group), a cyano group, a hydroxy group, a C1-C8 alkylcarbonyl group, a C1-C8 alkoxycarbonyl group, a C1-C8 alkylcarbonyloxy group, a C1-C8 alkylcarbonylamino group, a amino group which may be substituted (the substituent being 1 to 3 substituents which may be the same or different selected from the group consisting of a C1-C8 alkyl group, a C1-C8 alkoxy group, a C1-C8 alkylcarbonyl group, a halogenated C1-C8 alkyl group and the phenyl group ], a C2-C8 alkenyloxycarbonyl group which may be substituted { the substituent being a C3-C8 cycloalkyl group, a cyano group and a benzoyl group which may be substituted (the substituent being a halogen atom, a C1-C8 alkyl group 1 to 3 substituents selected from the group consisting of C1 to C8 haloalkyl, C1 to C8 alkoxycarbonyl, nitro and C1 to C8 alkylsulfonyl), 1 to 3 substituents selected from the group consisting of C1 to C8 alkoxycarbonyl, nitro and C1 to C8 alkylsulfonyl, C3 to C8 alkenyloxycarbonyl which may be substituted { the substituent is a substituent selected from the group consisting of oxo and benzoyl which may be substituted (the substituent is a substituent selected from the group consisting of halogen atom, C1 to C8 alkyl, C1 to C8 haloalkyl, C1 to C8 alkoxycarbonyl, nitro and C1 to C8 alkylsulfonyl which may be the same or different), 1 to 2 substituents selected from the group consisting of phenyl, nitro and C1 to C8 alkoxy which may be substituted (the substituent is a substituent selected from the group consisting of halogen atom and phenyl which may be the same or different), phenoxy, optionally substituted 5-or 6-membered hetero-epoxycarbonyl group {1 nitrogen atom, oxygen atom or sulfur atom in the ring of the heterocyclic ring, may further contain 1 to 2 nitrogen atoms. The substituent is the same or different 1 to 3 substituents selected from a halogen atom, a C1 to C8 alkyl group, a phenoxy group which may be substituted (the substituent is the same or different 1 to 3 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 the same or different 1 to 3 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 hetero epoxy sulfonyl group which may be substituted { the ring of the heterocyclic ring may contain 1 nitrogen atom, oxygen atom or sulfur atom, and may further contain 1 to 2 nitrogen atoms }. The substituent is a halogen atom, a C1-C8 alkyl group, a optionally substituted phenoxy group (the substituent is a same or different 1-3 substituent 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 an optionally substituted benzoyl group (the substituent is a same or different 1-3 substituent 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), a same or different 1-3 substituent selected from a halogen atom, a mercapto formyl group substituted with a halogen, a 3-8 membered heterocyclic (thio) carbonyl group { the ring of the heterocyclic ring may contain 1 nitrogen atom, oxygen atom or sulfur atom, and optionally contain 1-2 nitrogen atoms, and optionally may contain 1-2 carbon atoms within the heterocyclic ring containing 1-5-to 6 carbon atoms. The substituent is a halogen atom, a C1-C8 alkyl group which may be substituted (the substituent is the same or different substituent selected from the group consisting of a halogen atom and a phenyl group), a C1-C8 alkylcarbonyl group, a C1-C8 alkoxycarbonyl group which may be substituted (the substituent is the same or different 1-3 halogen atoms), a nitro group, a hydroxyl group, a C1-C8 alkoxy group, a phenoxy group, a C1-C8 alkylthio group, a C2-C8 alkenylthio group and a phenylthio group, a 5-14 membered condensed bicyclic or tricyclic heterocyclic (thio) carbonyl group which may be substituted (the heterocyclic ring contains 1 nitrogen atom, oxygen atom or sulfur atom, and may contain 1 to 2 nitrogen atoms or oxygen atom), a 5-or 6 heterocyclic (thio) carbonyl group which may be selected from the halogen atom and a C1-C8 alkyl group, a 5-or 6 heterocyclic (thio) carbonyl group which may contain 1 to 3 halogen atom, a cycloalkyl group which may be substituted (the heterocyclic ring) or a C1-C8 alkoxycarbonyl group which may contain 1 to 2 nitrogen atom, an oxygen atom or sulfur atom, a cycloalkyl group which may contain 1-C2 nitrogen atom, an alkoxy group which may be selected from the C1-C8 alkoxycarbonyl group, a cycloalkyl group which may contain 1-C8 carbon atom, a cycloalkyl group which may be substituted (the heterocyclic) and a cycloalkyl group which may contain 1-C8 carbon atom, a cycloalkyl group which may be substituted, a cycloalkyl group which may be selected from the C1-C8 carbon atom, a cycloalkyl group which may be substituted, a cycloalkyl group which may be selected from the carbon atom which may be a carbon atom, a carbon atom which may be different from the carbon atom, a carbon atom which may be C18 carbon atom, a carbon atom which may be substituted, a carbon atom which may be C18 carbon atom which may be C carbon atom which may be substituted, and a carbon atom which may be substituted Phenyloxy (thio) carbonyl, phenylthio (thio) carbonyl, phenylC 1-C8 alkyloxy (thio) carbonyl or phenylC 1-C8 alkylthio (thio) carbonyl which are identical or different and are selected from halogen atom, C1-C8 alkyl, cyano, C1-C8 alkylcarbonyl, C1-C8 alkoxycarbonyl, nitro and C1-C8 alkoxy, condensed polycyclic hydrocarbyloxy (thio) carbonyl, condensed polycyclic hydrocarbylthio (thio) carbonyl, 5-or 6-membered hetero-epoxy (thio) carbonyl which may be substituted or 5-or 6-membered heterocyclic thio (thio) carbonyl { the ring of the heterocyclic ring 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, an optionally substituted phenoxy group (the substituent is an identical or different 1-3 substituent selected from the group consisting of 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 an optionally substituted benzoyl group (the substituent is an identical or different 1-3 substituent selected from the group consisting of 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), an optionally substituted aminomethyl (thio) acyl group { the substituent is an identical or different 1-3 substituent selected from the group consisting of an optionally substituted C1-C8 alkyl group (the substituent is an identical or different 1-C8 alkoxycarbonyl group selected from the group consisting of a halogen atom, a C1-C8 alkoxycarbonyl group, a cyano group, a phenyl group and a C1-C8 alkoxy group), an identical or different 1-C8 alkoxycarbonyl group, an optionally substituted phenyl group, an identical or different C1-C8 alkoxycarbonyl group, an optionally substituted alkoxycarbonyl group, a C1-C8 alkoxycarbonyl group and an identical or different C1-C8 alkoxycarbonyl group }(Het is a 5-6 membered heterocyclic ring containing, in addition to the C and N atoms in the 1-position, 0 to 3 atoms or groups as constituent parts of the ring: O, NR b、C＝O,Ra and R b independently represent hydrogen, C1-C8 alkyl), C1-C8 alkyl sulfoxide which may be substituted, C1-C8 alkylsulfonyl, C2-C8 alkenylsulfonyl or C3-C8 cycloalkylsulfonyl which is one or more substituents which may be the same or different from each other selected from the group consisting of halogen atom, C1-C8 alkylsulfonyl, phenylsulfonyl which may be substituted, benzylsulfonyl or naphthylsulfonyl which may be substituted by one or more substituents which may be the same or different from each other selected from the group consisting of halogen atom, C1-C8 alkyl, halogenated C1-C8 alkyl, cyano, C1-C8 alkylcarbonyl, C1-C8 alkoxycarbonyl, nitro, C1-C8 alkoxy, halogenated C1-C8 alkoxy, C1-C8 alkylsulfonyl, optionally substituted aminoacyl which may be substituted (which is one or more substituents which may be the same or different from each other selected from the group consisting of halogen atom, C1-C8 alkyl, C1-C8 haloalkyl, C3-C3 cycloalkyl which may be the same or different from the group consisting of { C1-C8 alkyl } which may be substituted by one or more than one or more substituents which may be the same selected from the group consisting of halogen atom, C1-C8 alkyl, halogen atom, C3-C3 alkyl, C3-C3 cycloalkyl which may be substituted or C1-C8 alkyl which may be substituted, alkoxy which may be substituted by one or more than one of which may be substituted from the substituents which may be selected from the group consisting of C1-C8 alkoxy, alkoxy which may be substituted, the optionally substituted C3-C8 alkenyloxysulfonyl group { the substituent is the same or different 1-2 substituents selected from oxo and optionally substituted benzoyl (the substituent is the same or different 1-3 substituents selected from halogen atom, C1-C8 alkyl group, C1-C8 haloalkyl group, C1-C8 alkoxycarbonyl group, nitro group and C1-C8 alkylsulfonyl group) }, and the optionally substituted 5-or 6-membered hetero epoxysulfonyl group { the ring of the heterocyclic ring may contain 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 optionally substituted phenoxy group (the substituent is a same or different 1-3 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 an optionally substituted benzoyl group (the substituent is a same or different 1-3 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), a 5-10 membered aromatic heterocyclic sulfonyl group or a 5-10 membered hetero epoxy sulfonyl group { the ring of the heterocyclic ring may contain 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 optionally substituted phenoxy group (the substituent is 1-3 substituents selected from the group consisting of a halogen atom, a C1-C8 alkyl group, a C1-C8 haloalkyl group, a C3-C8 cycloalkyl group and a C1-C8 alkoxycarbonyl group, which may be the same or different), a 2, 3-dihydro-1H-indenyloxy group and an optionally substituted benzoyl group (the substituent is 1-3 substituents selected from the group consisting of 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, which may be the same or different), a C1-C8 alkoxysulfonyl group, an optionally substituted C1-C8 alkylamino sulfonyl group (the substituent is 1-or more of the same or different substituents selected from the halogen atom),/>(Het is a 5-6 membered heterocyclic ring containing, in addition to the N atoms in the C and 1-positions, 0 to 3 atoms or groups as ring components: O, NR b、C＝O,Ra and R b independently represent hydrogen, C1-C8 alkyl), di (C1-C8 alkyl) phosphoryl, di (C1-C8 alkyl) thiophosphoryl.
Preferably, the method can be that, C1-C10-alkyl (thio) carbonyl which may be substituted { the substituent being 1 or more identical or different substituents selected from fluorine, chlorine, bromine, C3-C6-cycloalkyl, C1-C6-alkoxy, C1-C6-alkylthio, C1-C6-alkoxycarbonyl, C1-C6-alkylcarbonyl, C1-C6-alkylcarbonyloxy, optionally substituted phenyl, phenylthio, phenoxy or benzyloxy (the substituent being identical or different 1-3 substituents selected from fluorine, chlorine, bromine, C1-C6-alkyl, C1-C6-alkoxy }, C3-C6-cycloalkyl (thio) carbonyl, optionally substituted C2-C6-alkenyl (thio) carbonyl { the substituent being identical or different substituent selected from fluorine, chlorine, bromine, C1-C6-alkoxy, optionally substituted phenyl, phenylthio or phenoxy (the substituent being identical or different 1-3 substituents selected from fluorine, chlorine, bromine, C1-C6-alkyl }, optionally substituted phenyl 1 or more identical or different substituents selected from 1 to 3 identical or different substituents selected from C1-C6 alkoxy), a benzylic (thio) acyl group or a naphthylic (thio) acyl group which may be substituted { the substituent is an identical or different substituent selected from fluorine, chlorine, bromine, an identical or different C1-C6 alkyl group or a C1-C6 alkoxy group which is an identical or different substituent selected from fluorine, chlorine, bromine and phenyl, cyano, hydroxy, C1-C6 alkylcarbonyl, C1-C6 alkoxycarbonyl, C1-C6 alkylcarbonyloxy, C1-C6 alkylcarbonylamino, an amino group which may be substituted (the substituent is an identical or different substituent selected from C1-C6 alkyl, C1-C6 alkoxy, C1-C6 alkylcarbonyl, halogenated C1-C6 alkyl and phenyl), phenyl, 1-3 substituents selected from nitro and phenoxy groups, optionally substituted 3-8 membered heterocyclic (thio) carbonyl { the heterocyclic ring being The substituent is selected from fluorine, chlorine, bromine, C1-C6 alkyl (the substituent is selected from fluorine, chlorine, bromine and phenyl groups of 1 or more of the same or different substituents), C1-C6 alkoxycarbonyl, substituted phenyl (the substituent is selected from fluorine, chlorine, bromine of the same or different 1-3 substituents), nitro, hydroxyl, C1-C6 alkoxy, phenoxy, C1-C6 alkylthio, C2-C6 alkenylthio and phenylthio of the same or different 1-3 substituents }, substituted 5-14 membered condensed bicyclic or tricyclic heterocyclic (thio) carbonyl (the heterocyclic ring is/>) The substituent is the same or different 1 to 3 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 substituent is the same or different 1 to 3 substituents selected from fluorine, chlorine, bromine, C1 to C6 alkoxy and phenyl), C3 to C6 cycloalkyloxy (thio) carbonyl, C3 to C6 cycloalkylthio (thio) carbonyl, phenoxy (thio) carbonyl which may be substituted, phenylthio (thio) carbonyl, phenylC 1 to C6 alkylthio (thio) carbonyl or phenylC 1 to C6 alkylthio (the substituent is the same or different 1 to 3 substituents selected from fluorine, chlorine, bromine, C1 to C6 alkyl, cyano, C1 to C6 alkoxycarbonyl, nitro and C1 to C6 alkoxy), methyl (thio) carbonyl which may be substituted { C1 to C6 alkylthio (thio) carbonyl which may be substituted) is the same or different 1 to C6 alkoxy (thio) carbonyl which may be substituted { C1 to C6 alkylthio (thio) carbonyl }, phenyl which may be substituted { C1 to C6 alkoxy (thio) carbonyl, C1 to C6 alkylthio (thio) carbonyl which may be substituted { C1 to C6 alkoxy } which may be substituted or may be substituted 1 to C6 alkoxy (thio) carbonyl which may be substituted { C1 to C6 alkoxy }, C1 to C6 alkoxycarbonyl, C1 to C6 alkoxycarbonyl, nitro }, which may be substituted { may be substituted C1 to be substituted or different from C1 to C6 alkoxy (alkoxycarbonyl }.C to C1 to C6 alkoxycarbonyl, and the substituent which may be substituted(Het is/> R a and R b independently represent hydrogen, C1-C6 alkyl), C1-C6 alkyl sulfoxide which may be substituted, C1-C6 alkylsulfonyl, C2-C6 alkenylsulfonyl or C3-C6 cycloalkylsulfonyl which is selected from the group consisting of fluorine, chlorine, bromine, C1-C6 alkylsulfonyl and1 or more identical or different substituents, phenylsulfonyl which may be substituted, benzylsulfonyl or naphthylsulfonyl which may be substituted, is selected from the group consisting of fluorine, chlorine, bromine, C1-C6 alkyl, halogenated C1-C6 alkyl, cyano, C1-C6 alkylcarbonyl, C1-C6 alkoxycarbonyl, nitro, C1-C6 alkoxy, halogenated C1-C6 alkoxy, C1-C6 alkylsulfonyl and substituted aminoacyl which may be substituted (which is C1-C6 alkyl), which may be substituted phenoxy which is selected from the group consisting of fluorine, chlorine, bromine, C1-C6 alkyl, C1-C8 cycloalkyl which may be substituted and 3-C1-C6 alkoxycarbonyl which may be substituted or different from the group consisting of fluorine, chlorine, bromine, C1-C6 alkyl, C1-C8 cycloalkyl which may be substituted, and 3-C6 alkoxycarbonyl which may be substituted or different from the group which may be substituted by 1-C6 alkoxycarbonyl which may be substituted The substituent is the same or different 1-3 substituents selected from fluorine, chlorine, bromine, C1-C6 alkyl, phenoxy which can be substituted (the substituent is the same or different 1-3 substituents selected from fluorine, chlorine, bromine, C1-C6 alkyl, C1-C6 haloalkyl, C3-C6 cycloalkyl and C1-C6 alkoxycarbonyl), C1-C6 alkylamino sulfonyl which can be substituted (the substituent is the same or different 1 or more substituents selected from fluorine, chlorine and bromine)(Het is/>R a and R b independently represent hydrogen, C1-C6 alkyl), di (C1-C6 alkyl) phosphoryl, di (C1-C6 alkyl) thiophosphoryl-bonded compound.
The oxime derivative is an oxime group bonded to the oxygen atom of the hydroxyl group at the 4-position of the pyridazine ringR 11、R22 may be, for example, each independently represents hydrogen, a C1-C18 alkyl group or a C2-C18 alkenyl group which may be substituted (the substituent is the same or different 1-to 3-substituents selected from the group consisting of 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, a phenylacyl group or a 5-to 6-membered aromatic heterocyclic group which may be selected from the group consisting of 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 alkoxycarbonyl group, a hydroxyl group, a carboxyl group, a mercapto group, an amino group, a cyano group, a nitro group and a C1-C8 alkylsulfonyl group, or the like, or a C1-to 3-membered aromatic heterocyclic group which may contain at least one heteroatom such as oxygen, sulfur or 11、R22, a saturated or 5-membered heterocyclic ring which may contain at least one atom, 5-to 5-membered oxygen, sulfur atom, or the like.
Preferably, R 11、R22 each independently represents hydrogen, a C1-C10 alkyl group or a C2-C10 alkenyl group which may be substituted (the substituent is 1 or more of the same or different substituents selected from fluorine, chlorine, bromine, C1-C6 alkoxy, C1-C6 alkylthio, C1-C6 alkylamino), a phenyl group which may be substituted, a phenyl acyl group or a 5-6 membered aromatic heterocyclic group (the aromatic heterocyclic group is The substituent is the same or different 1-3 substituents selected from fluorine, chlorine, bromine, C1-C6 alkyl, C3-C6 cycloalkyl, C1-C6 haloalkyl, C1-C6 alkylcarbonyl, C1-C6 alkoxy, C1-C6 alkoxycarbonyl, C1-C6 alkylamino, hydroxy, carboxyl, mercapto, amino, cyano, nitro and C1-C6 alkylsulfonyl), or R 11、R22 forms a 5-6 membered saturated carbocyclic ring or a 5-6 membered heterocyclic ring (containing at least one heteroatom such as oxygen, sulfur, nitrogen).
The hydroxylamine derivative is a hydroxylamine group bonded to the oxygen atom of the hydroxyl group at the 4-position of the pyridazine ringThe compound of (C) may be, for example, R 11'、R22' independently represents hydrogen, a C1-C18 alkyl group or a C2-C18 alkenyl group which may be substituted (the substituent is 1 to 3 substituents which may be the same or different and are selected from the group consisting of 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 1 to 3 substituents which may be the same or different and are selected from the group consisting of 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 group, a C1-C8 alkylamino group, a hydroxyl group, a carboxyl group, a mercapto group, an amino group, a cyano group, a nitro group and a C1-C8 alkylsulfonyl group), a C1-C18 alkoxycarbonyl group benzoyl group which may be substituted [ the substituent is 1 to 3 substituents selected from the group consisting of a halogen atom, a C1 to C8 alkyl group which may be substituted, a C2 to C8 alkenyl group, a C2 to C8 alkynyl group or a C3 to C8 cycloalkyl group (the substituent is 1 to 3 substituents which may be the same or different from one another selected from the group consisting of a halogen atom and a phenyl group), cyano group, a C1 to C8 alkylcarbonyl group, a C1 to C8 alkoxycarbonyl group, a C1 to C8 alkylsulfonyl group, a C2 to C8 alkenyloxycarbonyl group which may be substituted { the substituent is the same or different from one another selected from the group consisting of a C3 to C8 cycloalkyl group, cyano group and a benzoyl group which may be substituted (the substituent is 1 to 3 substituents which may be the same or different from one another selected from the group consisting of 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 }), C3-C8 cycloalkenyl oxycarbonyl { the substituent is selected from oxo and optionally substituted benzoyl (the substituent is selected from halogen atom, C1-C8 alkyl, C1-C8 haloalkyl, C1-C8 alkoxycarbonyl, nitro and C1-C8 alkylsulfonyl groups of the same or different 1-2 substituents }, hydroxy, carboxyl, mercapto, amino, phenyl, nitro, optionally substituted C1-C8 alkoxy, C1-C8 alkylamino or C1-C8 alkylthio (the substituent is selected from halogen atom and phenyl of the same or different 1-3 substituents), phenoxy, optionally substituted 5-or 6-membered hetero-epoxy carbonyl { the heterocyclic ring contains 1 nitrogen atom, oxygen atom or sulfur atom, may contain 1-2 nitrogen atoms. The substituent is the same or different 1 to 3 substituents selected from a halogen atom, a C1 to C8 alkyl group, a phenoxy group which may be substituted (the substituent is the same or different 1 to 3 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), a2, 3-dihydro-1H-indenyloxy group and a benzoyl group which may be substituted (the substituent is the same or different 1 to 3 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 a5 or 6 membered hetero epoxy sulfonyl group which may be substituted { the ring of the heterocyclic ring may contain 1 nitrogen atom, oxygen atom or sulfur atom, and may further contain 1 to 2 nitrogen atoms }. The substituent is the same or different 1 to 3 substituents selected from the group consisting of a halogen atom, a C1 to C8 alkyl group, a phenoxy group which may be substituted (the substituent is the same or different 1 to 3 substituents selected from the group consisting of 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), a2, 3-dihydro-1H-indenyloxy group and a benzoyl group which may be substituted (the substituent is the same or different 1 to 3 substituents selected from the group consisting of 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 11'、R22' may each independently represent hydrogen, C1-C10 alkyl or C2-C10 alkenyl which may be substituted (the substituent being 1 or more identical or different substituents selected from fluorine, chlorine, bromine), C1-C10 alkoxycarbonyl, phenyl which may be substituted or benzoyl which may be 1 to 3 identical or different substituents selected from fluorine, chlorine, bromine, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C1-C6 haloalkyl, C1-C6 alkylcarbonyl, C1-C6 alkoxy, C1-C6 alkoxycarbonyl, C1-C6 alkylamino, hydroxy, carboxy, mercapto, amino, cyano, nitro and C1-C6 alkylsulfonyl.
The ether derivative is a compound obtained by bonding the following group to the oxygen atom of the hydroxyl group at the 4-position of the pyridazine ring, and may be, for example, C1-C18 alkyl which may be substituted or C2-C18 alkenyl which may be substituted is selected from the group consisting of halogen atom, C1-C8 alkoxy, C1-C8 alkylthio, C1-C8 alkylamino, di-C1-C8 alkylamino, C1-C8 alkoxycarbonyl, and 1 or more identical or different substituents selected from the group consisting of C1-C8 alkoxycarbonyloxy, phenyl which may be substituted, benzyl or benzoyl C1-C8 alkyl which may be substituted is selected from the group consisting of halogen atom, C2-C8 alkyl which may be substituted, C2-C8 alkynyl which may be substituted or C3-C8 cycloalkyl which may be selected from the group consisting of halogen atom and phenyl, cyano which may be substituted by 1-C3 substituents selected from the group consisting of identical or different substituents selected from the group consisting of halogen atom, C1-C8 alkoxycarbonyl, C1-C8 alkylsulfonyl which may be substituted, C2-C8 alkenyloxycarbonyl which may be substituted { the substituent is selected from the group consisting of C3-C8 cycloalkyl which may be substituted, cyano which may be substituted by C1-C8 alkoxycarbonyl, and C1-C8 alkylsulfonyl which may be substituted by identical or different from the group selected from the group consisting of C1-C8 alkoxycarbonyl which may be substituted { C2-C8 alkoxycarbonyl which may be substituted }, benzoyl which may be substituted by identical or different from the group selected from the group consisting of C1-C8 alkoxycarbonyl, C1-C8 alkoxycarbonyl which may be substituted by the group which may be substituted by C1-C8 alkoxycarbonyl, and C1-C8 alkoxycarbonyl which may be substituted { C1-C8 alkoxycarbonyl which may be substituted by C1-C may be substituted or may be substituted by C substituted, hydroxy, carboxyl, mercapto, amino, phenyl, nitro, optionally substituted C1-C8 alkoxy, C1-C8 alkylamino or C1-C8 alkylthio (the substituents being 1-3 substituents selected from halogen atoms and phenyl groups, which may be the same or different), phenoxy, optionally substituted 5-or 6-membered heteroaryloxycarbonyl { 1 nitrogen atom, oxygen atom or sulfur atom in the ring of the heterocycle, optionally 1-2 nitrogen atoms in the ring. The substituent is the same or different 1 to 3 substituents selected from a halogen atom, a C1 to C8 alkyl group, a phenoxy group which may be substituted (the substituent is the same or different 1 to 3 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), a2, 3-dihydro-1H-indenyloxy group and a benzoyl group which may be substituted (the substituent is the same or different 1 to 3 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 hetero epoxy sulfonyl group which may be substituted { the ring of the heterocyclic ring may contain 1 nitrogen atom, oxygen atom or sulfur atom, and may further contain 1 to 2 nitrogen atoms }. The substituent is the same or different 1 to 3 substituents selected from the group consisting of a halogen atom, a C1 to C8 alkyl group, a phenoxy group which may be substituted (the substituent is the same or different 1 to 3 substituents selected from the group consisting of 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), a2, 3-dihydro-1H-indenyloxy group and a benzoyl group which may be substituted (the substituent is the same or different 1 to 3 substituents selected from the group consisting of 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, it may be C8-C18 alkyl or C8-C18 alkenyl, substituted C1-C10 alkyl or C2-C10 alkenyl (the substituent is 1 or more substituents selected from fluorine, chlorine, bromine, C1-C6 alkoxy, C1-C6 alkylthio, C1-C6 alkylamino, C1-C6 alkoxycarbonyl, C1-C6 alkoxycarbonyloxy), phenyl, benzyl or benzoyl C1-C6 alkyl which may be substituted (the substituent is 1 to 3 substituents selected from fluorine, chlorine, bromine, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C1-C6 haloalkyl, C1-C6 alkylcarbonyl, C1-C6 alkoxy, C1-C6 alkoxycarbonyl, C1-C6 alkylamino, hydroxy, carboxy, mercapto, amino, cyano, nitro and C1-C6 alkylsulfonyl).
The preparation method of the pyridine ring substituted pyridazinol compound comprises the following steps:
(1) Adopting a compound II and a compound III to carry out Suzuki reaction to prepare a compound shown in a general formula IV;
(2) Carrying out halogenation reaction on a compound shown in a general formula IV to prepare a compound shown in a general formula V;
(3) Preparing a compound shown in a general formula I by adopting hydrolysis of the compound shown in the general formula V;
the chemical reaction equation is as follows:
L 1 and L 2 each independently represent halogen, preferably chlorine, bromine, iodine.
The reaction temperatures are in the range from 20 to 150℃and preferably from 50 to 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)2Cl2 or Ni (dppf) Cl 2, the base is one or more than two of Et3N、NaHCO3、KOAc、K2CO3、K3PO4、Na2CO3、CsF、Cs2CO3、t-BuONa、EtONa、KOH and NaOH, and the solvent is a 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 agent, a catalyst and a solvent, wherein the halogenating agent 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 alkali and 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 alkali is preferably NaOH, KOH, potassium acetate and sodium acetate, and the solvent is preferably water and DMSO.
The chemical reaction equations for preparing the ester and ether derivatives are as follows:
wherein Q 1 is halogen, preferably chlorine or bromine;
the chemical reaction equations for preparing the oxime and hydroxylamine derivatives thereof are as follows:
wherein Q 2 is halogen, preferably chlorine or fluorine.
The reaction for preparing the ester and ether derivatives thereof and the second step of reaction for preparing the oxime and hydroxylamine derivatives thereof are carried out in the presence of alkali and a solvent, wherein the alkali is selected from 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 in the reaction for preparing the oxime and hydroxylamine derivatives thereof is carried out in the presence of a halogenating reagent and a solvent, wherein the halogenating reagent is Phenofluor/cesium fluoride or POCl 3, and the solvent is one or more than two of toluene, 1, 2-dichloroethane and DMF; the reaction temperatures are all selected from the range of 0 to 120 ℃, preferably 20 to 80 ℃.
The compounds of the present invention may exist in the form of one or more stereoisomers. The various isomers include enantiomers, diastereomers, and geometric isomers. It is within the scope of the invention for these isomers to include mixtures of these isomers.
A herbicide composition comprises (I) pyridine ring substituted pyridazinol compounds shown in a general formula I and derivatives thereof.
Preferably, (ii) one or more additional herbicides and/or safeners are also included.
More preferably, (iii) an agrochemically acceptable formulation aid is also included.
The additional herbicide is selected from one of HPPD inhibitor, hormone and PDS inhibitor; preferably, the HPPD inhibitor is sulcotrione, mesotrione, topramezone, cyclosulcotrione, fluroxypyr, fursulcotrione, bicyclosulcotrione, lancotrione, carfentrazone-ethyl, cyclofluroxypyr, triazolsulcotrione, topramezone, sulfonyloxadiazon, topramezone, pyraclon, tolpyralate, fenquinotrione, isoxaflutole; the hormone is fluroxypyr, fluroxypyr ester, quinclorac, clomefenamic acid, 2-methyl-4-chloro, 2-methyl-4-chlorophenoxypropionic acid, MCPB, 2, 4-D-propionic acid, 2,4-DB, dicamba, picloram, triclopyr, clopyralid, triclopyr and derivatives thereof, and the PDS inhibitor is fludioxonil, furbenuron, diflufenican, fluopicolide, fluobutachlor, fluazinam, and fluazinam.
Among them, fluroxypyr derivatives include, but are not limited to: fluroxypyr isooctyl ester; 2-methyl-4-chloro, 2-methyl-4-chlorophenoxypropionic acid, MCPB derivatives include, but are not limited to: sodium salt, potassium salt, dimethyl ammonium salt, isopropyl amine salt, etc., and methyl ester, ethyl ester, isooctyl ester, ethyl thioester, etc.; 2,4-D, 2,4-D propionic acid, 2,4-DB derivatives including but not limited to: salts such as sodium salt, potassium salt, dimethylammonium salt, triethanolamine salt, isopropylamine salt, choline, etc., and esters such as methyl ester, ethyl ester, butyl ester, isooctyl ester, etc.
A method for controlling harmful plants, which comprises applying a herbicidally effective amount of at least one of said pyridine ring substituted pyridazinol compounds and derivatives thereof or said herbicide composition on plants or in the area of harmful plants.
The use of at least one of the pyridine ring substituted pyridazinol compounds and derivatives thereof or the herbicide composition for controlling harmful plants.
Preferably, at least one of the pyridine ring-substituted pyridazinol compounds and derivatives thereof or the herbicide composition is used for controlling harmful plants in crops of useful plants.
More preferably, the useful crop is a transgenic crop or a genome editing technology treated crop.
The compounds of formula I of the present invention have outstanding herbicidal activity against a 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, rhizomes or other perennial organs and are difficult to control. In this regard, it is generally not important whether the substance is used before sowing, before germination or after germination. Particular mention is made of representative examples of monocotyledonous and dicotyledonous weed populations which can be controlled by the compounds of the invention, without limiting to defined species. Examples of weed species for which the active substance is effective include monocotyledonous plants: annual oat, rye, grass, myrtle, faradays, barnyard grass, crabgrass, green bristlegrass and sedge, and perennial glacial, bermudagrass, cogongrass and sorghum, and perennial sedge.
Regarding dicotyledonous weed species, the effects of which can be extended to species such as the annual galium, viola, veronica, sesamum, chickweed, amaranthus, sinapis, sweet potato, sida, chamomile and abutilon, and perennial weeds inula, thistle, sorangium and mugwort. The active substances of the invention effectively control harmful plants such as barnyard grass, arrowhead, alisma, chufa, kefir and sedge under the undetermined condition of rice sowing. If the compounds according to the invention are applied to the soil surface before germination, seedlings of the weeds can be completely prevented before the weeds grow or the growth can be stopped when the weeds grow out of the cotyledons and finally die completely after three to four weeks. The compounds of the invention have excellent activity against plants such as, for example, alachlorella, sessile sesamum, polygonum hydropiper, chickweed, vincristine She Popo, sterculia nobilis, pansy and amaranthus, galium and kochia.
Although the compounds of the invention have good herbicidal activity against monocotyledonous and dicotyledonous weeds, there is no or only insignificant damage to important commercial crop plants, such as wheat, barley, rye, rice, maize, sugar beet, cotton and soybean. Particularly well compatible with cereal crops such as wheat, barley and maize, particularly wheat. The compounds of the invention are therefore very suitable for the selective control of unwanted plants in agricultural crops or ornamental plants.
Due to their herbicidal properties, these active substances can be used for controlling harmful plants in known or to-be-developed genetically engineered plant cultivation. Transgenic plants generally have advantageous traits, such as resistance to specific pesticides, in particular specific herbicides, resistance to plant diseases or to pathogenic microorganisms of plant diseases, such as specific insect or fungal, bacterial or viral microorganisms. Other specific traits are related to the following conditions of the product, for example, quantity, quality, storage stability, composition and specific ingredients. As such, it is known to obtain transgenic plant products having increased starch content or improved starch quality or different fatty acid compositions.
The compounds of the formula I according to the invention and their derivatives are preferably used for economically important transgenic crops and ornamental plants, for example cereals, such as wheat, barley, rye, oats, millet, rice, cassava and maize, or for the cultivation of sugar beet, cotton, soya, rapeseed, potato, tomato, peas and other vegetable plants. The compounds of the formula I and their derivatives are preferably used as herbicides for cultivation of useful plants which are resistant to the deleterious effects of the herbicide or by genetic engineering.
Conventional methods of breeding plants having improved shapes over known plants include, for example, conventional mating methods and mutant breeding. In other words, new plants with improved traits can be obtained by means of genetic engineering methods (see, for example, EP-0221044A, EP-013624A). For example, several methods have been described:
To improve starch synthesis in plants, crop plants are altered by genetic engineering (e.g.WO 92/11376, WO 92/14827, WO 91/19806);
transgenic crop plants resistant to specific herbicides, to glufosinate herbicides (e.g. EP-024466 a, EP-024366A) or to glyphosate herbicides (WO 92/00377), or to sulfonylurea herbicides (EP-0257993 a, us-5013659A);
Transgenic crop plants, for example cotton, which are capable of producing a Bacillus thuringiensis toxin (Bt toxin) which is resistant to attack by specific pests on plants (EP-0142924A, EP-0193259A);
Transgenic crop plants with improved fatty acid composition (WO 91/13972).
Many techniques have been known for preparing transgenic plant molecules with improved traits (see, e.g., sambrook et al, 1989, molecular amplification, second edition of laboratory Manual, cold spring harbor laboratory Press, cold spring harbor, new York; or Winnacker "Gene und Klone" [ Gene and clone ], VCH WEINHEIM, second edition 1996 or Christou, "trends in plant science" 1 (1996) 423-431)). In order to achieve the manipulation of genetic engineering, it is possible to introduce nucleic acid molecules into plasmids, to which mutations or sequence changes occur by recombination of DNA sequences. Using the standard methods described above, it is possible, for example, to exchange substrates, to remove partial sequences or to add natural or synthetic sequences. To ligate DNA fragments to each other, it is possible to attach a conjugate or linker to the fragments.
Plant cells of the activity-reducing gene product 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 structured ribozyme which specifically cleaves the transcription product of the gene product.
For this purpose, it is possible to use DNA molecules which comprise the entire coding sequence of the gene product, including any flanking sequences which may be present, and DNA molecules which comprise only a portion of the coding sequence which must be sufficiently long to achieve an antisense effect in the cell. Sequences that have high homology but are not identical to the gene product coding sequence may also be used.
When expressing nucleic acid molecules in plants, the synthesized proteins can be localized in any desired plant cell compartment. However, for localization in a specific chamber, it is possible, for example, to ligate the coding region to the DNA sequence to ensure localization in a specific location. These sequences are known to those skilled in the art (see, e.g., 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).
The transgenic plant cells can be recombined onto the whole plant using known techniques. The transgenic plant may be 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, prohibiting or inhibiting homologous (=natural) genes or gene sequences, or by expression of heterologous (=external) genes or gene sequences.
When the active substances according to the invention are used on transgenic crops, there is often a special effect on the corresponding transgenic crops, in addition to the effect of suppressing harmful plants which is observed on other crops, for example the extent of weed control can be improved or enlarged, the application rate at the time of application is improved, preferably the combination of resistance of the transgenic crops and the herbicide properties is good, and the effect of the growth and yield of the transgenic crop plants is good. The invention therefore also provides the use of the compounds as herbicides for controlling harmful plants in transgenic crop plants.
In addition, the compounds of the invention can obviously regulate the growth of crop plants. These compounds are used to direct control of plant components and to promote harvest, such as desiccation and dwarf growth, by modulating plant metabolism. But they are also suitable for regulating and inhibiting unwanted plant growth without damaging the growth of the crop. Inhibition of plant growth plays a very important role in many monocot and dicot crops, as lodging can be reduced or prevented entirely.
The compounds of the present invention may be applied using general formulations, wettable powders, concentrated emulsions, sprayable solutions, powders or granules. Thus the present invention also provides herbicide compositions comprising the compounds of formula I. The compounds of formula I may be formulated in a variety of ways, depending on the usual biological and/or chemical physical parameters. Examples of suitable formulation choices are: wettable Powders (WP), water-Soluble Powders (SP), water-soluble concentrates, emulsion Concentrates (EC), emulsions such as oil-in-water and water-in-oil (EW), sprayable solutions, suspension Concentrates (SC), dispersible oil suspensions (OD), suspensions with oil or water as a diluent, miscible oil solutions, powders (DP), capsule Suspensions (CS), core (SEEDDRESSING) compositions, particles for broadcasting and soil application, spray particles, coated particles and absorbent particles, water-dispersible particles (WG), water-soluble particles (SG), ULV (ultra low volume) formulations, microcapsules and wax products. These individual formulation types are known and are described in, for example, winnacker-Ku chler, "CHEMISCHE TECHONOLOGIE" [ chemical Process ], volume 7, C.Hauser Verlag Munich, 4 th edition 1986; wade van Valkenburg, "PESTICIDE FORMULATIONS", MARCEL DEKKER, N.Y.,1973; martens, "SPRAY DRYING" handbook, 3 rd edition 1979,G.Goodwin Ltd.London.
The necessary formulation auxiliaries, such as inert substances, surfactants, solvents and other additives, are likewise known and are described in the following documents, for example in the handbook of powder diluent insecticides and carriers for Watkins, second edition, darland book Caldwell n.j.; h.v.01phen "entry to clay colloid chemistry", second edition, j.wiley and Sons, n.y.; marsden, "solvent guide", second edition, interscience, N.Y.1963; "annual report of detergents and emulsifiers" by McCutcheon, MC issuing company, ridgewood n.j.; sisley and Wood, "surfactant encyclopedia", chemical publishing company, n.y.1964; /> [ Ethylene oxide adduct surfactant ], wiss. Verlagagesel Stuttgart 1976; "CHEMISCHE TECHNOLOGIE" of Winnacker-Ku chler [ chemical Process ], volume 7, C.Hauser Verlag Munich, 4 th edition 1986.
Wettable powders are uniformly dispersible in water and include, in addition to the active substance, diluents or inert substances, ionic and nonionic surfactants (wetting agents, dispersants) such as polyethoxylated alkylphenols, polyethoxylated fatty alcohols, polyethoxylated fatty amines, fatty alcohol polyglycol ether sulfates, alkyl sulfonates, alkylphenyl sulfonates, sodium lignosulfonate, sodium 2,2 '-dinaphthyl-6, 6' -disulfonate, sodium dibutylnaphthalene sulfonate or sodium oleoyl methyltaurate. For the preparation of wettable powders, the active substances of the herbicides are finely ground, for example using customary equipment, such as hammer mills, fan mills and jet mills, with simultaneous or sequential incorporation of adjuvants.
The active substances are dissolved in organic solvents, such as butanol, cyclohexanone, dimethylformamide, xylene or higher-boiling aromatic compounds or hydrocarbons or mixtures of solvents, and one or more ionic and/or nonionic surfactants (emulsifiers) are added. Examples of emulsifiers that can be used are calcium alkylaryl sulfonates such as calcium dodecyl benzene sulfonate, or nonionic emulsifiers such as fatty acid polyglycol esters, alkyl aryl polyglycol ethers, fatty alcohol polyglycol ethers, propylene oxide-ethylene oxide condensation products, alkyl polyethers, sorbitan esters such as sorbitan fatty acid esters, or polyoxyethylene sorbitan esters such as polyoxyethylene sorbitan fatty esters.
The active substance and finely divided solid substance, for example talc, natural clays such as kaolin, bentonite and pyrophyllite, or diatomaceous earth, are ground to give a powder. Suspensions based on water or oil can be prepared, for example, by wet milling using commercially available bead mills, with or without the addition of surfactants of the other formulation type described above.
For example, an emulsion of an oil-in-water Emulsifier (EW) can be prepared using an aqueous organic solvent, using a stirrer, colloid mill and/or static mixer, and if desired, adding another formulation type surfactant 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 such as sand, kaolinite, granulating inert material with a binder such as polyvinyl alcohol, sodium polyacrylate or mineral oil. Suitable active substances may be granulated by the process of preparing fertilizer granules, if desired mixed with fertilizers. The water-suspended granules are prepared using conventional methods, such as spray-drying, fluid bed granulation, millstone granulation, mixing using a high-speed mixer, and extrusion without solid inert material.
For a method of preparation using millstones, fluidised beds, extruders and spray granules see the following processes, for example "SPRAY DRYING handbook" third edition 1979, g.goodwin inc., london; j.e. browning, "Agglomeration", chemistry and engineering 1967, page 147 ff; "Perry's Manual of engineers for chemistry", fifth edition, mcGraw-Hill, new York pages 1973,8-57. 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 1961 81-96 and J.D.Freyer, S.A.Evans "Manual for Weed Control", fifth edition, blackwell Scientific Rublications, oxford university 1968, pages 101-103.
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 the active substance in the wettable powder is, for example, from about 10 to 99% by weight, with the usual formulation components constituting the remainder to 100% by weight. The concentration of active substance in the emulsion concentrate may be about 1 to 90%, preferably 5 to 80% by weight. The powder formulations comprise from 1 to 30% by weight of active substance, generally preferably from 5 to 20% by weight of active substance, whereas the sprayable solutions comprise from about 0.05 to 80% by weight, preferably from 2 to 50% by weight of active substance. Regarding the content of the active substance in the water-suspendable granules, it is mainly based on whether the active substance is liquid or solid, and auxiliaries, fillers, etc. used in granulation. The content of active substances in the water-suspended granules is, for example, between 1 and 95% by weight, preferably between 10 and 80% by weight.
The formulations of the active substances mentioned may additionally comprise tackifiers, wetting agents, dispersants, emulsifiers, penetrants, preservatives, antifreezes, solvents, fillers, carriers, colorants, defoamers, evaporation inhibitors and in general pH and viscosity regulators customary in each case.
Based on these formulations, it is also possible to mix with other insecticide active substances, such as insecticides, acaricides, herbicides and fungicides, or with safeners, fertilizers and/or plant growth regulators, either pre-mixed or filled.
When used, commercially available formulations are diluted in a usual manner if necessary, for example in wettable powders, emulsion concentrates, suspensions and particles suspended in water. The powder, granules for soil application or solutions for broadcast and spray application generally do not require further dilution with inert substances prior to use. The amount of the compound of formula I required varies with external conditions such as temperature, humidity, nature of the herbicide used, etc. It may have a large variation, 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 the invention in any way. The scope of the claimed invention is indicated by the claims.
In view of the economics and diversity of compounds, we prefer to synthesize some compounds, selected portions of which are listed in tables 1-5 below. Specific compound structures and corresponding compound information are shown in tables 1-5. The compounds of tables 1-5 are only for better illustration of the present invention, but are not limiting of the present invention, and it should not be understood by those skilled in the art that the scope of the above subject matter of the present invention is limited to the following compounds.
Table 1 Structure of Compound (1) and 1 HNMR data thereof
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Table 2 Structure of Compound (2) and 1 HNMR data thereof
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TABLE 3 Structure of Compound (3) and 1 HNMR data thereof
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TABLE 4 Structure of group M in derivative Compound I
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TABLE 5 Structure of derivative Compound I' and 1 HNMR data thereof
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Several methods for preparing the compounds of the present invention are detailed 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. Those skilled in the art will appreciate that other synthetic routes may also be used to synthesize the compounds of the present invention. Although specific starting materials and conditions in the synthetic routes have been described below, they may be readily replaced with other similar starting materials and conditions, and variations or modifications of the preparation methods of the present invention, such as various isomers of the compounds, are included within 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, protection of the appropriate groups during the reaction, and the like.
The following examples of methods are provided to facilitate a further understanding of the methods of preparation of the present invention and the particular materials, types and conditions used are intended to be further illustrative of the invention and are not intended to limit the reasonable scope thereof. Reagents used in the synthetic compounds shown in the tables below 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 Compounds 1-7
(1) Compound 1-7-a (10 g,67 mmol), compound 1-7-b (10.5 g,67 mmol), potassium carbonate (27.8 g,201 mmol) were placed in a round bottom three-neck flask, 1, 4-dioxane (100 mL)/water (20 mL) was added and replaced with nitrogen three times, pd (dppf) Cl 2CH2Cl2 (0.2 g) was rapidly added under nitrogen protection and replaced with nitrogen three times, then the reaction solution replaced with nitrogen three times again, reacted at 100℃for 16 hours, after the completion of the high performance liquid chromatography detection reaction, the reaction system was concentrated and separated by column chromatography to obtain 12g (53 mmol, yield 80%) of compound 1-7-c (white solid).
(2) Compound 1-7-c (12 g,53 mmol), N-chlorosuccinimide (7.1 g,53 mmol), benzoyl peroxide (0.5 g, catalytic amount), acetonitrile (120 mL) were placed in a round bottom three-neck flask and reacted at 80℃for 16 hours, and a small amount of the starting material remained was detected by high performance liquid chromatography, concentrated and separated by column chromatography to give 6g (23 mmol, yield 43%) of compound 1-7-d (white solid).
(3) Compounds 1 to 7-d (1 g,3.8 mmol), potassium acetate (1.88 g,19 mmol) and 10mL DMSO are placed in a round bottom three-neck flask and reacted for 2 hours at 120 ℃, after the reaction is detected by high performance liquid chromatography, the reaction solution is cooled to 25 ℃, 1M HCl is added dropwise to the reaction solution until the pH of the solution is about 5, the temperature is controlled (not higher than 25 ℃), solids are separated out, the separated solids are filtered by suction, the solids are washed by a large amount of water, the solids are beaten and purified by methyl tert-butyl ether (20 mL) and a small amount of methanol (1 mL), and 500mg (2 mmol, yield 54%) of compounds 1 to 7 (gray solids) are obtained after the solid is filtered by suction and dried.
2. Synthesis of Compound I-1
Compound 1-1 was synthesized according to the above method 1, compound 1-1 (1 g,4.8 mmol), potassium carbonate (2 g,14.4 mmol), acetonitrile (20 mL) were placed in a round-bottomed flask, compound I-1-a (1.08 g,7.2 mmol) was added dropwise to the reaction system at 25℃and reacted at 25℃for 5 hours, after completion of the reaction by HPLC, the remaining potassium carbonate solid was filtered off from the reaction system, and the mother liquor was concentrated and separated by column chromatography to give 1g (3.1 mmol, yield 67%) of Compound I-1 (white solid).
3. Synthesis of Compound I-2
Compound 2-1 was synthesized according to the procedure 1 described above, compound 2-1 (2 g,9.6 mmol), potassium carbonate (4 g,28.8 mmol), compound I-2-a (2.4 g,14.4 mmol), acetonitrile (40 mL) were placed in a round bottom flask and reacted overnight (about 12 hours) at 25℃after which the reaction system was filtered to remove the remaining potassium carbonate solid, and the mother liquor was concentrated and isolated by prep-HPLC to give compound I-2 (600 mg, yield 18.5%) as a yellow solid.
4. Synthesis of Compound I-3
Compound 1-1 was synthesized according to the above method 1, and compound 1-1 (1 equivalent) was added to a 50mL single-neck eggplant-shaped bottle at room temperature,(1.1 Eq), potassium carbonate (3 eq) and acetonitrile (10V), and stirred for 6 hours at 80 ℃. TLC detects completion of the reaction, the reaction system was distilled off under reduced pressure to remove acetonitrile, dissolved in water (5V), extracted with ethyl acetate (5 v×3), distilled off 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 82% yield.
5. Synthesis of Compound I-4
Compound 1-1 was synthesized according to the above method 1, and Compound 1-1 (1 eq), triethylamine (3 eq) and methylene chloride (5V) were added under ice bath in a 50mL single-neck eggplant-shaped bottle, and added dropwise under ice bath(1.2 Eq.) and then stirred at room temperature for 30 minutes. TLC detects completion of the reaction, extraction with water (5V) and dichloromethane (5V x 3), distillation under reduced pressure removes dichloromethane and the residue is separated by column chromatography on silica gel (100 mesh to 200 mesh) to give the product in 76% yield.
6. Synthesis of Compound I-5
Compound 1-1 was synthesized by the method 1 described above, and compound 1-1 (1 equivalent), phenofluor (1.5 equivalent), cesium fluoride (3 equivalent) and toluene (10V) were added to a 50mL single-port eggplant-shaped bottle at room temperature, and the mixture was heated to 80 ℃ and stirred for 18 hours. TLC detects completion of the reaction, post-treatment intermediate compound I-5-a. In a separate 50mL single-necked eggplant bottle, the compound I-5-a (1 equivalent) was added at room temperature,(1.2 Eq), potassium carbonate (3 eq) and acetonitrile (10V), warmed to 80 ℃, stirred for 18h. TLC detects completion of the reaction, the reaction system was distilled off under reduced pressure to remove acetonitrile, dissolved in water (5V), extracted with ethyl acetate (5 v×3), distilled off 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 62% yield.
7. Synthesis of Compound I-6
Compound 1-1 was synthesized according to the above method 1, and Compound 1-1 (1 equivalent), POCl 3 (1.5 equivalent), 1, 2-dichloroethane (10V) and 5% N, N-dimethylformamide were added to a 50mL single-neck eggplant-shaped bottle at room temperature, and stirred for 6 hours while heating to 80 ℃. TLC checked for completion of the reaction, dissolved in water (5V), extracted with 1, 2-dichloroethane (5 V.times.3), distilled off under reduced pressure to remove 1, 2-dichloroethane to give compound I-6-a. In a separate 50mL single-neck eggplant-shaped bottle, the compound I-6-a (1 equivalent) was added at room temperature,(1.2 Eq), potassium hydroxide (3 eq) and N, N-dimethylformamide (10V), and the mixture was heated to 100℃and stirred for 18h. TLC detects completion of the reaction, dissolution with water (5V), extraction with ethyl acetate (5V x 3), distillation under reduced pressure to remove ethyl acetate, and separation of the residue by column chromatography on silica gel (100 mesh to 200 mesh) gives the product in 49% yield.
Biological activity evaluation:
the activity level criteria for pest plant destruction (i.e., growth control rate) are as follows:
10 grades: complete death;
stage 9: the growth control rate is more than 90 percent;
8 stages: the growth control rate is more than 80%;
7 stages: the growth control rate is more than 70%;
stage 6: the growth control rate is more than 60 percent;
5 stages: the growth control rate is more than 50%;
4 stages: the growth control rate is more than 40%;
3 stages: the growth control rate is more than 30%;
2 stages: the growth control rate is more than 20%;
stage 1: the growth control rate is lower than 20%;
level 0: has no effect.
The growth control rate is fresh weight control rate.
Post-emergence test experiment: monocotyledonous and dicotyledonous weed seeds and main crop seeds (wheat, corn, rice, soybean, cotton, rape, millet, sorghum) are placed in a plastic pot filled with soil, then covered with 0.5-2 cm of soil, allowed to grow in a good greenhouse environment, the test plants are treated in the 4-5 leaf stage after 2-3 weeks of sowing, the tested compounds of the invention are dissolved with acetone, tween 80 is added, diluted with water to a solution of a certain concentration, and sprayed onto the plants using a spray tower. The experimental effects of weeds after 3 weeks of cultivation in a greenhouse after application are shown in Table 6.
TABLE 6 post-emergence weed test for Compound I and its derivatives I
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Comparison experiment:
post-emergence test conditions were as above and the experimental results are shown in table 7.
Control compound a:
Control compound B:
TABLE 7 comparison of experimental results
Serial number of the compound Barnyard grass Kennel grass Crabgrass Indian rorippa herb Galvanic fibre All-grass of Populus Metering device
1-1 8 10 7 10 9 9 300 G/hectare
1-2 10 10 8 10 9 10 300 G/hectare
1-4 8 10 8 10 10 10 300 G/hectare
1-7 10 10 8 10 9 10 300 G/hectare
2-3 10 10 10 10 10 10 300 G/hectare
I-7 8 9 7 10 9 9 300 G/hectare
Control Compound A 0 2 1 3 5 6 300 G/hectare
Control Compound B 0 2 0 3 4 6 300 G/hectare
As is evident from the above table, the compounds of the present invention have significantly higher herbicidal activity than the control compounds A and B.
Pre-emergence test experiment:
Monocotyledonous and dicotyledonous weed seeds and main crop seeds (wheat, corn, rice, soybean, cotton, rape, millet, sorghum) are placed in a plastic pot filled with soil, then covered with 0.5-2 cm of soil, the tested compounds of the invention are respectively dissolved with acetone, then tween 80 is added, diluted with certain water into a solution with certain concentration, and sprayed immediately after sowing. After application, the pesticide is cultured in a greenhouse for 4 weeks, and experimental results are observed after 3 weeks, and most of the pesticide has a remarkable effect under the metering of 250 g/hectare, especially has good selectivity on weeds such as barnyard grass, pond, abutilon and the like, and many compounds have good selectivity on corn, wheat, rice, soybean and rape.
Evaluation of safety of transplanted rice and evaluation of weed control effect in paddy field:
After filling 1/1,000,000 hectare pot with paddy soil, seeds of barnyard grass, fluorescent rush, pennisetum alopecuroides and arrowhead were sown, and soil was lightly covered thereon. Then, the mixture is kept still in a greenhouse with water storage depth of 0.5-1 cm, and tubers of the arrowhead are planted after the second day or 2 days. Thereafter, the water storage depth was kept 3 to 4 cm, and at the time point when barnyard grass, fluorescent iris, pennisetum alopecuroides reached 0.5 leaf and Indian arrowhead reached the primary leaf stage, a wettable powder or an aqueous suspension of the suspension prepared by the compound of the present invention was prepared by a usual preparation method, and was subjected to a uniform dropping treatment with a pipette to obtain a predetermined amount of the active ingredient.
In addition, after filling 1/1,000,000 hectare pot with paddy field soil, leveling was performed to make the water storage depth 3-4 cm, and the rice (japonica rice) in 3-leaf period was transplanted at a transplanting depth of 3 cm the next day. The compounds of the present invention were treated as described above on day 5 after transplantation.
The growth states of barnyard grass, fluorescent rush, chinese pennisetum herb and Indian arrowhead on the 14 th day after the medicament treatment are observed by naked eyes respectively, the growth states of rice on the 21 st day after the medicament treatment are evaluated for weeding effect according to the activity standard grade of 1-10, and a plurality of compounds of the invention are found to have excellent activity and selectivity through experiments, especially for the Indian arrowhead and the barnyard grass.
Note that: barnyard grass, fluorescent rush, indian arrowhead and Chinese pennisetum seed are all collected from Heilongjiang, and have drug resistance to conventional doses of pyrazosulfuron-ethyl through detection.
Meanwhile, through many tests, the compound and the composition thereof have good selectivity on grass lawns such as zoysia, bermuda grass, festuca arundinacea, bluegrass, ryegrass, seashore paspalum and the like, and can prevent and remove a plurality of key grass weeds and broadleaf weeds. Tests on wheat, corn, rice, sugarcane, soybean, cotton, oil sunflower, potato, fruit trees, vegetables, etc. under different modes of application also showed excellent selectivity and commercial value.

Claims (22)

1. A pyridine ring substituted pyridazinol compound or a salt thereof, which is characterized in that the compound is shown as a general formula I:
X is selected from chlorine or pentafluoroethyl;
r is an integer between 0 and 4;
Y is independently selected from hydrogen, halogen or C 1～8 alkyl with or without halogen;
the salt refers to an agriculturally acceptable hydroxy derivative at the 4-position of the pyridazine ring in the general formula I.
2. A pyridalyl compound or a salt thereof according to claim 1, wherein,
R is 0,1, 2, 3 or 4;
y is independently selected from hydrogen, fluorine, chlorine, bromine or C 1～6 alkyl with or without fluorine, chlorine, bromine.
3. A pyridalyl compound or a salt thereof according to claim 2, wherein,
Y is independently selected from hydrogen, methyl, ethyl, fluoro, chloro, bromo or trifluoromethyl.
4. A pyridine ring-substituted pyridazinol compound or a salt thereof according to claim 3, which is selected from any one of the following compounds:
Sequence number X Y 2-3 Cl 3-,F 2-5 Cl 3-,Cl 2-10 Cl 2-,F 3-,F 2-11 Cl 2-,F 5-,F 2-13 Cl 3-,F 5-,F 2-23 Cl 3-,F 5-,Cl
Sequence number X Y 3-3 Cl 4-,F 3-7 Cl 4-,Cl 3-8 Cl 5-,Cl 3-18 Cl 3-,F 4-,F 3-19 Cl 3-,F 5-,F 3-30 Cl 3-,F 4-,Cl
。
5. The derivative of a pyridine ring-substituted pyridazinol compound according to any one of claims 1 to 4, wherein the derivative has a structural formula ofWherein,
M representsX, Y, r is defined in any one of claims 1 to 4.
6. The derivative of a pyridine ring-substituted pyridazinol compound according to claim 5, which is selected from any one of the following compounds:
7. A process for producing the pyridine ring-substituted pyridazinol compound according to any one of claims 1 to 4, or a salt thereof, comprising the steps of:
(1) Adopting a compound II and a compound III to carry out Suzuki reaction to prepare a compound shown in a general formula IV;
(2) Carrying out halogenation reaction on a compound shown in a general formula IV to prepare a compound shown in a general formula V;
(3) Preparing a compound shown in a general formula I by adopting hydrolysis of the compound shown in the general formula V;
the chemical reaction equation is as follows:
L 1 and L 2 each independently represent halogen, and X, Y, r is as defined in any one of claims 1 to 4.
8. The method for producing a pyridine ring-substituted pyridazinol compound or its salt according to claim 7, wherein L 1 and L 2 each independently represent chlorine, bromine or iodine.
9. The method for producing a pyridine ring-substituted pyridazinol compound or a salt thereof according to claim 7 or 8,
The reaction temperature is within the range of 20-150 ℃;
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)2Cl2 or Ni (dppf) Cl 2, the base is one or more than two of Et3N、NaHCO3、KOAc、K2CO3、K3PO4、Na2CO3、CsF、Cs2CO3、t-BuONa、EtONa、KOH and NaOH, and the solvent is a 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 agent, a catalyst and a solvent, wherein the halogenating agent 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, hydrochloric acid ethyl acetate solution.
10. The method for producing a pyridine ring-substituted pyridazinol compound or its salt according to claim 9,
The reaction temperature is within the range of 50-130 ℃;
In the step (3), the alkali is NaOH, KOH, potassium acetate or sodium acetate, and the solvent is water or DMSO.
11. A process for producing a derivative of a pyridine ring-substituted pyridazinol compound according to any one of claims 5 to 6, wherein a chemical reaction equation for producing the ester derivative thereof is as follows:
wherein Q 1 represents halogen, X, Y, M, r is as defined in any one of claims 5 to 6.
12. The process according to claim 11, wherein Q 1 represents chlorine or bromine.
13. The production method according to claim 11 or 12, wherein the reaction for producing the ester derivative thereof is carried out in the presence of a base selected from one or more 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 reaction temperature is selected from the range of 0-120 ℃.
14. The method of claim 13, wherein the reaction temperatures are each selected from the range of 20-80 ℃.
15. An herbicide composition comprising (i) the pyridine ring-substituted pyridazinol compound according to any one of claims 1 to 4 or a salt thereof or a derivative of the pyridine ring-substituted pyridazinol compound according to any one of claims 5 to 6
And (3) organisms.
16. A herbicidal composition according to claim 15, further comprising (ii) one or more additional herbicides and/or safeners.
17. A herbicide composition as claimed in claim 15 or 16, further comprising (iii) an agrochemically acceptable formulation adjuvant.
18. A herbicide composition as claimed in claim 16, wherein the further herbicide is selected from one of HPPD inhibitors, hormones, PDS inhibitors.
19. A herbicide composition as claimed in claim 18, wherein the HPPD inhibitor is sulcotrione, mesotrione, topramezone, cyclosulfamuron, fluroxypyr, fursulcotrione, bicyclosulcotrione lancotrione, topramezone, triazolsulcotrione, topramezone, sulfonylgrass pyrazole, pyrazolote, metazophos, tolpyralate, fenquinotrione, isoxaflutole; the hormone is fluroxypyr, fluroxypyr ester, quinclorac, clomefenamic acid, 2-methyl-4-chloro, 2-methyl-4-chlorophenoxypropionic acid, MCPB, 2, 4-D-propionic acid, 2,4-DB, dicamba, picloram, triclopyr, clopyralid and triclopyr, and the PDS inhibitor is fludioxonil, furbenone, diflufenican, fluopicolide, fluobutachlor, flubenoxameans and fluazinam.
20. A method for controlling harmful plants, which comprises applying a herbicidally effective amount of at least one of the pyridine ring-substituted pyridazinol compounds described in any one of claims 1 to 4 or salts thereof or the derivatives of the pyridine ring-substituted pyridazinol compounds described in any one of claims 5 to 6 or the herbicide composition described in any one of claims 15 to 19 on plants or in harmful plant areas.
21. Use of at least one of the pyridine ring-substituted pyridazinol compounds or salts thereof according to any one of claims 1 to 4 or derivatives of the pyridine ring-substituted pyridazinol compounds according to any one of claims 5 to 6 or the herbicide composition according to any one of claims 15 to 19 for controlling harmful plants.
22. The use according to claim 21, wherein the pyridine ring substituted pyridazinol compound or a salt thereof or a derivative of the pyridine ring substituted pyridazinol compound is used for controlling harmful plants in useful crops, which are transgenic crops or crops treated by genome editing technology.
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