CN109503556B - Quinazoline-2, 4-diketone derivative and preparation method and application thereof - Google Patents

Quinazoline-2, 4-diketone derivative and preparation method and application thereof Download PDF

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CN109503556B
CN109503556B CN201811060960.1A CN201811060960A CN109503556B CN 109503556 B CN109503556 B CN 109503556B CN 201811060960 A CN201811060960 A CN 201811060960A CN 109503556 B CN109503556 B CN 109503556B
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CN109503556A (en
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李义涛
张虎
刘鹏飞
刘倩
林健
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Dongguan dongyangguang pesticide R & D Co., Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/713—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with four or more nitrogen atoms as the only ring hetero atoms
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/82—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with three ring hetero atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links

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Abstract

The invention provides a quinazoline-2, 4-diketone derivative and a preparation method and application thereof, in particular to a quinazoline-2, 4-diketone derivative shown as a formula (I) and a composition containing the derivative. The invention also provides methods for preparing such derivatives and the use of such derivatives for the selective control of undesired plants in crops of useful plants; wherein, Q, W, Z, Y, R1、R2And R3Have the meaning as described in the present invention.

Description

Quinazoline-2, 4-diketone derivative and preparation method and application thereof
Technical Field
The present invention provides quinazoline-2, 4-dione derivatives that selectively control undesirable vegetation in useful crops and methods for their preparation.
Background
WO 2015/058519 and WO 2017/140612 disclose that quinazoline-2, 4-dione-6-carbonyl derivatives have herbicidal activity, however these known compounds do not always have a sufficiently broad spectrum of herbicidal activity and/or compatibility with crops.
Disclosure of Invention
The present invention provides quinazoline-2, 4-dione derivatives, and compositions containing such derivatives, which are useful for controlling the growth of undesirable plants.
In one aspect, the present invention provides a compound of formula (I) or a stereoisomer, a nitroxide, and acceptable salts thereof:
Figure BDA0001797086400000011
wherein:
q is Q1、Q2、Q3、Q4、Q5Or Q6，
Figure BDA0001797086400000012
Wherein R isa、Rb、RdAnd RhEach independently is hydrogen, C1-6Alkyl radical, C3-8Cycloalkyl radical, C2-6Alkenyl or C2-6An alkynyl group;
wherein R isc、Re、RfAnd RgEach independently of the others is hydrogen, halogen, cyano, hydroxy, C1-6Alkyl, halo C1-6Alkyl radical, C1-6Alkoxy radical, C3-8Cycloalkyl radical, C2-6Alkenyl or C2-6An alkynyl group;
x is oxygen or sulfur;
R1is hydrogen, C1-6Alkyl radical, C2-6Alkenyl radical, C2-6Alkynyl, C3-8Cycloalkyl radical, C3-8cycloalkyl-C1-3Alkyl or C6-10aryl-C1-3An alkyl group;
R2is hydrogen, hydroxy, amino, C1-6Alkyl, halo C1-6Alkyl radical, C1-3alkoxy-C1-3Alkyl, halo C1-3alkoxy-C1-3Alkyl radical, C2-6Alkenyl radical, C2-6Alkynyl, halo C2-6Alkenyl, halo C2-6Alkynyl, C6-14aryl-C1-3Alkyl radical, C3-8Cycloalkyl radical, C3-8cycloalkyl-C1-3Alkyl radical, C3-10Cycloalkenyl radical, C3-10Cycloalkenyl radical-C1-3Alkyl radical, C1-6Alkylcarbonyl group, C3-8Cycloalkyl carbonyl group, C1-6alkyl-O-C (═ O) -, C1-6Alkylamino radical, C3-8Cycloalkylamino, C1-6Alkylaminocarbonyl or C3-8A cycloalkylaminocarbonyl group;
or R2Is C6-14Aryl or C6-14aryl-S (O)2-；
Or R2Is a saturated, partially unsaturated or aromatic C containing 1,2,3,4 or 5 atoms selected from nitrogen, oxygen or sulfur atoms1-10Mono-or bis-heterocyclic;
wherein R is2Optionally substituted with 1,2,3,4 or 5 substituents selected from a 1;
R3is hydrogen, C1-6Alkyl, halo C1-6Alkyl radical, C2-6Alkenyl radical, C2-6Alkynyl, C3-8Cycloalkyl radical, C6-14Aryl or C6-14aryl-C1-3An alkyl group;
wherein R is3Optionally substituted with 1,2,3,4 or 5 substituents selected from a 2;
w is hydrogen, nitro, halogen, cyano, C1-6Alkyl radical, C1-6Alkoxy radical, C1-3alkoxy-C1-3Alkyl, halo C1-6Alkyl radical, C2-6Alkenyl, halo C2-6Alkenyl radical, C2-6Alkynyl, halo C2-6Alkynyl, C3-8Cycloalkyl radical, C3-8cycloalkyl-C1-6Alkyl radical, C1-6Alkylcarbonyl group, C1-6alkyl-C (═ O) -O-, C1-6alkyl-O-C (═ O) -, C1-6alkyl-S (O)n-、C1-6alkyl-O-C (═ O) -O-, R12R13N-SO2-、R12R13N-C (═ O) -or R14R15N-；
Wherein W is optionally substituted with 1,2,3,4 or 5 substituents selected from a 3;
wherein each of a1, a2, and A3 is independently halogen, hydroxy, cyano, nitro, oxo (═ O), C1-6Alkyl, halo C1-6Alkyl radical, C1-6Alkoxy, halo C1-6Alkoxy radical, C3-8Cycloalkyl radical, C2-6Alkenyl radical, C2-6Alkynyl, halo C2-6Alkenyl, halo C2-6Alkynyl, C6-14Aryl, halo C6-14Aryl radical, C6-14aryl-C1-6Alkyl radical, C6-14aryl-O-, C6-14aryl-S (O)2-、C6-14aryl-O-C1-6Alkyl, 5-10 membered heteroaryl, 3-10 membered heterocyclyl, C1-6Alkylcarbonyl group, C1-6alkyl-O-C (═ O) -, C1-6alkyl-S (O)n-、C1-6alkyl-C (═ O) -O-, R16R17N-C (═ O) -or R18R19N-；
Wherein n is 0, 1 or 2;
wherein R is12、R13、R16And R17Each independently is hydrogen or C1-6An alkyl group;
wherein R is14、R15、R18And R19Each independently is hydrogen, C1-6Alkyl radical, C1-6Alkylcarbonyl or C1-6alkyl-S (O)2-；
Z is hydrogen or C1-6An alkyl group;
y is hydrogen, nitro, halogen, cyano, C1-6Alkyl, halo C1-6Alkyl radical, C1-6Alkoxy or halo C1-6An alkoxy group.
In some embodiments, Q is Q1、Q2、Q3、Q4、Q5Or Q6，
Figure BDA0001797086400000021
Wherein R isa、Rb、RdAnd RhEach independently is hydrogen, C1-4Alkyl radical, C3-6Cycloalkyl radical, C2-4Alkenyl or C2-4An alkynyl group;
wherein R isc、Re、RfAnd RgEach independently of the others is hydrogen, halogen, cyano, hydroxy, C1-4Alkyl, halo C1-4Alkyl radical, C1-4Alkoxy radical, C3-6Cycloalkyl radical, C2-4Alkenyl or C2-4An alkynyl group;
R1is hydrogen, C1-4Alkyl radical, C2-4Alkenyl radical, C2-4Alkynyl, C3-6Cycloalkyl radical, C3-6cycloalkyl-C1-3Alkyl or C6-10aryl-C1-3An alkyl group.
In some further embodiments, Q is Q1、Q2、Q3、Q4、Q5Or Q6，
Figure BDA0001797086400000022
Wherein R isa、Rb、RdOr RhEach independently is hydrogen, -CH3、-CH2CH3、-CH2CH2CH3、-CH(CH3)2、-CH2CH2CH2CH3、-CH2CH(CH3)2、-C(CH3)3Or cyclopropyl;
wherein R isc、Re、RfAnd RgEach independently hydrogen, fluorine, chlorine, bromine, iodine, cyano, hydroxy, -CH3、-CH2CH3、-CH2CH2CH3、-CH(CH3)2、-CH2CH2CH2CH3、-CH2CH(CH3)2、-C(CH3)3、-CH2F、-CHF2、-CF3、-CH2Cl、-CHCl2、-CCl3、-OCH3or-OCH2CH3；
R1Is hydrogen, -CH3、-CH2CH3、-CH2CH2CH3、-CH(CH3)2、-CH2CH2CH2CH3、-CH2CH(CH3)2or-C (CH)3)3；
Or R1Is of the sub-structure:
Figure BDA0001797086400000023
in some embodiments, R3Is hydrogen, C1-4Alkyl, halo C1-4Alkyl radical, C2-4Alkenyl radical, C2-4Alkynyl, C3-6Cycloalkyl radical, C6-10Aryl or C6-10aryl-C1-3An alkyl group;
wherein R is3Optionally substituted with 1,2,3,4 or 5 substituents selected from a 2;
w is hydrogen, nitro, halogen, cyano, C1-4Alkyl radical, C1-4Alkoxy radical, C1-3alkoxy-C1-3Alkyl, halo C1-4Alkyl radical, C2-4Alkenyl, halo C2-4Alkenyl radical, C2-4Alkynyl, halo C2-4Alkynyl, C3-6Cycloalkyl radical, C3-6cycloalkyl-C1-4Alkyl radical, C1-4Alkylcarbonyl group, C1-4alkyl-C (═ O) -O-, C1-4alkyl-O-C (═ O) -, C1-4alkyl-S (O)n-、C1-4alkyl-O-C (═ O) -O-, R12R13N-SO2-、R12R13N-C (═ O) -or R14R15N-；
Wherein W is optionally substituted with 1,2,3,4 or 5 substituents selected from a 3;
wherein each of A2 and A3 is independently halogen, hydroxy, cyano, nitro, C1-4Alkyl, halo C1-4Alkyl radical, C1-4Alkoxy, halo C1-4Alkoxy radical, C3-6Cycloalkyl radical, C2-4Alkenyl radical, C2-4Alkynyl, halo C2-4Alkenyl, halo C2-4Alkynyl, C6-10Aryl, halo C6-10Aryl radical, C6-10aryl-C1-4Alkyl radical, C6-10aryl-O-, C6-10aryl-O-C1-4Alkyl radical, C1-4Alkylcarbonyl group, C1-4alkyl-O-C (═ O) -, C1-4alkyl-S (O)n-、C1-4alkyl-C (═ O) -O-, R16R17N-C (═ O) -or R18R19N-；
Wherein n is 0, 1 or 2;
wherein R is12、R13、R16And R17Each independently is hydrogen or C1-4An alkyl group;
wherein R is14、R15、R18And R19Each independently is hydrogen, C1-4Alkyl radical, C1-4Alkylcarbonyl or C1-4alkyl-S (O)2-；
Z is hydrogen or C1-4An alkyl group;
y is hydrogen, nitro, halogen, cyano, C1-4Alkyl, halo C1-4Alkyl radical, C1-4Alkoxy or halo C1-4An alkoxy group.
In still other embodiments, R3Is hydrogen, -CH3、-CH2CH3、-CH2CH2CH3、-CH(CH3)2、-CH2CH2CH2CH3、-CH2CH(CH3)2、-C(CH3)3、-CF3、-CH＝CH2、-CH2CH＝CH2、-CH＝CHCH3、-CH2CH2CH＝CH2、-CH2CH＝CHCH3、-C≡CH、-CH2-C≡CH、-CH2-C≡CCH3or-CH2CH2-C≡CH；
Or R3Is of the sub-structure:
Figure BDA0001797086400000031
wherein R is3Optionally substituted with 1,2,3,4 or 5 substituents selected from a 2;
w is hydrogen, fluorine, chlorine, bromine, iodine, cyano, -CH3、-CH2CH3、-CH2CH2CH3、-CH(CH3)2、-CH2CH2CH2CH3、-CH2CH(CH3)2、-C(CH3)3、-OCH3、-OCH2CH3、-CH2OCH3、-CH2OCH2CH3、-CH2CH2OCH3、-CH2CH2OCH2CH3、-CF3、-CH＝CH2、-CH2CH＝CH2、-CH＝CHCH3、-C≡CH、-CH2-C≡CH、-SCH3、-S(O)2CH3or-NH2；
Or W is the following sub-structure:
Figure BDA0001797086400000032
wherein W is optionally substituted with 1,2,3,4 or 5 substituents selected from a 3;
wherein each of A2 and A3 is independently fluorine, chlorine, bromine, iodine, hydroxy, cyano, nitro, -CH3、-CH2CH3、-CH2CH2CH3、-CH(CH3)2、-CH2CH2CH2CH3、-CH2CH(CH3)2、-C(CH3)3、-CF3、-OCH3、-OCH2CH3、-OCH2CH2CH3、-OCH(CH3)2、-OCH2CH2CH2CH3、-OCH2CH(CH3)2、-OC(CH3)3、-OCF3、-OCH2CF3、-C(＝O)CH3、-C(＝O)OCH3、-SCH3、-SCH2CH3、-S(O)CH3、-S(O)CH2CH3、-S(O)2CH3、-S(O)2CH2CH3、-OC(＝O)CH3、-OC(＝O)CH2CH3or-NH2；
Or each of A2 and A3 is independently of the substructure:
Figure BDA0001797086400000041
z is hydrogen, -CH3、-CH2CH3、-CH2CH2CH3、-CH(CH3)2、-CH2CH2CH2CH3、-CH2CH(CH3)2or-C (CH)3)3；
Y is hydrogen, nitro, fluorine, chlorine, bromine, iodine, cyano, -CH3、-CH2CH3、-CH2CH2CH3、-CH(CH3)2、-CH2CH2CH2CH3、-CH2CH(CH3)2、-C(CH3)3、-CF3、-OCH3、-OCH2CH3、-OCF3、-OCH2CF3or-OCF2CF3。
In some embodiments, R2Is hydrogen, hydroxy, amino, C1-4Alkyl, halo C1-4Alkyl radical, C1-3alkoxy-C1-3Alkyl, halo C1-3alkoxy-C1-3Alkyl radical, C2-4Alkenyl radical, C2-4Alkynyl, halo C2-4Alkenyl, halo C2-4Alkynyl, C6-10aryl-C1-3Alkyl radical, C3-6Cycloalkyl radical, C3-6cycloalkyl-C1-3Alkyl radical, C1-4Alkylcarbonyl group, C3-6Cycloalkyl carbonyl group, C1-4Alkylamino radical, C3-6Cycloalkylamino, C1-4Alkylaminocarbonyl or C3-6A cycloalkylaminocarbonyl group;
or R2Is C6-14Aryl or C6-14aryl-S (O)2-；
Or R2Is a saturated, partially unsaturated or aromatic C containing 1,2,3,4 or 5 atoms selected from nitrogen, oxygen or sulfur atoms1-9Mono-or bis-heterocyclic;
wherein R is2Optionally substituted with 1,2,3,4 or 5 substituents selected from a 1;
wherein each a1 is independently halogen, hydroxy, cyano, nitro, oxo (═ O), C1-4Alkyl, halo C1-4Alkyl radical, C1-4Alkoxy, halo C1-4Alkoxy radical, C3-6Cycloalkyl radical, C2-4Alkenyl radical, C2-4Alkynyl, halo C2-4Alkenyl, halo C2-4Alkynyl, C6-10Aryl, halo C6-10Aryl radical, C6-10aryl-C1-4Alkyl radical, C6-10aryl-O-, C6-10aryl-S (O)2-、C6-10aryl-O-C1-4Alkyl, 5-6 membered heteroaryl, 3-8 membered heterocyclyl, C1-4Alkylcarbonyl group, C1-4alkyl-O-C (═ O) -, C1-4alkyl-S (O)n-、C1-4alkyl-C (═ O) -O-, R16R17N-C (═ O) -or R18R19N-；
Wherein n is 0, 1 or 2;
wherein R is16And R17Each independently is hydrogen or C1-4An alkyl group;
wherein R is18And R19Each independently is hydrogen, C1-6Alkyl radical, C1-6Alkylcarbonyl or C1-6alkyl-S (O)2-。
In still other embodiments, R2Is hydrogen, hydroxy, amino, -CH3、-CH2CH3、-CH2CH2CH3、-CH(CH3)2、-CH2CH2CH2CH3、-CH2CH(CH3)2、-C(CH3)3、-CH2F、-CHF2、-CF3、-CH2Cl、-CHCl2、-CCl3、-CH2CH2F、-CH2CHF2、-CH2CF3、-CF2CF3、-CH2CH2CH2F、-CH2CH2CHF2、-CH2CH2CF3、-CH2CF2CF3、-CH(CF3)2、-CF(CF3)2、-CH2CH2CH2CH2F、-CH2CH2CH2CHF2、-CH2CH2CH2CF3、-CH2CH(CF3)2、-C(CF3)(CH3)2、-C(CF3)3、-CH2OCH3、-CH2OCH2CH3、-CH2OCH2CH2CH3、-CH2OCH(CH3)2、-CH2CH2OCH3、-CH2CH2OCH2CH3、-CH2CH2OCH2CH2CH3、-CH2CH2OCH(CH3)2、-CH2CH2CH2OCH3、-CH2CH(CH3)OCH3、-CH2CH2CH2OCH2CH3、-CH2CH(CH3)OCH2CH3、-CH2CH2CH2OCH2CH2CH3、-CH2CH2CH2OCH(CH3)2、-C(CH3)2OCH(CH3)2、-CH2OCF3、-CH2OCH2CF3、-CH2OCF2CF3、-CH2OCH2CH2CF3、-CH2OCH(CF3)2、-CH2OCF(CF3)2、-CH2CH2OCF3、-CH2CH2OCH2CF3、-CH2CH2OCF2CF3、-CH2CH2OCH2CH2CF3、-CH2CH2OCH(CF3)2、-CH2CH2OCF(CF3)2、-CH2CH2CH2OCF3、-CH2CH2CH2OCH2CF3、-CH2CH2CH2OCF2CF3、-CH2CH2CH2OCH2CH2CF3、-CH2CH2CH2OCH(CF3)2、-CH2CH2CH2OCF(CF3)2、-C(CH3)2OCH(CF3)2、-CH＝CH2、-CH2CH＝CH2、-CH＝CHCH3、-CH2CH2CH＝CH2、-CH2CH＝CHCH3、-C≡CH、-CH2-C≡CH、-CH2-C≡CCH3or-CH2CH2-C≡CH；
Or R2Is of the sub-structure:
Figure BDA0001797086400000051
wherein R is2Optionally substituted with 1,2,3,4 or 5 substituents selected from a 1;
wherein each a1 is independently fluoro, chloro, bromo, iodo, hydroxy, cyano, nitro, oxo (═ O), -CH3、-CH2CH3、-CH2CH2CH3、-CH(CH3)2、-CH2CH2CH2CH3、-CH2CH(CH3)2、-C(CH3)3、-CH2F、-CHF2、-CF3、-CH2Cl、-CHCl2、-CCl3、-CH2CH2F、-CH2CHF2、-CH2CF3、-CH2CH2CH2F、-CH2CH2CHF2、-CH2CH2CF3、-CH2CF2CF3、-CH(CF3)2、-CF(CF3)2、-CH2CH2CH2CH2F、-CH2CH2CH2CHF2、-CH2CH2CH2CF3、-CH2CH(CF3)2、-C(CF3)3、-OCH3、-OCH2CH3、-OCH2CH2CH3、-OCH(CH3)2、-OCH2CH2CH2CH3、-OCH2CH(CH3)2、-OC(CH3)3、-OCF3、-OCH2CF3、-OCF2CF3、-OCF(CF3)2、-CH＝CH2、-CH2CH＝CH2、-CH＝CHCH3、-CH2CH2CH＝CH2、-CH2CH＝CHCH3、-C≡CH、-CH2-C≡CH、-CH2-C≡CCH3、-CH2CH2-C≡CH、-C(＝O)CH3、-C(＝O)CH2CH3、-C(＝O)OCH3、-C(＝O)OCH2CH3、-SCH3、-SCH2CH3、-S(O)CH3、-S(O)CH2CH3、-S(O)2CH3、-S(O)2CH2CH3、-OC(＝O)CH3、-OC(＝O)CH2CH3or-NH2；
Or each a1 is independently of the substructure:
Figure BDA0001797086400000052
Figure BDA0001797086400000061
in another aspect, the invention provides a composition comprising a compound of the invention.
Further, the composition of the present invention comprises an agriculturally pharmaceutically acceptable surfactant and a carrier.
In another aspect, the invention provides the use of a compound of the invention or a composition comprising a compound of the invention in agriculture.
Detailed description of the invention
Definitions and general terms
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. All patents and publications referred to herein are incorporated by reference in their entirety.
The following definitions as used herein should be applied unless otherwise indicated. For the purposes of the present invention, the chemical elements are in accordance with the CAS version of the periodic Table of the elements, and the handbook of chemistry and Physics, 75 th edition, 1994. In addition, general principles of Organic Chemistry can be found in the descriptions of "Organic Chemistry", Thomas Sorrell, University Science Books, Sausaltito: 1999, and "March's Advanced Organic Chemistry" by Michael B.Smith and Jerry March, John Wiley & Sons, New York:2007, the entire contents of which are incorporated herein by reference.
The terms "optional" or "optionally" mean that the subsequently described event or circumstance may, but need not, occur, i.e., that the description includes instances where said event or circumstance occurs and instances where it does not. For example, "optionally substituted with 1,2,3, or 4 …" includes the case where the group is substituted with 1, or 2, or 3, or 4 of the substituents described, as well as the case where the group is not substituted with the substituents described. Further, when the group is substituted with 1 or more of the substituents, the substituents are independent of each other, that is, the 1 or more substituents may be different from each other or the same.
The compounds of the invention may be optionally substituted with one or more substituents, as described herein, in compounds of the general formula above, or as specifically exemplified, sub-classes, and classes of compounds encompassed by the invention. In general, the term "substituted" means that one or more hydrogen atoms in a given structure is replaced with a particular substituent. Unless otherwise indicatedAspects show that an optional substituent group can be substituted at each substitutable position of the group. When more than one position in a given formula can be substituted with one or more substituents selected from a particular group, the substituents may be substituted at each position, identically or differently. Wherein "one or more substituents" means one or more substituents, and the number of specific substituents is determined by the number of positions where the substituted group can be substituted. The substituent may be, but is not limited to, deuterium, oxo (═ O), halogen, cyano, nitro, hydroxyl, mercapto, carboxyl, amino, arylamino, aminoalkyl, alkyl, alkyloxy, alkylthio, alkenyl, alkynyl, hydroxyalkyl, haloalkyl, carbocyclyl, heterocyclyl, aryl, heteroaryl, -C (═ O) R, -ORa、-C(＝O)ORa、-OC(＝O)Ra、-SO2Ra、-NRbRc、-CONRbRc、-SO2NRbRc、-C(NRbRc)＝NRdOr ═ NRd(ii) a Wherein, R, Ra、Rb、RcAnd RdEach independently is hydrogen, cyano, amino, alkyl, alkylamino, arylamino, alkylthio, alkoxy, aryloxy, hydroxy, mercapto, alkyl, haloalkyl, carbocyclyl, heterocyclyl, aryl, heteroaryl, alkylsulfonyl, aminosulfonyl, hydroxyalkyl, aminoalkyl, alkylacyl, or aminoacyl. Wherein each alkylamino, arylamino, alkoxy, aryloxy, hydroxy, mercapto, alkyl, haloalkyl, carbocyclyl, heterocyclyl, aryl, heteroaryl, alkylsulfonyl, aminosulfonyl, hydroxyalkyl, aminoalkyl, alkanoyl, aminoacyl and alkylthio group of said substituents has the meaning described herein and may each be further mono-or polysubstituted, the same or different, by the substituents described herein.
In addition, unless otherwise explicitly indicated, the descriptions of the terms "… independently" and "… independently" and "… independently" used in the present invention are interchangeable and should be understood in a broad sense to mean that the specific items expressed between the same symbols do not affect each other in different groups or that the specific items expressed between the same symbols in the same groups do not affect each other.
In the various parts of this specification, substituents of the disclosed compounds are disclosed in terms of group type or range. It is specifically intended that the invention includes each and every independent subcombination of the various members of these groups and ranges. For example, the term "C1-6Alkyl "means in particular independently disclosed methyl, ethyl, C3Alkyl radical, C4Alkyl radical, C5Alkyl and C6An alkyl group. "C1-4Alkyl refers specifically to independently disclosed methyl, ethyl, C3Alkyl (i.e. propyl, including n-propyl and isopropyl), C4Alkyl (i.e., butyl, including n-butyl, isobutyl, sec-butyl, and tert-butyl).
The term "alkyl" or "alkyl group" as used herein, denotes a saturated, straight or branched chain monovalent hydrocarbon radical containing from 1 to 20 carbon atoms, wherein the alkyl group may be optionally substituted with one or more substituents as described herein. Unless otherwise specified, alkyl groups contain 1-20 carbon atoms. In some embodiments, the alkyl group contains 1 to 12 carbon atoms; in other embodiments, the alkyl group contains 1 to 6 carbon atoms; in still other embodiments, the alkyl group contains 1 to 4 carbon atoms; in other embodiments, the alkyl group contains 1 to 3 carbon atoms. The term "C1-6Alkyl "denotes an alkyl group containing 1 to 6 carbon atoms.
Examples of alkyl groups include, but are not limited to, methyl (Me, -CH)3) Ethyl group (Et, -CH)2CH3) N-propyl (n-Pr, -CH)2CH2CH3) Isopropyl group (i-Pr, -CH (CH)3)2) N-butyl (n-Bu, -CH)2CH2CH2CH3) Isobutyl (i-Bu, -CH)2CH(CH3)2) Sec-butyl (s-Bu, -CH (CH)3)CH2CH3) Tert-butyl (t-Bu, -C (CH)3)3) N-pentyl (-CH)2CH2CH2CH2CH3) 2-pentyl (-CH (CH)3)CH2CH2CH3) 3-pentyl (-CH (CH)2CH3)2) 2-methyl-2-butyl (-C (CH)3)2CH2CH3) 3-methyl-2-butyl (-CH (CH)3)CH(CH3)2) 3-methyl-1-butyl (-CH)2CH2CH(CH3)2) 2-methyl-1-butyl (-CH)2CH(CH3)CH2CH3) N-hexyl (-CH)2CH2CH2CH2CH2CH3) 2-hexyl (-CH (CH)3)CH2CH2CH2CH3) 3-hexyl (-CH (CH)2CH3)(CH2CH2CH3) 2-methyl-2-pentyl (-C (CH))3)2CH2CH2CH3) 3-methyl-2-pentyl (-CH (CH)3)CH(CH3)CH2CH3) 4-methyl-2-pentyl (-CH (CH)3)CH2CH(CH3)2) 3-methyl-3-pentyl (-C (CH)3)(CH2CH3)2) 2-methyl-3-pentyl (-CH (CH)2CH3)CH(CH3)2) 2, 3-dimethyl-2-butyl (-C (CH)3)2CH(CH3)2) 3, 3-dimethyl-2-butyl (-CH (CH)3)C(CH3)3) N-heptyl, n-octyl, and the like.
The term "alkenyl" denotes a straight or branched chain monovalent hydrocarbon radical containing 2 to 12 carbon atoms, wherein at least one carbon-carbon sp is present2A double bond, wherein the alkenyl group may be optionally substituted with one or more substituents described herein, including the positioning of "cis" and "tans", or the positioning of "E" and "Z". In some embodiments, alkenyl groups contain 2 to 8 carbon atoms; in other embodiments, alkenyl groups contain 2 to 6 carbon atoms; in still other embodiments, the alkenyl group contains 2 to 4 carbon atoms. Examples of alkenyl groups include, but are not limited to, ethylAlkenyl (-CH ═ CH)2) Allyl (-CH)2CH＝CH2) Allyl (-CH ═ CHCH)3) And so on.
The term "alkynyl" denotes a straight or branched chain monovalent hydrocarbon radical containing 2 to 12 carbon atoms, wherein there is at least one carbon-carbon sp triple bond, wherein the alkynyl radical may be optionally substituted with one or more substituents as described herein. In some embodiments, alkynyl groups contain 2-8 carbon atoms; in other embodiments, alkynyl groups contain 2-6 carbon atoms; in still other embodiments, alkynyl groups contain 2-4 carbon atoms. Examples of alkynyl groups include, but are not limited to, ethynyl, propynyl, and the like.
The term "cycloalkyl" refers to a monovalent or polyvalent, non-aromatic, saturated monocyclic, bicyclic, or tricyclic ring system containing from 3 to 12 ring carbon atoms. In some embodiments, cycloalkyl groups contain from 3 to 10 ring carbon atoms; in other embodiments, cycloalkyl groups contain from 3 to 8 ring carbon atoms; in still other embodiments, cycloalkyl groups contain 3 to 6 ring carbon atoms. Examples of cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and the like. The cycloalkyl group may be optionally substituted with one or more substituents described herein.
The term "cycloalkenyl" refers to partially unsaturated, non-aromatic monocyclic, bicyclic, or tricyclic ring systems containing from 3 to 12 ring carbon atoms. In some embodiments cycloalkenyl groups contain 3 to 10 ring carbon atoms; in other embodiments, cycloalkenyl groups contain from 3 to 8 ring carbon atoms; in still other embodiments, cycloalkenyl groups contain 3 to 6 ring carbon atoms. Examples of cycloalkenyl groups include, but are not limited to, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, and the like. The cycloalkenyl group can be optionally substituted with one or more substituents described herein.
The term "aryl" denotes monocyclic, bicyclic and tricyclic aryl groups containing 6 to 14 ring atoms, or 6 to 12 ring atoms, or 8 to 12 ring atoms, or 6 to 10 ring atoms, wherein one or more attachment points in the aromatic system are in phase with the rest of the moleculeAnd (4) connecting. The term "aryl" may be used interchangeably with the terms "aromatic ring" or "aromatic ring". The aryl group includes a ring system formed by fusing an aromatic ring and an aromatic ring or a non-aromatic carbocyclic ring. Examples of the aryl group may include phenyl, naphthyl, anthryl, 1,2,3, 4-tetrahydronaphthyl, 2, 3-dihydro-1H-indenyl, bicyclo [4,2,0 ]]Oct-1 (6),2, 4-trienyl. The aryl group may be substituted or unsubstituted, wherein the substituent may be, but is not limited to, fluoro, chloro, bromo, oxo (═ O), cyano, nitro, carboxy, hydroxy, amino, aminomethyl, aminoacyl, methylamino, phenylamino, hydroxymethyl, methylsulfonyl, aminosulfonyl, acetyl, methoxy, phenoxy, trifluoromethoxy, methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, cyclopropyl, cyclopentyl, cyclohexyl, tetrahydrofuranyl, tetrahydrothienyl, tetrahydropyrrolyl, imidazolyl, imidazolinyl, piperidinyl, piperazinyl, morpholinyl, thienyl, thiazolyl, furyl, pyrrolyl, phenyl, pyridinyl, pyrimidinyl, -C (═ NH) NH2Or trifluoromethyl, and the like.
The terms "heterocyclyl" and "heterocycle" are used interchangeably herein and refer to a saturated or partially unsaturated monocyclic, bicyclic, or tricyclic ring system containing 3 to 12 ring atoms, wherein at least one ring atom is selected from the group consisting of nitrogen, sulfur, and oxygen atoms, and wherein any ring in the heterocyclic ring system is non-aromatic. Unless otherwise specified, heterocyclyl may be carbon-or nitrogen-based, and-CH2-the group may optionally be replaced by-C (═ O) -. The sulfur atom of the ring may optionally be oxidized to the S-oxide. The nitrogen atom of the ring may optionally be oxidized to an N-oxygen compound. In some embodiments, heterocyclyl is a 5-12 atom heterocyclyl; in other embodiments, heterocyclyl is a heterocyclyl consisting of 5 to 8 atoms; in still other embodiments, heterocyclyl is a 5-7 atom heterocyclyl; in still other embodiments, heterocyclyl is a heterocyclyl consisting of 5-6 atoms. The heterocyclic group may also be a bicyclic heterocyclic group; in some embodiments, heterocyclyl is a 7-12 atom bicyclic heterocyclyl; in other embodiments, heterocyclyl is a bicyclic heterocycle consisting of 7-10 atomsA cyclic group; in still other embodiments, the heterocyclyl is a bicyclic heterocyclyl consisting of 8-10 atoms.
Examples of heterocyclyl groups include, but are not limited to: oxiranyl, azetidinyl, oxetanyl, pyrrolidinyl, pyrazolidinyl, dihydrothienyl, 1, 3-dioxocyclopentyl, 1, 3-dioxocyclohexyl, 1, 4-dioxocyclohexyl, dithiocyclopentyl, tetrahydropyranyl, tetrahydrothiopyranyl, piperidinyl, 1, 2-dihydropyridinyl, morpholinyl, thiomorpholinyl, hexahydropyrimidyl, 1, 6-dihydropyrimidyl, 1, 2-dihydropyrazinyl, 1, 3-oxazinyl, piperazinyl, oxazolidinyl, dioxanyl, dithianyl, thiaxanyl, homopiperazinyl, homopiperidinyl, oxepinyl, thiepanyl, 2-oxa-5-azabicyclo [2.2.1]Hept-5-yl. In heterocyclic radicals of-CH2Examples of-groups substituted by-C (═ O) -include, but are not limited to, 2-oxopyrrolidin-1-yl, oxo-1, 3-thiazolidinyl, 2-oxooxazolidin-3-yl, 2-oxopiperidin-1-yl, 3-oxomorpholinyl, 2-oxopiperazin-1-yl, 3, 5-dioxopiperidinyl, 2-oxotetrahydropyrimidin-1 (2H) -yl and 2-oxodihydropyrimidin-1 (2H) -yl. Examples of heterocyclic sulfur atoms that are oxidized include, but are not limited to, sulfolane, 1-dioxothiomorpholinyl, and 1, 1-dioxo-1, 2-thiomorpholinyl. The heterocyclyl group may be substituted or unsubstituted, wherein the substituent may be, but is not limited to, fluoro, chloro, bromo, oxo (═ O), cyano, nitro, carboxy, hydroxy, amino, aminomethyl, aminoacyl, methylamino, phenylamino, hydroxymethyl, methylsulfonyl, aminosulfonyl, acetyl, methoxy, phenoxy, trifluoromethoxy, methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, cyclopropyl, cyclopentyl, cyclohexyl, tetrahydrofuranyl, tetrahydrothienyl, tetrahydropyrrolyl, imidazolyl, imidazolinyl, piperidinyl, piperazinyl, morpholinyl, thienyl, thiazolyl, furyl, pyrrolyl, phenyl, pyridinyl, pyrimidinyl, -C (═ NH) NH2Or trifluoromethyl, and the like.
In some embodiments, heterocyclyl is a 5-6 atom heterocyclyl and refers to saturated or partially unsaturated groups containing 5 or 6 ring atomsAnd wherein at least one ring atom is selected from the group consisting of nitrogen, sulfur and oxygen atoms. Examples of heterocyclic groups consisting of 5 to 6 atoms include, but are not limited to: pyrrolidinyl, pyrrolinyl, pyrazolinyl, pyrazolidinyl, imidazolinyl, imidazolidinyl, tetrahydrofuranyl, dihydrofuranyl, tetrahydrothienyl, oxazolidinyl, piperidinyl, 1, 2-dihydropyridinyl, morpholinyl, thiomorpholinyl, hexahydropyrimidyl, 1, 6-dihydropyrimidyl, 1, 2-dihydropyrazinyl, 1, 3-oxazinylalkyl, piperazinyl, 1,2,3, 6-tetrahydropyridinyl, 1,2,3, 4-tetrahydropyrimidinyl, 2, 5-dihydro-1H-pyrrolyl and the like. -CH in a heterocyclic radical of 5-6 atoms2The group-may be substituted with-C (═ O) -or the sulfur atom therein may be oxidized to S-oxide. And said heterocyclyl group of 5-6 atoms may be optionally substituted with one or more substituents as described herein.
The term "heteroaryl" denotes monocyclic, bicyclic and tricyclic ring systems containing 5 to 12 ring atoms, or 5 to 10 ring atoms, or 5 to 6 ring atoms, wherein at least one ring is aromatic and at least one ring contains one or more heteroatoms of nitrogen, sulfur and oxygen, wherein one or more attachment points in the heteroaromatic ring system are attached to the rest of the molecule. The term "heteroaryl" may be used interchangeably with the terms "heteroaromatic ring" or "heteroaromatic compound". The heteroaryl group includes a ring system formed by fusing a heteroaromatic ring and an aromatic ring, a heteroaromatic ring and a heteroaromatic ring, or a heteroaromatic ring and a non-aromatic carbocyclic ring or heterocyclic ring. In some embodiments, a 5-10 atom heteroaryl group contains 1,2,3, or 4 heteroatoms independently selected from oxygen, sulfur, and nitrogen. In some embodiments, heteroaryl is 7-12 atom consisting heteroaryl comprising 1,2,3, or 4 heteroatoms independently selected from O, S and N; the heteroaryl group of 7 to 12 atoms may be a monocyclic ring system or a bicyclic ring system comprising two rings. In other embodiments, heteroaryl is 7-10 atom consisting of heteroaryl containing 1,2,3, or 4 heteroatoms independently selected from oxygen, sulfur, and nitrogen; the heteroaryl group consisting of 7 to 10 atoms may be a monocyclic ring system or a bicyclic ring system comprising two rings. The heteroaromatic compoundThe group may be substituted or unsubstituted, wherein the substituent may be, but is not limited to, fluoro, chloro, bromo, oxo (═ O), cyano, nitro, carboxy, hydroxy, amino, aminomethyl, aminoacyl, methylamino, phenylamino, hydroxymethyl, methylsulfonyl, aminosulfonyl, acetyl, methoxy, phenoxy, trifluoromethoxy, methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, cyclopropyl, cyclopentyl, cyclohexyl, tetrahydrofuranyl, tetrahydrothienyl, tetrahydropyrrolyl, imidazolyl, imidazolinyl, piperidinyl, piperazinyl, morpholinyl, thienyl, thiazolyl, furyl, pyrrolyl, phenyl, pyridinyl, pyrimidinyl, guanidino (═ NH) NH2)、-N＝C＝S、-C(＝NH)NH2Or trifluoromethyl, and the like.
Examples of heteroaryl groups include, but are not limited to, furyl, imidazolyl (e.g., 1H-imidazol-1-yl), isoxazolyl, oxazolyl (e.g., 2-oxazolyl) pyrrolyl, 1,3, 4-oxadiazolyl, 2-pyridyl, 3-pyridyl, 4-pyridyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, pyridazinyl (e.g., 3-pyridazinyl), thiazolyl (e.g., 2-thiazolyl), 2-thienyl, 3-thienyl, pyrazolyl (e.g., 4-pyrazolyl, 1H-pyrazol-1-yl), pyrazinyl, 1,3, 5-triazinyl, triazolyl, tetrazolyl, and the like; the following bicyclic rings are also included, but are in no way limited to these: benzopyrrole, 6, 7-dihydrothieno [3,2-c ] pyridin-5 (4H) -yl, 1, 3-dioxoisoindolin-2-yl, pyrimidoimidazolyl, benzimidazolyl, benzofuranyl, dihydrobenzofuranyl, benzothiophenyl, indolyl (e.g., 1H-indol-1-yl), isoindolin-2-yl, benzo [ d ] thiazol-2-yl, indazolyl (e.g., 1H-indazol-1-yl, etc.), quinolyl (e.g., 2-quinolyl, 3-quinolyl, 4-quinolyl), isoquinolyl (e.g., 1-isoquinolyl, 3-isoquinolyl or 4-isoquinolyl), 5,6,7, 8-tetrahydroquinolyl, 3, 4-dihydro-2H-pyrano [3,2-b ] pyridyl, 2, 3-dihydro- [1,4] dioxino [2,3-b ] pyridyl, 2, 3-dihydrobenzo [ b ] [1,4] dioxino, 6, 7-dihydro-5H-cyclopenta [3,2-b ] pyridyl, 2, 3-dihydrofuro [3,2-b ] pyridine, quinolinonyl, dihydroquinolinonyl and the like.
The term "alkoxy" denotes an alkyl group which is attached to the molecule through an oxygen atomThe remainder being linked, wherein the alkyl group has the meaning as described herein. In some embodiments, alkoxy groups contain 1 to 6 carbon atoms; in other embodiments, the alkoxy group contains 1 to 4 carbon atoms; in still other embodiments, alkoxy groups contain 1-3 carbon atoms. The alkoxy group may be optionally substituted with one or more substituents described herein. Examples of alkoxy groups include, but are not limited to, methoxy (MeO, -OCH)3) Ethoxy (EtO, -OCH)2CH3) 1-propoxy (n-PrO, n-propoxy, -OCH)2CH2CH3) And so on.
The term "alkylamino" denotes an amino group substituted by one or two alkyl groups, wherein the alkyl groups have the meaning as described herein. Examples include, but are not limited to, N-methylamino, N-ethylamino, N, N-dimethylamino, N, N-diethylamino, and the like.
The term "cycloalkylamino" denotes an amino group substituted by one or two cycloalkyl groups, wherein the cycloalkyl groups have the meaning as described herein. Examples include, but are not limited to, N-cyclopropylamino, and the like.
The term "alkylcarbonyl" means that an alkyl group is attached to the rest of the molecule through a carbonyl group (-C (═ O) -), wherein the alkyl group has the meaning described herein. Examples include, but are not limited to, CH3-C (═ O) -, etc.
The term "cycloalkylcarbonyl" denotes a cycloalkyl group attached to the rest of the molecule through a carbonyl group (-C (═ O) -), wherein the cycloalkyl group has the meaning described herein. Examples of such include, but are not limited to,
Figure BDA0001797086400000091
and the like.
The term "alkylaminocarbonyl" denotes an alkylamino group attached to the rest of the molecule through a carbonyl group (-C (═ O) -), wherein the alkylamino group has the meaning described herein. Examples include, but are not limited to, N-dimethylamino-C (═ O) -, and the like.
The term "cycloalkylaminocarbonyl" denotes a cycloalkylamino group attached to the rest of the molecule via a carbonyl group (-C (═ O) -), wherein the cycloalkylamino group has the meaning described herein. Examples of such include, but are not limited to,
Figure BDA0001797086400000092
and the like.
The term "cycloalkyl-alkyl" means that the cycloalkyl group is attached to the rest of the molecule through an alkyl group, wherein the cycloalkyl group and the alkyl group have the meaning described herein. Examples of such include, but are not limited to,
Figure BDA0001797086400000093
and the like.
The term "aryl-alkyl" means that the aryl group is attached to the rest of the molecule through an alkyl group, wherein the aryl group and the alkyl group have the meaning described herein. Examples of such include, but are not limited to,
Figure BDA0001797086400000101
and the like.
The term "alkoxy-alkyl" means that the alkoxy group is attached to the rest of the molecule through an alkyl group, wherein the alkoxy group and the alkyl group have the meaning described herein. Examples include, but are not limited to, -CH2OCH3And so on.
The term "cycloalkenyl-alkyl" denotes a cycloalkenyl group attached to the rest of the molecule through an alkyl group, i.e., an alkyl group substituted with one or more cycloalkenyl groups, wherein alkyl groups and cycloalkenyl groups have the meaning as described herein.
The term "haloalkyl" means an alkyl group substituted with one or more halo groups. Examples of such include, but are not limited to, -CF3And so on.
The term "haloalkoxy" denotes an alkoxy group substituted with one or more halogen groups, examples of which includeBut is not limited to, -OCF3And so on.
The term "haloaryl" denotes an aryl group substituted with one or more halogen groups, examples of which include, but are not limited to,
Figure BDA0001797086400000102
and the like.
The term "haloalkoxy-alkyl" denotes an alkoxy-alkyl group substituted with one or more halogen groups, examples of which include, but are not limited to, CF3OCH2-, etc.
The term "haloalkenyl" denotes an alkenyl group substituted with one or more halogen groups.
The term "haloalkynyl" denotes an alkynyl group substituted with one or more halo groups.
The term "halogen" refers to fluorine (F), chlorine (Cl), bromine (Br) or iodine (I).
The "acceptable salts" according to the invention include acid addition salts and base addition salts, suitable bases being hydroxides, carbonates, bicarbonates, especially sodium, potassium, magnesium, and calcium salts of alkali metals and alkaline earth metals, and ammonium, having (C)1-C4) Primary, secondary and tertiary amines of alkyl radicals, (C)1-C4) Mono-, di-and trialkanolamines of alkanols, choline and choline chloride.
The salt may be a salt added with an inorganic acid such as hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid or phosphoric acid, or a salt added with an organic acid such as formic acid, carbonic acid, and alkanoic acids such as acetic acid, trifluoroacetic acid, trichloroacetic acid and propionic acid, and glycolic acid, thiocyanic acid, lactic acid, succinic acid, citric acid, benzoic acid, cinnamic acid, oxalic acid, saturated or mono-or di-unsaturated C6-C20Fatty acids, alkylsulfuric monoesters, alkylsulfonic acids (sulfonic acids having a linear or branched alkyl group of 1 to 20 carbon atoms), arylsulfonic acids or arylsulfonic acids (aromatic groups bearing one or two sulfonic acid groups, e.g. phenyl and naphthyl), alkylphosphonic acids (phosphonic acids having a linear or branched alkyl group of 1 to 20 carbon atoms), arylphosphonic acidsOr aryl diphosphonic acids (aromatic groups bearing one or two phosphonic acid groups, such as phenyl and naphthyl), wherein the alkyl and aryl groups may bear other substituents, such as p-toluenesulfonic acid, salicylic acid, p-aminosalicylic acid, 2-phenoxybenzoic acid, 2-acetoxybenzoic acid, and the like.
Detailed description of the Compounds of the invention
The invention aims to provide a compound for controlling weeds, a composition and a preparation containing the compound and application of the compound as a herbicide.
In one aspect, the present invention provides a compound of formula (I) or a stereoisomer, a nitroxide, and acceptable salts thereof:
Figure BDA0001797086400000103
wherein:
q is Q1、Q2、Q3、Q4、Q5Or Q6，
Figure BDA0001797086400000111
Wherein R isa、Rb、RdAnd RhEach independently is hydrogen, alkyl, cycloalkyl, alkenyl or alkynyl;
wherein R isc、Re、RfAnd RgEach independently is hydrogen, halogen, cyano, hydroxy, alkyl, haloalkyl, alkoxy, cycloalkyl, alkenyl, or alkynyl;
x is oxygen or sulfur;
R1is hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl-alkyl or aryl-alkyl;
R2is hydrogen, hydroxy, amino, alkyl, haloalkyl, alkoxy-alkyl, haloalkoxy-alkyl, alkenyl, alkynyl, haloalkenyl, haloalkynyl, aryl-alkyl, cycloalkyl-alkyl, cycloalkenyl-alkyl, alkylCarbonyl, cycloalkylcarbonyl, alkyl-O-C (═ O) -, alkylamino, cycloalkylamino, alkylaminocarbonyl, or cycloalkylaminocarbonyl;
or R2Is aryl or aryl-S (O)2-；
Or R2Is a saturated, partially unsaturated or aromatic mono-or bi-heterocyclic ring containing 1,2,3,4 or 5 atoms selected from nitrogen, oxygen or sulfur atoms;
wherein R is2Optionally substituted with 1,2,3,4 or 5 substituents selected from a 1;
R3is hydrogen, alkyl, haloalkyl, alkenyl, alkynyl, cycloalkyl, aryl or aryl-alkyl;
wherein R is3Optionally substituted with 1,2,3,4 or 5 substituents selected from a 2;
w is hydrogen, nitro, halogen, cyano, alkyl, alkoxy-alkyl, haloalkyl, alkenyl, haloalkenyl, alkynyl, haloalkynyl, cycloalkyl-alkyl, alkylcarbonyl, alkyl-C (═ O) -O-, alkyl-O-C (═ O) -, alkyl-s (O)n-, alkyl-O-C (═ O) -O-, R12R13N-SO2-、R12R13N-C (═ O) -or R14R15N-；
Wherein W is optionally substituted with 1,2,3,4 or 5 substituents selected from a 3;
wherein each of a1, a2, and A3 is independently halogen, hydroxy, cyano, nitro, oxo (═ O), alkyl, haloalkyl, alkoxy, haloalkoxy, cycloalkyl, alkenyl, alkynyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aryl-alkyl, aryl-O-, aryl-s (O)2-, aryl-O-alkyl, heteroaryl, heterocyclyl, alkylcarbonyl, alkyl-O-C (═ O) -, alkyl-s (O)n-, alkyl-C (═ O) -O-, R16R17N-C (═ O) -or R18R19N-；
Wherein n is 0, 1 or 2;
wherein R is12、R13、R16And R17Each independently is hydrogen or alkyl;
wherein R is14、R15、R18And R19Each independently hydrogen, alkyl, alkylcarbonyl or alkyl-S (O)2-；
Z is hydrogen or alkyl;
y is hydrogen, nitro, halogen, cyano, alkyl, haloalkyl, alkoxy or haloalkoxy.
In some embodiments, Q is Q1、Q2、Q3、Q4、Q5Or Q6，
Figure BDA0001797086400000112
Wherein R isa、Rb、RdAnd RhEach independently is hydrogen, C1-6Alkyl radical, C3-8Cycloalkyl radical, C2-6Alkenyl or C2-6An alkynyl group;
wherein R isc、Re、RfAnd RgEach independently of the others is hydrogen, halogen, cyano, hydroxy, C1-6Alkyl, halo C1-6Alkyl radical, C1-6Alkoxy radical, C3-8Cycloalkyl radical, C2-6Alkenyl or C2-6An alkynyl group;
x is oxygen or sulfur;
R1is hydrogen, C1-6Alkyl radical, C2-6Alkenyl radical, C2-6Alkynyl, C3-8Cycloalkyl radical, C3-8cycloalkyl-C1-3Alkyl or C6-10aryl-C1-3An alkyl group;
R2is hydrogen, hydroxy, amino, C1-6Alkyl, halo C1-6Alkyl radical, C1-3alkoxy-C1-3Alkyl, halo C1-3alkoxy-C1-3Alkyl radical, C2-6Alkenyl radical, C2-6Alkynyl, halo C2-6Alkenyl, halo C2-6Alkynyl, C6-14aryl-C1-3Alkyl radical, C3-8Cycloalkyl radical, C3-8cycloalkyl-C1-3Alkyl radical, C3-10Cycloalkenyl radical, C3-10Cycloalkenyl radical-C1-3Alkyl radical, C1-6Alkylcarbonyl group, C3-8Cycloalkyl carbonyl group, C1-6alkyl-O-C (═ O) -, C1-6Alkylamino radical, C3-8Cycloalkylamino, C1-6Alkylaminocarbonyl or C3-8A cycloalkylaminocarbonyl group;
or R2Is C6-14Aryl or C6-14aryl-S (O)2-；
Or R2Is a saturated, partially unsaturated or aromatic C containing 1,2,3,4 or 5 atoms selected from nitrogen, oxygen or sulfur atoms1-10Mono-or bis-heterocyclic;
wherein R is2Optionally substituted with 1,2,3,4 or 5 substituents selected from a 1;
R3is hydrogen, C1-6Alkyl, halo C1-6Alkyl radical, C2-6Alkenyl radical, C2-6Alkynyl, C3-8Cycloalkyl radical, C6-14Aryl or C6-14aryl-C1-3An alkyl group;
wherein R is3Optionally substituted with 1,2,3,4 or 5 substituents selected from a 2;
w is hydrogen, nitro, halogen, cyano, C1-6Alkyl radical, C1-6Alkoxy radical, C1-3alkoxy-C1-3Alkyl, halo C1-6Alkyl radical, C2-6Alkenyl, halo C2-6Alkenyl radical, C2-6Alkynyl, halo C2-6Alkynyl, C3-8Cycloalkyl radical, C3-8cycloalkyl-C1-6Alkyl radical, C1-6Alkylcarbonyl group, C1-6alkyl-C (═ O) -O-, C1-6alkyl-O-C (═ O) -, C1-6alkyl-S (O)n-、C1-6alkyl-O-C (═ O) -O-, R12R13N-SO2-、R12R13N-C (═ O) -or R14R15N-；
Wherein W is optionally substituted with 1,2,3,4 or 5 substituents selected from a 3;
wherein each of a1, a2, and A3 is independently halogen, hydroxy, cyano, nitro, oxo (═ O), C1-6Alkyl, halo C1-6Alkyl radical, C1-6Alkoxy, halo C1-6Alkoxy radical, C3-8Cycloalkyl radical, C2-6Alkenyl radical, C2-6Alkynyl, halo C2-6Alkenyl, halo C2-6Alkynyl, C6-14Aryl, halo C6-14Aryl radical, C6-14aryl-C1-6Alkyl radical, C6-14aryl-O-, C6-14aryl-S (O)2-、C6-14aryl-O-C1-6Alkyl, 5-10 membered heteroaryl, 3-10 membered heterocyclyl, C1-6Alkylcarbonyl group, C1-6alkyl-O-C (═ O) -, C1-6alkyl-S (O)n-、C1-6alkyl-C (═ O) -O-, R16R17N-C (═ O) -or R18R19N-；
Wherein n is 0, 1 or 2;
wherein R is12、R13、R16And R17Each independently is hydrogen or C1-6An alkyl group;
wherein R is14、R15、R18And R19Each independently is hydrogen, C1-6Alkyl radical, C1-6Alkylcarbonyl or C1-6alkyl-S (O)2-；
Z is hydrogen or C1-6An alkyl group;
y is hydrogen, nitro, halogen, cyano, C1-6Alkyl, halo C1-6Alkyl radical, C1-6Alkoxy or halo C1-6An alkoxy group.
In some embodiments, Q is Q1、Q2、Q3、Q4、Q5Or Q6，
Figure BDA0001797086400000121
Wherein R isa、Rb、RdAnd RhEach independently is hydrogen, C1-4Alkyl radical, C3-6Cycloalkyl radical, C2-4Alkenyl or C2-4An alkynyl group;
wherein R isc、Re、RfAnd RgEach of which isIndependently hydrogen, halogen, cyano, hydroxy, C1-4Alkyl, halo C1-4Alkyl radical, C1-4Alkoxy radical, C3-6Cycloalkyl radical, C2-4Alkenyl or C2-4Alkynyl.
In other embodiments, Q is Q1、Q2、Q3、Q4、Q5Or Q6，
Figure BDA0001797086400000131
Wherein R isa、Rb、RdAnd RhEach independently is hydrogen, -CH3、-CH2CH3、-CH2CH2CH3、-CH(CH3)2、-CH2CH2CH2CH3、-CH2CH(CH3)2、-C(CH3)3Or cyclopropyl;
wherein R isc、Re、RfAnd RgEach independently hydrogen, fluorine, chlorine, bromine, iodine, cyano, hydroxy, -CH3、-CH2CH3、-CH2CH2CH3、-CH(CH3)2、-CH2CH2CH2CH3、-CH2CH(CH3)2、-C(CH3)3、-CH2F、-CHF2、-CF3、-CH2Cl、-CHCl2、-CCl3、-CH2CH2F、-CH2CHF2、-CH2CF3、-CH2CH2CH2F、-OCH3、-OCH2CH3、-OCH2CH2CH3、-CH＝CH2、-CH2CH＝CH2、-CH＝CHCH3、-CH2CH2CH＝CH2、-CH2CH＝CHCH3、-C≡CH、-CH2-C≡CH、-CH2-C≡CCH3or-CH2CH2-C≡CH。
In still other embodiments, Rc、Re、RfAnd RgEach independently of the other, of the following sub-formulae:
Figure BDA0001797086400000132
in some embodiments, R1Is hydrogen, C1-4Alkyl radical, C2-4Alkenyl radical, C2-4Alkynyl, C3-6Cycloalkyl radical, C3-6cycloalkyl-C1-3Alkyl or C6-10aryl-C1-3An alkyl group.
In other embodiments, R1Is hydrogen, -CH3、-CH2CH3、-CH2CH2CH3、-CH(CH3)2、-CH2CH2CH2CH3、-CH2CH(CH3)2、-C(CH3)3、-CH＝CH2、-CH2CH＝CH2or-CH2-C≡CH。
In still other embodiments, R1Is of the sub-structure:
Figure BDA0001797086400000133
in some embodiments, R3Is hydrogen, C1-4Alkyl, halo C1-4Alkyl radical, C2-4Alkenyl radical, C2-4Alkynyl, C3-6Cycloalkyl radical, C6-10Aryl or C6-10aryl-C1-3An alkyl group;
wherein R is3Optionally substituted with 1,2,3,4 or 5 substituents selected from a 2;
wherein each A2 is independently halogen, hydroxy, cyano, nitro, C1-4Alkyl, halo C1-4Alkyl radical, C1-4Alkoxy, halo C1-4Alkoxy radical, C3-6Cycloalkyl radical, C2-4Alkenyl radical, C2-4Alkynyl, halo C2-4Alkenyl, haloGeneration C2-4Alkynyl, C6-10Aryl, halo C6-10Aryl radical, C6-10aryl-C1-4Alkyl radical, C6-10aryl-O-, C6-10aryl-O-C1-4Alkyl radical, C1-4Alkylcarbonyl group, C1-4alkyl-O-C (═ O) -, C1-4alkyl-S (O)n-、C1-4alkyl-C (═ O) -O-, R16R17N-C (═ O) -or R18R19N-；
Wherein n is 0, 1 or 2;
wherein R is16And R17Each independently is hydrogen or C1-4An alkyl group;
wherein R is18And R19Each independently is hydrogen, C1-4Alkyl radical, C1-4Alkylcarbonyl or C1-4alkyl-S (O)2-。
In other embodiments, R3Is hydrogen, -CH3、-CH2CH3、-CH2CH2CH3、-CH(CH3)2、-CH2CH2CH2CH3、-CH2CH(CH3)2、-C(CH3)3、-CF3、-CH＝CH2、-CH2CH＝CH2、-CH＝CHCH3、-CH2CH2CH＝CH2、-CH2CH＝CHCH3、-C≡CH、-CH2-C≡CH、-CH2-C≡CCH3or-CH2CH2-C≡CH。
In still other embodiments, R3Is of the sub-structure:
Figure BDA0001797086400000134
in still other embodiments, R3Optionally substituted with 1,2,3,4 or 5 substituents selected from a 2;
wherein each A2 is independently fluorine, chlorine, bromine, iodine, hydroxy, cyano, nitro, -CH3、-CH2CH3、-CH2CH2CH3、-CH(CH3)2、-CH2CH2CH2CH3、-CH2CH(CH3)2、-C(CH3)3、-CH2F、-CHF2、-CF3、-CH2Cl、-CHCl2、-CCl3、-CH2CH2F、-CH2CHF2、-CH2CF3、-CH2CH2CH2F、-CH2CH2CHF2、-CH2CH2CF3、-CH2CF2CF3、-CH(CF3)2、-CF(CF3)2、-CH2CH2CH2CH2F、-CH2CH2CH2CHF2、-CH2CH2CH2CF3、-CH2CH(CF3)2、-C(CF3)(CH3)2、-C(CF3)3、-OCH3、-OCH2CH3、-OCH2CH2CH3、-OCH(CH3)2、-OCH2CH2CH2CH3、-OCH2CH(CH3)2、-OC(CH3)3、-OCF3、-OCH2CF3、-OCF2CF3、-OCF(CF3)2、-CH＝CH2、-CH2CH＝CH2、-CH＝CHCH3、-CH2CH2CH＝CH2、-CH2CH＝CHCH3、-C≡CH、-CH2-C≡CH、-CH2-C≡CCH3or-CH2CH2-C≡CH、-C(＝O)CH3、-C(＝O)CH2CH3、-C(＝O)OCH3、-C(＝O)OCH2CH3、-SCH3、-SCH2CH3、-S(O)CH3、-S(O)CH2CH3、-S(O)2CH3、-S(O)2CH2CH3、-OC(＝O)CH3、-OC(＝O)CH2CH3or-NH2；
Or each a2 is independently of the substructure:
Figure BDA0001797086400000141
in some embodiments, W is hydrogen, nitro, halogen, cyano, C1-4Alkyl radical, C1-4Alkoxy radical, C1-3alkoxy-C1-3Alkyl, halo C1-4Alkyl radical, C2-4Alkenyl, halo C2-4Alkenyl radical, C2-4Alkynyl, halo C2-4Alkynyl, C3-6Cycloalkyl radical, C3-6cycloalkyl-C1-4Alkyl radical, C1-4Alkylcarbonyl group, C1-4alkyl-C (═ O) -O-, C1-4alkyl-O-C (═ O) -, C1-4alkyl-S (O)n-、C1-4alkyl-O-C (═ O) -O-, R12R13N-SO2-、R12R13N-C (═ O) -or R14R15N-；
Wherein W is optionally substituted with 1,2,3,4 or 5 substituents selected from a 3;
wherein each A3 is independently halogen, hydroxy, cyano, nitro, C1-4Alkyl, halo C1-4Alkyl radical, C1-4Alkoxy, halo C1-4Alkoxy radical, C3-6Cycloalkyl radical, C2-4Alkenyl radical, C2-4Alkynyl, halo C2-4Alkenyl, halo C2-4Alkynyl, C6-10Aryl, halo C6-10Aryl radical, C6-10aryl-C1-4Alkyl radical, C6-10aryl-O-, C6-10aryl-O-C1-4Alkyl radical, C1-4Alkylcarbonyl group, C1-4alkyl-O-C (═ O) -, C1-4alkyl-S (O)n-、C1-4alkyl-C (═ O) -O-, R16R17N-C (═ O) -or R18R19N-；
Wherein n is 0, 1 or 2;
wherein R is12、R13、R16And R17Each independently is hydrogen or C1-4An alkyl group;
wherein R is14、R15、R18And R19Each independently is hydrogen, C1-4Alkyl radical, C1-4Alkylcarbonyl or C1-4alkyl-S (O)2-。
In other embodiments, W is hydrogen, fluoro, chloro, bromo, iodo, cyano, -CH3、-CH2CH3、-CH2CH2CH3、-CH(CH3)2、-CH2CH2CH2CH3、-CH2CH(CH3)2、-C(CH3)3、-OCH3、-OCH2CH3、-OCH2CH2CH3、-OCH(CH3)2、-OCH2CH2CH2CH3、-OCH2CH(CH3)2、-OC(CH3)3、-CH2OCH3、-CH2OCH2CH3、-CH2OCH2CH2CH3、-CH2OCH(CH3)2、-CH2CH2OCH3、-CH2CH2OCH2CH3、-CH2CH2OCH2CH2CH3、-CH2CH2OCH(CH3)2、-CH2CH2CH2OCH3、-CH2CH2CH2OCH2CH3、-CH2CH2CH2OCH2CH2CH3、-CH2CH2CH2OCH(CH3)2、-C(CH3)2OCH(CH3)2、-CH2F、-CHF2、-CF3、-CH＝CH2、-CH2CH＝CH2、-CH＝CHCH3、-C≡CH、-CH2-C≡CH、-SCH3、-S(O)2CH3or-NH2。
In still other embodiments, W is of the sub-formula:
Figure BDA0001797086400000151
in still other embodiments, W is optionally substituted with 1,2,3,4, or 5 substituents selected from a 3;
wherein each A3 is independently fluorine, chlorine, bromine, iodine, hydroxy, cyano, nitro, -CH3、-CH2CH3、-CH2CH2CH3、-CH(CH3)2、-CH2CH2CH2CH3、-CH2CH(CH3)2、-C(CH3)3、-CH2F、-CHF2、-CF3、-CH2Cl、-CHCl2、-CCl3、-CH2CH2F、-CH2CHF2、-CH2CF3、-CH2CH2CH2F、-CH2CH2CHF2、-CH2CH2CF3、-CH2CF2CF3、-CH(CF3)2、-CF(CF3)2、-CH2CH2CH2CH2F、-CH2CH2CH2CHF2、-CH2CH2CH2CF3、-CH2CH(CF3)2、-C(CF3)(CH3)2、-C(CF3)3、-OCH3、-OCH2CH3、-OCH2CH2CH3、-OCH(CH3)2、-OCH2CH2CH2CH3、-OCH2CH(CH3)2、-OC(CH3)3、-OCF3、-OCH2CF3、-OCF2CF3、-OCF(CF3)2、-CH＝CH2、-CH2CH＝CH2、-CH＝CHCH3、-CH2CH2CH＝CH2、-CH2CH＝CHCH3、-C≡CH、-CH2-C≡CH、-CH2-C≡CCH3or-CH2CH2-C≡CH、-C(＝O)CH3、-C(＝O)CH2CH3、-C(＝O)OCH3、-C(＝O)OCH2CH3、-SCH3、-SCH2CH3、-S(O)CH3、-S(O)CH2CH3、-S(O)2CH3、-S(O)2CH2CH3、-OC(＝O)CH3、-OC(＝O)CH2CH3or-NH2；
Or each a3 is independently of the substructure:
Figure BDA0001797086400000152
in some embodiments, Z is hydrogen or C1-4An alkyl group.
In other embodiments, Z is hydrogen, -CH3、-CH2CH3、-CH2CH2CH3、-CH(CH3)2、-CH2CH2CH2CH3、-CH2CH(CH3)2or-C (CH)3)3。
In some embodiments, Y is hydrogen, nitro, halogen, cyano, C1-4Alkyl, halo C1-4Alkyl radical, C1-4Alkoxy or halo C1-4An alkoxy group.
In other embodiments, Y is hydrogen, nitro, fluoro, chloro, bromo, iodo, cyano, -CH3、-CH2CH3、-CH2CH2CH3、-CH(CH3)2、-CH2CH2CH2CH3、-CH2CH(CH3)2、-C(CH3)3、-CF3、-OCH3、-OCH2CH3、-OCF3、-OCH2CF3or-OCF2CF3。
In some embodiments, R2Is hydrogen or hydroxyAmino group, C1-4Alkyl, halo C1-4Alkyl radical, C1-3alkoxy-C1-3Alkyl, halo C1-3alkoxy-C1-3Alkyl radical, C2-4Alkenyl radical, C2-4Alkynyl, halo C2-4Alkenyl, halo C2-4Alkynyl, C6-10aryl-C1-3Alkyl radical, C3-6Cycloalkyl radical, C3-6cycloalkyl-C1-3Alkyl radical, C1-4Alkylcarbonyl group, C3-6Cycloalkyl carbonyl group, C1-4Alkylamino radical, C3-6Cycloalkylamino, C1-4Alkylaminocarbonyl or C3-6A cycloalkylaminocarbonyl group.
In other embodiments, R2Is C6-14Aryl or C6-14aryl-S (O)2-。
In still other embodiments, R2Is a saturated, partially unsaturated or aromatic C containing 1,2,3,4 or 5 atoms selected from nitrogen, oxygen or sulfur atoms1-9Mono-or bis-heterocyclic.
In still other embodiments, R2Optionally substituted with 1,2,3,4 or 5 substituents selected from A1,
wherein each a1 is independently halogen, hydroxy, cyano, nitro, oxo (═ O), C1-4Alkyl, halo C1-4Alkyl radical, C1-4Alkoxy, halo C1-4Alkoxy radical, C3-6Cycloalkyl radical, C2-4Alkenyl radical, C2-4Alkynyl, halo C2-4Alkenyl, halo C2-4Alkynyl, C6-10Aryl, halo C6-10Aryl radical, C6-10aryl-C1-4Alkyl radical, C6-10aryl-O-, C6-10aryl-S (O)2-、C6-10aryl-O-C1-4Alkyl, 5-6 membered heteroaryl, 3-8 membered heterocyclyl, C1-4Alkylcarbonyl group, C1-4alkyl-O-C (═ O) -, C1-4alkyl-S (O)n-、C1-4alkyl-C (═ O) -O-, R16R17N-C (═ O) -or R18R19N-；
Wherein n is 0, 1 or 2;
wherein R is16And R17Each independently is hydrogen or C1-4An alkyl group;
wherein R is18And R19Each independently is hydrogen, C1-6Alkyl radical, C1-6Alkylcarbonyl or C1-6alkyl-S (O)2-。
In some embodiments, R2Is hydrogen, hydroxy, amino, -CH3、-CH2CH3、-CH2CH2CH3、-CH(CH3)2、-CH2CH2CH2CH3、-CH2CH(CH3)2、-C(CH3)3、-CH2F、-CHF2、-CF3、-CH2Cl、-CHCl2、-CCl3、-CH2CH2F、-CH2CHF2、-CH2CF3、-CF2CF3、-CH2CH2CH2F、-CH2CH2CHF2、-CH2CH2CF3、-CH2CF2CF3、-CH(CF3)2、-CF(CF3)2、-CH2CH2CH2CH2F、-CH2CH2CH2CHF2、-CH2CH2CH2CF3、-CH2CH(CF3)2、-C(CF3)(CH3)2、-C(CF3)3、-CH2OCH3、-CH2OCH2CH3、-CH2OCH2CH2CH3、-CH2OCH(CH3)2、-CH2CH2OCH3、-CH2CH2OCH2CH3、-CH2CH2OCH2CH2CH3、-CH2CH2OCH(CH3)2、-CH2CH2CH2OCH3、-CH2CH(CH3)OCH3、-CH2CH2CH2OCH2CH3、-CH2CH(CH3)OCH2CH3、-CH2CH2CH2OCH2CH2CH3、-CH2CH2CH2OCH(CH3)2、-C(CH3)2OCH(CH3)2、-CH2OCF3、-CH2OCH2CF3、-CH2OCF2CF3、-CH2OCH2CH2CF3、-CH2OCH(CF3)2、-CH2OCF(CF3)2、-CH2CH2OCF3、-CH2CH2OCH2CF3、-CH2CH2OCF2CF3、-CH2CH2OCH2CH2CF3、-CH2CH2OCH(CF3)2、-CH2CH2OCF(CF3)2、-CH2CH2CH2OCF3、-CH2CH2CH2OCH2CF3、-CH2CH2CH2OCF2CF3、-CH2CH2CH2OCH2CH2CF3、-CH2CH2CH2OCH(CF3)2、-CH2CH2CH2OCF(CF3)2、-C(CH3)2OCH(CF3)2、-CH＝CH2、-CH2CH＝CH2、-CH＝CHCH3、-CH2CH2CH＝CH2、-CH2CH＝CHCH3、-C≡CH、-CH2-C≡CH、-CH2-C≡CCH3、-CH2CH2-C≡CH、-C(＝O)CH3or-C (═ O) CH2CH3。
In other embodiments, R2Is of the sub-structure:
Figure BDA0001797086400000161
Figure BDA0001797086400000171
in still other embodiments, R2Optionally substituted with 1,2,3,4 or 5 substituents selected from a 1;
wherein each a1 is independently fluoro, chloro, bromo, iodo, hydroxy, cyano, nitro, oxo (═ O), -CH3、-CH2CH3、-CH2CH2CH3、-CH(CH3)2、-CH2CH2CH2CH3、-CH2CH(CH3)2、-C(CH3)3、-CH2F、-CHF2、-CF3、-CH2Cl、-CHCl2、-CCl3、-CH2CH2F、-CH2CHF2、-CH2CF3、-CH2CH2CH2F、-CH2CH2CHF2、-CH2CH2CF3、-CH2CF2CF3、-CH(CF3)2、-CF(CF3)2、-CH2CH2CH2CH2F、-CH2CH2CH2CHF2、-CH2CH2CH2CF3、-CH2CH(CF3)2、-C(CF3)3、-OCH3、-OCH2CH3、-OCH2CH2CH3、-OCH(CH3)2、-OCH2CH2CH2CH3、-OCH2CH(CH3)2、-OC(CH3)3、-OCF3、-OCH2CF3、-OCF2CF3、-OCF(CF3)2、-CH＝CH2、-CH2CH＝CH2、-CH＝CHCH3、-CH2CH2CH＝CH2、-CH2CH＝CHCH3、-C≡CH、-CH2-C≡CH、-CH2-C≡CCH3or-CH2CH2-C≡CH、-C(＝O)CH3、-C(＝O)CH2CH3、-C(＝O)OCH3、-C(＝O)OCH2CH3、-SCH3、-SCH2CH3、-S(O)CH3、-S(O)CH2CH3、-S(O)2CH3、-S(O)2CH2CH3、-OC(＝O)CH3、-OC(＝O)CH2CH3or-NH2；
Or each a1 is independently of the substructure:
Figure BDA0001797086400000172
in still other embodiments, R2Is shown in the following sub-structural formula,
Figure BDA0001797086400000173
Figure BDA0001797086400000181
Figure BDA0001797086400000191
in another aspect, the present invention provides compounds of one of the following structures or stereoisomers, nitroxides and acceptable salts thereof, but not limited to these compounds:
Figure BDA0001797086400000192
Figure BDA0001797086400000201
Figure BDA0001797086400000211
Figure BDA0001797086400000221
Figure BDA0001797086400000231
in another aspect, the present invention provides a composition comprising at least one compound of the invention as active substance.
In some embodiments, the compositions of the present invention further comprise an agriculturally pharmaceutically acceptable surfactant and a carrier.
In still other embodiments, the compositions of the present invention comprise additional active agents, wherein the additional active agents are one or more of herbicides, fungicides, acaricides, nematicides, insecticides, arthropodicides, safeners, and growth regulators.
In another aspect, the invention provides the use of a compound of the invention or a composition comprising a compound of the invention in agriculture.
In some embodiments, the present invention provides the use of a compound of the present invention or a composition comprising a compound of the present invention as a herbicide in agriculture.
In some embodiments, the present invention provides the use of a compound of the present invention or a composition comprising a compound of the present invention as a fungicide or insecticide in agriculture.
In some embodiments, the invention provides for the use of a compound of the invention or a composition comprising a compound of the invention in other fields.
Compositions and formulations of the compounds of the invention
The invention also relates to compositions comprising one of the compounds of formula (I) according to the invention. Such compositions further comprise, inter alia, adjuvants as defined below.
Suitable auxiliaries are solvents, liquid carriers, solid carriers or fillers, surfactants, dispersants, emulsifiers, wetting agents, adjuvants, solubilizers, penetration enhancers, protective colloids, adhesives, thickeners, humectants, repellents, attractants, feeding stimulants, compatibilizers, bactericides, antifreezes, defoamers, colorants, tackifiers and binders.
Suitable solvents and liquid carriers are water and organic solvents, such as mineral oil fractions of medium to high boiling point, e.g. kerosene, diesel oil; oils of vegetable or animal origin; aliphatic, cyclic and aromatic hydrocarbons, such as toluene, paraffins, tetrahydronaphthalene, alkylated naphthalenes; alcohols, such as ethanol, propanol, butanol, benzyl alcohol, cyclohexanol; glycols; DMSO; ketones, such as cyclohexanone; esters, such as lactate, carbonate, fatty acid ester, γ -butyrolactone; a fatty acid; a phosphonate ester; amines; amides, such as N-methylpyrrolidone, fatty acid dimethylamide; and mixtures thereof.
Suitable solid carriers or fillers are mineral earths, for example silicates, silica gels, talc, kaolin, limestone, lime, chalk, clay, dolomite, diatomaceous earth, bentonite, calcium sulfate, magnesium oxide; polysaccharides, such as cellulose, starch; fertilizers, such as ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas; products of vegetable origin, such as cereal flour, bark flour, wood flour and nut shell flour, and mixtures thereof.
Suitable surfactants are surface-active substances, such as anionic, cationic, nonionic and amphoteric surfactants, block polymers, polyelectrolytes, and mixtures thereof. Such surfactants can be used as emulsifiers, dispersants, solubilizers, wetting agents, penetration enhancers, protective colloids or adjuvants.
Suitable anionic surfactants include alkali metal salts of fatty acids, salts of aliphatic monoesters of sulphuric acid (e.g. sodium lauryl sulphate), salts of sulphonated aromatic compounds (e.g. sodium dodecylbenzenesulphonate, calcium dodecylbenzenesulphonate, butylnaphthalene sulphonate and mixtures of sodium di-isopropyl-naphthalene sulphonate and sodium tri-isopropyl-naphthalene sulphonate), ether sulphates, alcohol ether sulphates (e.g. sodium laureth-3-sulphate), ether carboxylates (e.g. sodium laureth-3-carboxylate), phosphate esters (products from the reaction between one or more fatty alcohols and phosphoric acid (predominantly mono-esters) or phosphorus pentoxide (predominantly di-esters), e.g. the reaction between lauryl alcohol and tetraphosphoric acid; alternatively these products may be ethoxylated), sulphosuccinamates, paraffin or olefin sulphonates, mixtures of such compounds, Taurates and lignosulfonates.
Suitable nonionic surfactants include condensation products of alkylene oxides, such as ethylene oxide, propylene oxide, butylene oxide or mixtures thereof, with fatty alcohols, such as oleyl alcohol or cetyl alcohol, or with alkylphenols, such as octylphenol, nonylphenol or octylcresol; partial esters derived from long chain fatty acids or hexitol anhydrides; condensation products of said partial esters with ethylene oxide; block polymers (comprising ethylene oxide and propylene oxide); an alkanolamide; monoesters (e.g., fatty acid polyglycol esters); amine oxides (e.g., lauryl dimethyl amine oxide); and lecithin.
Suitable cationic surfactants are quaternary surfactants, such as quaternary ammonium compounds having 1 or 2 hydrophobic groups, or salts of long chain primary amines. Suitable amphoteric surfactants are betaines and imidazolines.
Suitable adjuvants are compounds which have negligible or even no pesticidal activity per se and which improve the biological properties of the compounds I on the target. Examples are surfactants, mineral or vegetable oils and other auxiliaries.
Suitable thickeners are polysaccharides (e.g. xanthan gum, carboxymethylcellulose), inorganic clays (organically modified or unmodified), polycarboxylates and silicates.
Suitable anti-freeze agents are ethylene glycol, propylene glycol, urea and glycerol.
Suitable antifoams are polysiloxanes, silicone emulsions, long-chain alcohols, fatty acids and their salts, and also fluoroorganics and mixtures thereof.
Suitable colorants (e.g., red, blue or green colored) are pigments and water-soluble dyes of low water solubility. Examples are inorganic colorants (e.g., iron oxide, titanium oxide, iron hexacyanoferrate) and organic colorants (e.g., alizarin colorants, azo colorants and phthalocyanine colorants).
Suitable tackifiers or adhesives are polyvinylpyrrolidone, polyvinyl acetate, polyvinyl alcohol, polyacrylates, biowaxes or synthetic waxes and cellulose ethers.
If appropriate, further additional components may also be present, for example protective colloids, binders, adhesives, thixotropic substances, penetrants, stabilizers, chelating agents (sequestrants), complexing agents. In general, the active ingredient may be combined with any solid or liquid additive commonly used for formulation purposes.
The agricultural herbicides according to the invention can be applied in the form of their formulations or in the Use forms prepared therefrom, which are known from handbooks (Manual on development and Use of FAO Specifications for Plant Protection Products), 5 th edition, 1999. The forms of use include Dustable Powders (DP), Soluble Powders (SP), water-Soluble Granules (SG), water-dispersible granules (WG), Wettable Powders (WP), Granules (GR) (slow or fast release), soluble concentrates (SL), oil miscible liquids (OL), ultra low volume liquids (UL), Emulsifiable Concentrates (EC), Dispersible Concentrates (DC), emulsions (oil-in-water (EW) and water-in-oil (EO)), Microemulsions (ME), Suspension Concentrates (SC), aerosols, Capsule Suspensions (CS) and seed treatment formulations. The type of formulation chosen will depend on the technical problem to be solved and the physical, chemical and biological properties possessed by the compounds of formula (I).
Application of the inventive compounds and compositions
The herbicides of the present invention can be used by spraying plants, applying to soil, applying to the surface of water. The amount of the active ingredient is appropriately determined to meet the purpose of use. The content of the active ingredient is appropriately determined depending on the purpose.
The amount of the compound of the present invention to be used depends on the kind of the compound to be used, the target weed, the tendency of weed to appear, environmental conditions, the kind of herbicide, and the like.
The present invention provides a method for controlling weeds in crops of useful plants, which method comprises applying a compound of the invention or a composition thereof to a plant (e.g. a harmful plant, such as a monocotyledonous or dicotyledonous weed or an undesired crop plant), to a seed (e.g. a cereal, a seed or a vegetative propagule (e.g. a tuber or a shoot part)) or to an area where the plant is growing (e.g. a cultivation area). The compounds according to the invention can be applied before sowing (if appropriate also by incorporation into the soil), before emergence or after emergence. Specific examples of monocotyledonous and dicotyledonous weeds that can be controlled by the compounds of the present invention are shown below, but it is not intended to limit the list to a particular species.
Monocotyledonous weeds: aegilops (aegiops), Agropyron (Agropyron), Agrostis (Agrostis), Alopecurus (Alopecurus), pseudoagrostis (Apera), Avena (Avena), Brachiaria (Brachiaria), Bromus (broomus), tribulus (cenchus), kombucus (comulina), bermudagrass (Cynodon), sedge (cypress), thatch (dipterocarpa), datura (dactyloteron), Digitaria (Digitaria), barnyard (Echinochloa), Eleocharis (elocharocharis), eleusifolia (Eleocharis), setaria (olens), setaria (setaria), setaria (leptochloaria), setaria (leptochloaria), setaria) (leptochloaria), setaria (leptochloaria (setaria), setaria, Scirpus (Scirpus), Setaria (Setaria) or Sorghum (Sorghum).
Dicotyledonous weeds: abutilon (Abutilon), Amaranthus (Amaranthus), Ambrosia (Ambrosia), Malva (Andoa), Chrysanthemum (Anthemis), Rosa (Aphanes), Artemisia (Artemisia), Atriplex (Atriplex), Bellis (Bellis), Bidens (Bidens), Capsella (Capsella), Carduus (Carduus), Asplenium (Cassia), Centaurela (Centaurea), Chenopodium (Chenopodium), Cirsium (Cirsium), Convolvulus (Convolvulus), Datura (Datura), Achillea (Desmodium), Acronychia (Emex), Glycyrrhiza (Eugenium), Euphorbia (Occidum), Nepalea (Galeopsis), achyranthes (Galium), Hypericum (Verticicum), Mucora (Pilus), Pimpilus (Pimenta), Pimenta) and Pimenta (Pimenta) to (Pimenta), Pimpil (Pimenta), Pimenta) to obtain (Pimenta), Pimenta (Pimenta) to obtain (Pimenta), Pimenta) to (Pimpil (Pimenta), Pi, Poppy (Papaver), Pharbitis (Pharbitis), Plantago (Plantago), Polygonum (Polygonum), Portulaca (Portulaca), Ranunculus (Ranunculus), Raphanus (Raphanus), Rorippa (Rorippa), zygium (Rotala), Rumex (Rumex), Salsola (Salsola), Senecio (Senecio), Sesbania (Sesbania), rhodomyrtus (Sida), brassica (Sinapis), Solanum (Solanum), endive (Sonchus), cuspidatum (spironollea), Stellaria (stella), british (Taraxacum), pennycress (Thlasi), Trifolium (trillium), nettle (Urtica), Veronica (Veronica), violaxacum (Xanthomonas), or Xanthium (Xanthomonas).
Although having a significant herbicidal activity against monocotyledonous and dicotyledonous weeds, the compounds according to the invention have little damage, depending on their structure and their application rate, to economically important crop plants, such as dicotyledonous crops of the following genera: groundnut (Arachis), beetroot (Beta), Brassica (brassicaica), Cucumis (Cucumis), Cucurbita (Cucurbita), Helianthus (Helianthus), Daucus (Daucus), Glycine (Glycine), Gossypium (Gossypium), Ipomoea (Ipomoea), Lactuca (Lactuca), Linum (Linum), Lycopersicon (Lycopersicon), Miscanthus (cisanthus), Nicotiana (Nicotiana), Phaseolus (Phaseolus), Pisum (Pisum), Solanum (Solanum), Vicia, or monocotyledonous crops of the following genera: allium (Allium), Ananas (Ananas), Asparagus (Asparagus), Avena (Avena), Hordeum (Hordeum), Oryza (Oryza), Panicum (Panicum), Saccharum (Saccharum), Secale (Secale), Sorghum (Sorghum), Triticale (Triticale), Triticum (Triticum) and Zea (Zea). For these reasons, the compounds according to the invention are very suitable for selectively controlling the growth of undesired plants in plant crops, such as agriculturally useful plants or ornamental plants.
The compounds of the formula (I) according to the invention can, if desired, also be used in combination with other active ingredients, for example other herbicides and/or insecticides and/or acaricides and/or nematicides and/or arthropodicides and/or fungicides and/or plant growth regulators and/or safeners. These mixtures, and the use of these mixtures for controlling the growth of weeds and/or undesired vegetation, form yet further aspects of the invention. For the avoidance of doubt, inventive mixtures also include mixtures of two or more different compounds of formula (I). In particular, the present invention also relates to a composition according to the invention comprising, in addition to the compound of formula (I), at least one further herbicide.
General synthetic procedure
In this specification, a structure is dominant if there is any difference between the chemical name and the chemical structure. In general, the compounds of the present invention may be prepared by the methods described herein, wherein the substituents are as defined in (I), unless otherwise indicated. The following synthetic schemes and examples serve to further illustrate the context of the invention.
Those skilled in the art will recognize that: the chemical reactions described herein may be used to suitably prepare a number of other compounds of the invention, and other methods for preparing the compounds of the invention are considered to be within the scope of the invention. For example, the synthesis of those non-exemplified compounds according to the present invention can be successfully accomplished by those skilled in the art by modification, such as appropriate protection of interfering groups, by the use of other known reagents (other than those described herein), or by some routine modification of reaction conditions. In addition, the reactions disclosed herein or known reaction conditions are also recognized as being applicable to the preparation of other compounds of the present invention.
The chromatographic column is a silica gel column filled with 300-400 mesh silica gel. NMR spectral data were measured by Bruker Avance 400 NMR spectrometer or Bruker Avance III HD 600 NMRMeasured by resonance spectrometer, CDC13,DMSO-d6,CD3OD or acetone-d6As solvent (reported in ppm) TMS (0ppm) or chloroform (7.25ppm) was used as reference standard. When multiple peaks occur, the following abbreviations will be used: s (singleton), d (doublet), t (triplet ), m (multiplet, multiplet), br (broad ), dd (doublet of doublets, quartet), dt (doublet of triplets), ddd (doublet of doublet of doublets), ddt (doublet of doublet of triplets, doublet of doublets), dddd (doublet of doublet of doublets, doublet of doublets), and double doublet of doublets. Coupling constants are expressed in hertz (Hz).
The conditions for low resolution Mass Spectrometry (MS) data determination were: agilent 6120Quadrupole HPLC-MS (column model: Zorbax SB-C18,2.1X 30mm,3.5 μm,6min, flow rate 0.6mL/min, mobile phase 5% -95% (CH with 0.1% formic acid)3CN) in (H containing 0.1% formic acid)2Proportion in O)), at 210/254nm with UV detection, using electrospray ionization mode (ESI).
The following acronyms are used throughout the invention:
CDC13 deuterated chloroform
g
mg of
mmol millimole
mL of
The following reaction scheme describes the steps for preparing the compounds disclosed herein. Wherein R is1、R2、R3Q, W, Z, Y and X have the meanings described in the present invention.
Synthetic schemes
Synthesis scheme 1
Figure BDA0001797086400000271
The compounds of formula (I) can be synthesized by the methods disclosed in synthesis scheme 1. Wherein Hal is halogen. Compound 1 is reacted with methanol under acidic conditions to give compound 2. The compound 2 is reduced to obtain a compound 3. Compound 3 reacts with compound 4 to give compound 5. Reaction of compound 5 with compound 6 under basic conditions affords compound 7. And hydrolyzing the compound 7 to obtain a compound 8. The compound 8 reacts with the compound 9 to obtain the compound (I).
Examples
Example 1: synthesis of 1-ethyl-N- (1-methyl-1H-tetrazol-5-yl) -2, 4-dioxo-3- (o-tolyl) -1,2,3, 4-tetrahydroquinazoline-6-carboxamide
Figure BDA0001797086400000272
Step 1: synthesis of dimethyl 4-nitroisophthalate
4-Nitro-isophthalic acid (10.0g,47.3mmol) was dissolved in a mixed solvent of anhydrous toluene (30mL) and anhydrous methanol (20mL) at room temperature, concentrated sulfuric acid (3mL) was added, and the reaction was refluxed for 3 days. After the reaction was terminated, the solvent was removed under reduced pressure, and ethyl acetate (100mL) was added to the residue, washed with water, washed with a saturated sodium bicarbonate solution, washed with a saturated common salt solution, dried over anhydrous sodium sulfate, and the solvent was removed to obtain 10.1g of a white solid, yield: 89 percent.
MS(ES-API,pos.ion)m/z:262.0[M+Na]+；
1H NMR(400MHz,DMSO-d6)δ(ppm):8.35(s,1H),8.32(d,J＝8.4Hz,1H),8.18(d,J＝8.4Hz,1H),3.93(s,3H),3.88(s,3H)。
Step 2: synthesis of dimethyl 4-aminoisophthalate
Dimethyl 4-nitroisophthalate (6.54g,27.3mmol) and palladium on carbon (0.65g) were dissolved in ethyl acetate (90mL) at room temperature, hydrogen was passed through the solution, the temperature of the oil bath was slowly raised to 45 ℃ and the reaction was stopped after 6 hours. The palladium-carbon is removed by suction filtration, and the solvent is removed to obtain 5.43g of white solid, the yield is as follows: 95 percent. MS (ES-API, pos.ion) M/z 210.1[ M + H [ ]]+。
And step 3: synthesis of methyl 2, 4-dioxo-3- (o-tolyl) -1,2,3, 4-tetrahydroquinazoline-6-carboxylate
Dimethyl 4-aminoisophthalate (2.75g,13.1mmol) and o-tolylisocyanate (2.1g,15.7mmol) were dissolved in dry pyridine (19mL) at room temperature and reacted at 100 ℃ for 24 hours. After the reaction was stopped, water (60mL) was added to the reaction solution to precipitate a solid, which was then filtered by suction to obtain 3.4g of a white solid, yield: 83 percent.
MS(ES-API,pos.ion)m/z:310.9[M+H]+。
And 4, step 4: synthesis of methyl 1-ethyl-2, 4-dioxo-3- (o-tolyl) -1,2,3, 4-tetrahydroquinazoline-6-carboxylate
Methyl 2, 4-dioxo-3- (o-tolyl) -1,2,3, 4-tetrahydroquinazoline-6-carboxylate (1.7g,5.47mmol), cesium carbonate (2.14g,6.56mmol) and iodoethane (1.7g,10.9mmol) were dissolved in dry N, N-dimethylformamide (14mL) in that order at room temperature and reacted at room temperature for 4 hours. The reaction solution was slowly poured into water (60mL), extracted with ethyl acetate (50mLx 3), dried over anhydrous sodium sulfate, and separated by column chromatography [ petroleum ether/ethyl acetate (v/v) ═ 1/1], and the resulting product was recrystallized to give 1.4g of a white solid, yield: 75 percent.
MS(ES-API,pos.ion)m/z:338.9[M+H]+。
And 5: synthesis of 1-ethyl-2, 4-dioxo-3- (o-tolyl) -1,2,3, 4-tetrahydroquinazoline-6-carboxylic acid
Methyl 1-ethyl-2, 4-dioxo-3- (o-tolyl) -1,2,3, 4-tetrahydroquinazoline-6-carboxylate (1.41g,4.16mmol), lithium hydroxide monohydrate (0.35g,8.34mmol) were dissolved in tetrahydrofuran/methanol/water (v/v/v ═ 1/1/1,60mL) at room temperature and reacted at 45 ℃ for 4 hours. The solvent was removed under reduced pressure, the residue was dissolved in water, the aqueous phase was acidified to pH 1 with hydrochloric acid, extracted with ethyl acetate, and after stirring for 3 hours a solid precipitated which was filtered off with suction to give 1.0g of a white solid, yield: 74 percent.
MS(ES-API,pos.ion)m/z:324.9[M+H]+。
Step 6: synthesis of 1-ethyl-N- (1-methyl-1H-tetrazol-5-yl) -2, 4-dioxo-3- (o-tolyl) -1,2,3, 4-tetrahydroquinazoline-6-carboxamide
1-Ethyl-2, 4-dioxo-3- (o-tolyl) -1,2,3, 4-tetrahydroquinazoline-6-carboxylic acid (200mg,0.61mmol), 1-hydroxybenzotriazole (208mg,1.54mmol), N-diisopropylethylamine (80mg,0.61mmol) and N, N' -diisopropylcarbodiimide (195mg,1.54mmol) were dissolved in this order in dry dichloromethane (8mL) at room temperature, and after stirring at room temperature for 2 hours, 1-methyl-5-aminotetrazole (153mg,1.54mmol) was added and reacted at room temperature for 12 hours. The solvent was removed under reduced pressure, and the concentrated solution was subjected to column chromatography [ petroleum ether/ethyl acetate (v/v) ═ 5/1] to give 113mg of a pale yellow solid, yield: 45 percent.
MS(ES-API,pos.ion)m/z:406.0[M+H]+；
1H NMR(600MHz,DMSO-d6)δ(ppm):12.14(s,1H),8.77(s,1H),8.40(d,J＝8.4Hz,1H),7.75(d,J＝9.0Hz,1H),7.42–7.35(m,2H),7.33–7.27(m,2H),4.22(q,J＝6.9Hz,2H),2.49(s,3H),2.06(s,3H),1.28(t,J＝6.9Hz,3H)。
The target compounds in table 1 were obtained by a similar synthesis method to that of example 1 using the corresponding materials.
TABLE 1
Figure BDA0001797086400000281
Figure BDA0001797086400000291
Figure BDA0001797086400000301
Figure BDA0001797086400000311
Figure BDA0001797086400000321
Figure BDA0001797086400000331
Figure BDA0001797086400000341
Figure BDA0001797086400000351
Figure BDA0001797086400000361
Figure BDA0001797086400000371
Figure BDA0001797086400000381
Figure BDA0001797086400000391
Figure BDA0001797086400000401
Figure BDA0001797086400000411
Figure BDA0001797086400000421
Figure BDA0001797086400000431
Test example
Test example 1
The herbicidal activity of the compound of the present invention on crowndaisy hemp, crab grass, redroot amaranth, barnyard grass, snakehead gut and green bristlegrass was tested
The test method comprises the following steps: taking a flowerpot with the inner diameter of 6cm, filling composite soil (garden soil: seedling raising matrix is 1:2, v/v) to the position 3/4 of the flowerpot, directly sowing the garland hemp, the crab grass, the redroot amaranth, the barnyard grass, the snakehead and the green bristlegrass (the bud rate is more than or equal to 85 percent), covering 0.2cm of soil, and waiting until weeds grow to about 3-leaf stage for later use. Dissolving each compound with N, N-dimethylformamide according to the dose of 300 g/hectare, diluting with distilled water to prepare a liquid medicine with the concentration of 0.2g/L, applying the liquid medicine by an automatic spray tower, transferring the liquid medicine into a greenhouse for culturing after the liquid medicine on the leaf surfaces of the weeds is dried, and investigating the result after 15 days.
The test results show that: the compound of the invention has good herbicidal activity on crowndaisy hemp, crab grass, redroot amaranth, barnyard grass, snakehead intestine and green bristlegrass.
Test example 2
The compounds of the present invention were tested for their herbicidal activity against abutilon, purslane, cockspur grass, and moleplant seed
The test method comprises the following steps: stem and leaf spraying method: and (3) loading soil in a flowerpot with the length and the width of 7.0cm to 3/4 positions, directly sowing the pretreated weed target seeds, covering soil with the soil for about 1.0cm, and performing spray treatment when the seedlings grow to be of a proper age. After the compounds are applied according to the set dosage, the compounds are transferred to the outdoor for culture, and the activity (%) of weeds is checked 21 days later,
wherein the evaluation standard of the growth inhibition rate of the weeds is as follows:
weed suppression Rate (%) Activity evaluation criteria
≥90％ Class A
80％～90％ Class B
70％～79％ Class C
Less than 70% Class D
The test results show that: under the dosage of 1000g ai/ha, part of the compounds of the invention have good herbicidal activity on Abutilon, purslane, Echinochloa crusgalli and Euphorbia lathyris, such as the activity of example 6, example 8, example 9, example 13, example 15, example 17, example 19, example 22 and example 24 on the crown jute is grade A, and the activity of example 23 on the crown jute is grade B; example 8, example 13, example 15, example 17, example 19, example 20, example 22 and example 23 had a class a activity on purslane and example 6 and example 24 had a class B activity on purslane; the activity against barnyard grass of example 17 and example 19 was grade A, and the activity against barnyard grass of example 8 was grade B; the activity of example 4, example 6, example 8, example 13, example 15, example 17, example 18, example 19, example 20 and example 24 on caper euphorbia seed is class a, and the activity of example 9 on caper euphorbia seed is class B.

Claims (7)

1. A compound which is a compound of formula (I) or a stereoisomer of a compound of formula (I) and acceptable salts thereof:
Figure FDA0002448320250000011
wherein:
q is Q1，
Figure FDA0002448320250000012
Wherein R isaIs hydrogen or C1-4An alkyl group;
x is oxygen;
R1is hydrogen;
R2is C6-14An aryl group;
wherein R is2Optionally substituted with 1 or 2 substituents selected from a 1;
R3is hydrogen or C1-4An alkyl group;
w is hydrogen;
wherein each A1 is independently halogenHydroxy, cyano, nitro, C1-4Alkyl, halo C1-4Alkyl radical, C1-4Alkoxy or halo C1-4An alkoxy group;
z is hydrogen;
y is hydrogen.
2. The compound of claim 1, wherein,
q is Q1，
Figure FDA0002448320250000013
Wherein R isaIs hydrogen, -CH3、-CH2CH3、-CH2CH2CH3、-CH(CH3)2、-CH2CH2CH2CH3、-CH2CH(CH3)2or-C (CH)3)3。
3. The compound of claim 1, wherein,
R3is hydrogen, -CH3、-CH2CH3、-CH2CH2CH3、-CH(CH3)2、-CH2CH2CH2CH3、-CH2CH(CH3)2or-C (CH)3)3。
4. The compound of claim 1, wherein,
R2is of the sub-structure:
Figure FDA0002448320250000014
wherein R is2Optionally substituted with 1 or 2 substituents selected from a 1;
wherein each A1 is independently fluorine, chlorine, bromine, iodine, hydroxy, cyano, nitro, -CH3、-CH2CH3、-CH2CH2CH3、-CH(CH3)2、-CH2CH2CH2CH3、-CH2CH(CH3)2、-C(CH3)3、-CH2F、-CHF2、-CF3、-OCH3or-OCF3。
5. A compound having one of the following structures or a stereoisomer thereof, and acceptable salts thereof:
Figure FDA0002448320250000021
Figure FDA0002448320250000031
6. a composition comprising a compound of any one of claims 1-5, further comprising an agriculturally pharmaceutically acceptable surfactant and a carrier.
7. A compound according to any one of claims 1 to 5 or a composition according to claim 6 for use as a herbicide in agriculture.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104395304A (en) * 2012-04-27 2015-03-04 巴斯夫欧洲公司 Substituted n-(tetrazol-5-yl)- and n-(triazol-5-yl)arylcarboxamide compounds and their use as herbicides
CN104557739A (en) * 2013-10-25 2015-04-29 华中师范大学 Triketone compound and preparation method and application thereof
AR107646A1 (en) * 2016-02-18 2018-05-16 Bayer Cropscience Ag QUINAZOLINDION-6-CARBOXAMIDS AND ITS USE AS HERBICIDES

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104395304A (en) * 2012-04-27 2015-03-04 巴斯夫欧洲公司 Substituted n-(tetrazol-5-yl)- and n-(triazol-5-yl)arylcarboxamide compounds and their use as herbicides
CN104557739A (en) * 2013-10-25 2015-04-29 华中师范大学 Triketone compound and preparation method and application thereof
AR107646A1 (en) * 2016-02-18 2018-05-16 Bayer Cropscience Ag QUINAZOLINDION-6-CARBOXAMIDS AND ITS USE AS HERBICIDES

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