CN114957217A - Compound containing 2-trifluoromethyl picolinamide structure, preparation method and application thereof, herbicide and application thereof - Google Patents

Compound containing 2-trifluoromethyl picolinamide structure, preparation method and application thereof, herbicide and application thereof Download PDF

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CN114957217A
CN114957217A CN202210657410.8A CN202210657410A CN114957217A CN 114957217 A CN114957217 A CN 114957217A CN 202210657410 A CN202210657410 A CN 202210657410A CN 114957217 A CN114957217 A CN 114957217A
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compound
substituted
alkyl
formula
halogen
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蔡卓梅
陈利军
杨光富
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Wuhan Zhihui Nongyao Technology Co.,Ltd.
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Central China Normal University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a 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
    • 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
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • A01N47/36—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the group >N—CO—N< directly attached to at least one heterocyclic ring; Thio analogues thereof
    • 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
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • A01N47/38—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the group >N—CO—N< where at least one nitrogen atom is part of a heterocyclic ring; Thio analogues thereof
    • 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
    • A01N51/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds having the sequences of atoms O—N—S, X—O—S, N—N—S, O—N—N or O-halogen, regardless of the number of bonds each atom has and with no atom of these sequences forming part of a heterocyclic ring
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P13/00—Herbicides; Algicides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
    • 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
    • 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
    • C07D413/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing three or more hetero rings

Abstract

The invention relates to the field of new pesticide compounds, and discloses a compound containing a 2-trifluoromethyl picolinamide structure, a preparation method and application thereof, a herbicide and application thereof. The compound containing the 2-trifluoromethyl pyridine amide structure provided by the invention has excellent herbicidal activity and obviously excellent safety to crops.

Description

Compound containing 2-trifluoromethyl picolinamide structure, preparation method and application thereof, herbicide and application thereof
Technical Field
The invention relates to the field of new pesticide compounds, in particular to a compound containing a 2-trifluoromethyl picolinamide structure, a preparation method and application thereof, and a herbicide and application thereof.
Background
The generation of farmland weeds threatens the yield of crops, and also seriously reduces the quality of global grain crops, thereby causing huge economic loss.
However, compared with an artificial weeding mode, the farmland chemical weeding mode has the advantages of higher efficiency, labor saving and the like, and becomes an important measure which is most depended on by farmers at present.
With the rapid development of chemical weeding in farmland, relatively limited chemical herbicides are used in large quantities for a long time, the problem of global drug-resistant weeds is highlighted, and the rapid occurrence and development of the drug-resistant weeds cause the harm of the farmland weeds to be aggravated and the difficulty in preventing and removing the weeds to be increased.
The grain yield is influenced by various factors such as natural conditions, the grain consumption is further aggravated by the continuous increase of the global population, people are forced to rapidly develop agricultural production technology and perfect farming modes, and new herbicidal compounds and compositions are required to be developed to treat reinforced weeds and improve the grain yield.
Disclosure of Invention
The invention aims to provide a herbicide compound which has a novel structure and excellent herbicidal activity.
In order to achieve the above object, a first aspect of the present invention provides a compound having a 2-trifluoromethylpicolinamide structure, the compound having a structure represented by formula (I):
Figure BDA0003688726440000011
wherein, in the formula (I),
q is a group represented by the formula (Q1) or the formula (Q2); in the formula (Q1), R 1 Is selected from C 1-6 Alkyl groups of (a); in the formula (Q2), R 2 Selected from H and C 1-6 Alkyl groups of (a);
x is absent, or X is selected from S, O, imino、C 1-6 Alkyl-substituted imino of (A), C 3-6 Cycloalkyl-substituted imino, sulfonyl, sulfoxido of (a);
r is selected from halogen, substituted or unsubstituted C 1-12 Alkyl, substituted or unsubstituted phenyl, C 3-12 Substituted or unsubstituted pyrazolyl, substituted or unsubstituted pyrazolonyl, -CONR 1 R 2 、-COR 3 、-SO 2 R 4 ；R 1 And R 2 Each independently selected from H, C 1-6 Or R is 1 And R 2 Are cyclized together to form a 3-8 membered ring with or without an O atom; r 3 And R 4 Each independently selected from C 1-6 Alkyl of (C) 1-6 Alkyl-substituted phenyl of (1), C 1-6 Alkyl-substituted amino of (a);
the optional substituents on R are selected from halogen and C 1-6 Alkyl, halogen substituted C 1-6 Alkyl of (C) 1-6 Alkoxy group of (C) 1-6 Alkyl-substituted phenyl, phenoxy, C 1-6 Alkyl-substituted phenoxy, halogen-substituted phenoxy, amino, -CONH 2 、C 3-6 A cycloalkyl group of (a).
A second aspect of the present invention provides a process for preparing a compound containing a 2-trifluoromethylpicolinamide structure as defined in the first aspect, which process comprises: carrying out a first contact reaction on a compound shown in a formula (II), a condensing agent and a compound shown in a formula (III) in the presence of a solvent;
optionally, the method further comprises: carrying out a second contact reaction on the product obtained after the first contact reaction and a raw material capable of providing a group shown by R-X-;
Figure BDA0003688726440000021
wherein, in formula (II), formula (III) and the starting material capable of providing a group represented by R-X-, the definition of each substituent corresponds to the same as that described in the first aspect.
A third aspect of the present invention provides the use of a compound as described in the first aspect as a herbicide for the control of weeds.
In a fourth aspect, the present invention provides a herbicide comprising a herbicidally effective amount of an active ingredient which is at least one of the compounds set forth in the first aspect.
A fifth aspect of the invention provides the use of a compound of the first aspect or a herbicide of the fourth aspect for controlling weeds in a field planted with a crop selected from any one of peanut, soybean, cotton, wheat, rice and corn.
The compound containing the 2-trifluoromethyl pyridine amide structure provided by the invention has excellent herbicidal activity and obviously excellent safety to crops.
Specifically, the compound containing a 2-trifluoromethylpicolinamide structure according to the present invention has a significant inhibitory effect on weeds including broadleaf weeds, grassy weeds and cyperaceae weeds, and is highly safe to crops.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
Interpretation of terms
“C 1 -C 12 The "alkyl group" of (a) represents an alkyl group having 1 to 12 carbon atoms, and includes a straight-chain alkyl group, a branched-chain alkyl group, and may be, for example, a straight-chain alkyl group having 1,2, 3,4, 5, 6, 7, 8, 9, 10, 11 or 12 carbon atoms in total, a branched-chain alkyl group, and may be, for example, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a tert-butyl group, a n-pentyl group, an isopentyl group, a n-hexyl group, and the like. And, if "C 1 -C 12 With a substitution other than alkylWhen it is a group, the number of carbon atoms of the substituent(s) present therein is not counted as "C 1 -C 12 The carbon number of the alkyl group of (1); for example, when "C 12 When a methoxy group is present as a substituent on "alkyl group of (1), a methoxy-substituted C 12 The total number of carbon atoms of the alkyl group of (2) is 13. For "C 1 -C 6 Alkyl of (2), "" C 1 -C 3 The same applies to the alkyl group "and the like, except that the number of carbon atoms is different.
"halogen" means fluorine, chlorine, bromine, iodine.
“C 1-6 The "alkoxy group" of (b) represents an alkoxy group having 1 to 6 carbon atoms, and includes a linear alkoxy group and a branched alkoxy group, and examples thereof include linear alkoxy groups and branched alkoxy groups having 1,2, 3,4, 5 and 6 carbon atoms in total, and examples thereof include a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, a n-butoxy group, an isobutoxy group, a tert-butoxy group, a n-pentoxy group, an isopentoxy group and a n-hexoxy group.
"imino" is a group represented by-NH-, wherein the N atom is attached to the parent nuclear structure.
“C 3-12 The "cycloalkyl group" of (2) represents a cycloalkyl group having 3 to 12 ring carbon atoms, and may be, for example, a cyclopropyl group, methylcyclopropyl group, ethylcyclopropyl group, cyclopentyl group, methylcyclopentyl group, cyclohexyl group or the like. "C 3-6 The same applies to the cycloalkyl group "and the like, except that the number of carbon atoms is different.
“C 1-6 The alkyl-substituted imino group of (a) is-NR 0 -a group of formula (I) wherein the N atom is attached to the parent structure, R 0 Is C 1-6 Alkyl group of (1). "C 3-6 With a similar interpretation except that R is 0 Is C 3-6 A cycloalkyl group of (a).
The "substituent optionally present on R" means that the substituent may be present or absent, and when polysubstitution is possible, polysubstitution may be achieved at a position that can be substituted, the kind of the substituent in the case of polysubstitution is not particularly required, and may be the same kind of substituent or a different kind of substituent, and the substituent optionally present on R may be bonded to the parent structure through an arbitrary position that can form a bond.
"substituted or unsubstituted pyrazolyl" means that the group provided by the pyrazole can be attached to the parent nuclear structure through any position capable of forming a bond.
"substituted or unsubstituted pyrazolonyl" means that the group provided by the pyrazolone can be attached to the parent nucleus structure via any position capable of forming a bond.
As previously mentioned, a first aspect of the present invention provides a compound comprising a 2-trifluoromethylpicolinamide structure having the structure shown in formula (I):
Figure BDA0003688726440000031
wherein, in the formula (I),
q is a group represented by the formula (Q1) or the formula (Q2); in the formula (Q1), R 1 Is selected from C 1-6 Alkyl groups of (a); in the formula (Q2), R 2 Selected from H and C 1-6 Alkyl groups of (a);
x is absent, or X is selected from S, O, imino, C 1-6 Alkyl-substituted imino of (A), C 3-6 Cycloalkyl-substituted imino, sulfonyl, sulfoxido of (a);
r is selected from halogen, substituted or unsubstituted C 1-12 Alkyl, substituted or unsubstituted phenyl, C 3-12 Substituted or unsubstituted pyrazolyl, substituted or unsubstituted pyrazolonyl, -CONR 1 R 2 、-COR 3 、-SO 2 R 4 ；R 1 And R 2 Each independently selected from H, C 1-6 Or R is 1 And R 2 Together form a 3-8 membered ring with or without an O atom; r 3 And R 4 Each independently selected from C 1-6 Alkyl of (C) 1-6 Alkyl-substituted phenyl of (1), C 1-6 Alkyl-substituted amino of (a);
the optional substituents on R are selected from halogen and C 1-6 Alkyl, halogen substituted C 1-6 Alkyl of (C) 1-6 Alkoxy group of (C) 1-6 Alkyl-substituted phenyl, phenoxy, C 1-6 Alkyl-substituted phenoxy, halogen-substituted phenoxy, amino, -CONH 2 、C 3-6 A cycloalkyl group of (a).
Preferably, in formula (I), Q is a group represented by formula (Q1) or formula (Q2); in the formula (Q1), R 1 Is selected from C 1-3 More preferably R 1 Is methyl; in the formula (Q2), R 2 Selected from H and C 1-3 More preferably R 2 Is methyl.
Preferably, in formula (I), X is absent or is selected from S, O, imino, C 1-3 Alkyl-substituted imino of (A), C 3-6 Cycloalkyl-substituted imino, sulfonyl, sulfoxido of (a); more preferably, X is absent or selected from S, O, imino, C 1-3 Alkyl-substituted imino of (A), C 3 Cycloalkyl-substituted imino, sulfone, sulfoxide groups of (a).
Preferably, in formula (I), R is selected from halogen, substituted or unsubstituted C 1-10 Alkyl, substituted or unsubstituted phenyl, C 3-10 Substituted or unsubstituted pyrazolyl, substituted or unsubstituted pyrazolonyl, -CONR 1 R 2 、-COR 3 、-SO 2 R 4 ；R 1 And R 2 Each independently selected from H, C 1-6 Or R is 1 And R 2 Together form a 3-6 membered ring with or without an O atom; r 3 And R 4 Each independently selected from C 1-6 Alkyl of (C) 1-4 Alkyl-substituted phenyl of (1), C 1-4 Alkyl-substituted amino of (a); more preferably, R is selected from halogen, substituted or unsubstituted C 1-10 Alkyl, substituted or unsubstituted phenyl, C 3-8 Substituted or unsubstituted pyrazolyl, substituted or unsubstituted pyrazolonyl, -CONR 1 R 2 、-COR 3 、-SO 2 R 4 ；R 1 And R 2 Each independently selected from H, C 1-6 Or R is 1 And R 2 Together with or without a proO3-6 membered ring of the subgroup; r 3 And R 4 Each independently selected from C 1-6 Alkyl of (C) 1-4 Alkyl-substituted phenyl of (1), C 1-4 Alkyl-substituted amino group of (1).
Preferably, in formula (I), the substituents optionally present on R are selected from halogen, C 1-6 Alkyl, halogen substituted C 1-6 Alkyl of (C) 1-6 Alkoxy group of (C) 1-6 Alkyl-substituted phenyl, phenoxy, C 1-6 Alkyl-substituted phenoxy, halogen-substituted phenoxy, amino, -CONH 2 、C 3-6 A cycloalkyl group of (a).
According to a preferred embodiment, in formula (I),
q is a group represented by the formula (Q1) or the formula (Q2); in the formula (Q1), R 1 Is selected from C 1-3 Alkyl groups of (a); in the formula (Q2), R 2 Selected from H and C 1-3 Alkyl groups of (a);
x is absent, or X is selected from S, O, imino, C 1-3 Alkyl-substituted imino of (A), C 3-6 Cycloalkyl-substituted imino, sulfonyl, sulfoxido of (a);
r is selected from halogen, substituted or unsubstituted C 1-10 Alkyl, substituted or unsubstituted phenyl, C 3-10 Substituted or unsubstituted pyrazolyl, substituted or unsubstituted pyrazolonyl, -CONR 1 R 2 、-COR 3 、-SO 2 R 4 ；R 1 And R 2 Each independently selected from H, C 1-6 Or R is 1 And R 2 Are cyclized together to form a 3-6 membered ring with or without an O atom; r 3 And R 4 Each independently selected from C 1-6 Alkyl of (C) 1-4 Alkyl-substituted phenyl of (1), C 1-4 Alkyl-substituted amino of (a);
the optional substituents on R are selected from halogen and C 1-6 Alkyl, halogen substituted C 1-6 Alkyl of (C) 1-6 Alkoxy group of (C) 1-6 Alkyl-substituted phenyl, phenoxy, C 1-6 Alkyl-substituted phenoxy, halogen-substituted phenoxy, amino, -CONH 2 、C 3-6 A cycloalkyl group of (a).
According to another preferred embodiment, in formula (I),
q is a group represented by the formula (Q1) or the formula (Q2); in the formula (Q1), R 1 Is methyl; in the formula (Q2), R 2 Is methyl;
x is absent, or X is selected from S, O, imino, C 1-3 Alkyl-substituted imino of (A), C 3 Cycloalkyl-substituted imino, sulfonyl, sulfoxido of (a);
r is selected from halogen, substituted or unsubstituted C 1-10 Alkyl, substituted or unsubstituted phenyl, C 3-8 Substituted or unsubstituted pyrazolyl, substituted or unsubstituted pyrazolonyl, -CONR 1 R 2 、-COR 3 、-SO 2 R 4 ；R 1 And R 2 Each independently selected from H, C 1-6 Or R is 1 And R 2 Together form a 3-6 membered ring with or without an O atom; r 3 And R 4 Each independently selected from C 1-6 Alkyl of (C) 1-4 Alkyl-substituted phenyl of (1), C 1-4 Alkyl-substituted amino of (a);
the optional substituents on R are selected from halogen and C 1-6 Alkyl, halogen substituted C 1-6 Alkyl of (C) 1-6 Alkoxy group of (C) 1-6 Alkyl-substituted phenyl, phenoxy, C 1-6 Alkyl-substituted phenoxy, halogen-substituted phenoxy, amino, -CONH 2 、C 3-6 A cycloalkyl group of (a).
According to a particularly preferred embodiment, the compound of formula (I) is any one of compound 1 to compound 104:
compound 1:
Figure BDA0003688726440000051
compound 2:
Figure BDA0003688726440000052
compound 3:
Figure BDA0003688726440000053
compound 4:
Figure BDA0003688726440000054
compound 5:
Figure BDA0003688726440000061
compound 6:
Figure BDA0003688726440000062
compound 7:
Figure BDA0003688726440000063
compound 8:
Figure BDA0003688726440000064
compound 9:
Figure BDA0003688726440000065
compound 10:
Figure BDA0003688726440000066
compound 11:
Figure BDA0003688726440000067
compound 12:
Figure BDA0003688726440000068
compound 13:
Figure BDA0003688726440000069
compound 14:
Figure BDA00036887264400000610
compound 15:
Figure BDA00036887264400000611
compound 16:
Figure BDA00036887264400000612
compound 17:
Figure BDA00036887264400000613
compound 18:
Figure BDA00036887264400000614
compound 19:
Figure BDA00036887264400000615
compound 20:
Figure BDA00036887264400000616
compound 21:
Figure BDA00036887264400000617
compound 22:
Figure BDA00036887264400000618
compound 23:
Figure BDA0003688726440000071
compound 24:
Figure BDA0003688726440000072
compound 25:
Figure BDA0003688726440000073
compound 26:
Figure BDA0003688726440000074
compound 27:
Figure BDA0003688726440000075
compound 28:
Figure BDA0003688726440000076
compound 29:
Figure BDA0003688726440000077
compound 30:
Figure BDA0003688726440000078
compound 31:
Figure BDA0003688726440000079
compound 32:
Figure BDA00036887264400000710
compound 33:
Figure BDA00036887264400000711
compound 34:
Figure BDA00036887264400000712
compound 35:
Figure BDA00036887264400000713
compound 36:
Figure BDA00036887264400000714
compound 37:
Figure BDA00036887264400000715
compound 38:
Figure BDA00036887264400000716
compound 39:
Figure BDA00036887264400000717
compound 40:
Figure BDA00036887264400000718
compound 41:
Figure BDA0003688726440000081
compound 42:
Figure BDA0003688726440000082
compound 43:
Figure BDA0003688726440000083
compound 44:
Figure BDA0003688726440000084
compound 45:
Figure BDA0003688726440000085
compound 46:
Figure BDA0003688726440000086
compound 47:
Figure BDA0003688726440000087
compound 48:
Figure BDA0003688726440000088
compound 49:
Figure BDA0003688726440000089
compound 50:
Figure BDA00036887264400000810
compound 51:
Figure BDA00036887264400000811
compound 52:
Figure BDA00036887264400000812
compound 53:
Figure BDA00036887264400000813
compound 54:
Figure BDA00036887264400000814
compound 55:
Figure BDA00036887264400000815
compound 56:
Figure BDA00036887264400000816
compound 57:
Figure BDA00036887264400000817
compound 58:
Figure BDA00036887264400000818
compound 59:
Figure BDA0003688726440000091
compound 60:
Figure BDA0003688726440000092
compound 61:
Figure BDA0003688726440000093
compound 62:
Figure BDA0003688726440000094
compound 63:
Figure BDA0003688726440000095
compound 64:
Figure BDA0003688726440000096
compound 65:
Figure BDA0003688726440000097
compound 66:
Figure BDA0003688726440000098
compound 67:
Figure BDA0003688726440000099
compound 68:
Figure BDA00036887264400000910
compound 69:
Figure BDA00036887264400000911
compound 70:
Figure BDA00036887264400000912
compound 71:
Figure BDA00036887264400000913
compound 72:
Figure BDA00036887264400000914
compound 73:
Figure BDA00036887264400000915
compound 74:
Figure BDA00036887264400000916
compound 75:
Figure BDA00036887264400000917
compound 76:
Figure BDA00036887264400000918
compound 77:
Figure BDA0003688726440000101
compound 78:
Figure BDA0003688726440000102
compound 79:
Figure BDA0003688726440000103
compound 80:
Figure BDA0003688726440000104
compound 81:
Figure BDA0003688726440000105
compound 82:
Figure BDA0003688726440000106
compound 83:
Figure BDA0003688726440000107
compound 84:
Figure BDA0003688726440000108
compound 85:
Figure BDA0003688726440000109
compound 86:
Figure BDA00036887264400001010
compound 87:
Figure BDA00036887264400001011
compound 88:
Figure BDA00036887264400001012
compound 89:
Figure BDA00036887264400001013
compound 90:
Figure BDA00036887264400001014
compound 91:
Figure BDA00036887264400001015
compound 92:
Figure BDA00036887264400001016
compound 93:
Figure BDA0003688726440000111
compound 94:
Figure BDA0003688726440000112
compound 95:
Figure BDA0003688726440000113
compound 96:
Figure BDA0003688726440000114
compound 97:
Figure BDA0003688726440000115
compound 98:
Figure BDA0003688726440000116
compound 99:
Figure BDA0003688726440000117
compound 100:
Figure BDA0003688726440000118
compound 101:
Figure BDA0003688726440000119
compound 102:
Figure BDA00036887264400001110
compound 103:
Figure BDA00036887264400001111
compound 104:
Figure BDA00036887264400001112
the present invention does not require any particular method for preparing the compounds of the first aspect, and a person skilled in the art can determine a suitable synthetic route to obtain the compounds of the first aspect of the invention based on the structural formulae provided herein in combination with knowledge known in the art of organic synthesis. However, in order to achieve significantly higher yields and purities, the present invention provides a preferred process as described in the second aspect for preparing the compounds as described in the first aspect of the invention.
As previously mentioned, a second aspect of the present invention provides a process for preparing a compound containing a 2-trifluoromethylpicolinamide structure as defined in the first aspect, which process comprises: carrying out a first contact reaction on a compound shown in a formula (II), a condensing agent and a compound shown in a formula (III) in the presence of a solvent;
optionally, the method further comprises: carrying out a second contact reaction on the product obtained after the first contact reaction and a raw material capable of providing a group shown by R-X-;
Figure BDA0003688726440000121
wherein, in formula (II), formula (III) and the starting material capable of providing a group represented by R-X-, the definition of each substituent corresponds to the same as that described in the first aspect.
Preferably, the conditions of the contacting include: the reaction temperature is 20-100 ℃; the reaction time is 2-8 h.
Preferably, the solvent is at least one selected from the group consisting of dichloromethane, chloroform, dichloroethane, acetonitrile, toluene, tetrahydrofuran and benzene.
The invention has no special requirements on the proportional relation of the dosage of the raw materials, and a person skilled in the art can determine the appropriate proportional relation of the dosage according to the reaction characteristics in the field of organic synthesis and the characteristics of the reaction formula.
Preferably, the condensing agent is selected from DCC (dicyclohexylcarbodiimide), DIC (1, 3-diisopropylcarbodiimide), EDCI (1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride), CDI (N, N' -carbonyldiimidazole), at least one of HATU (O- (7-azabenzotriazol-1-yl) -N, N, N ', N' -tetramethyluronium hexafluorophosphate), HBTU (O- (benzotriazol-1-yl) -N, N, N ', N' -tetramethyluronium hexafluorophosphate), TBTU (2- (1H-benzotriazol-L-1-yl) -1,1,3, 3-tetramethyluronium tetrafluoroborate), PyBOP (1H-benzotriazol-1-yloxytripyrrolidinyl hexafluorophosphate).
Preferably, the first contact reaction may also be carried out in the presence of a basic substance selected from at least one of pyridine, triethylamine, DMAP (4-dimethylaminopyridine), DIPEA (N, N-diisopropylethylamine), DBU (1, 8-diazabicyclo [5.4.0] undec-7-ene), sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide.
In addition, the synthesis method according to the second aspect of the present invention may further include conventional post-treatments, such as filtration, solvent removal, drying, column chromatography, etc., which are well known to those skilled in the art, and the present invention is not described herein in detail, and those skilled in the art should not be construed as limiting the present invention.
It should be noted that, according to the present invention, the types of X and R groups defined in the compound having a 2-trifluoromethylpicolinamide structure are different, and the second contact reaction described in the second aspect of the present invention may be optionally followed by further reactions to obtain the target compound, and those skilled in the art can determine a suitable synthetic route according to the structural features of the target compound in combination with the examples provided in the following of the present invention, which are not repeated herein, and those skilled in the art should not be construed as limiting the present invention.
As mentioned above, a third aspect of the present invention provides the use of a compound as described in the first aspect as a herbicide for the control of weeds.
Preferably, the weeds are selected from at least one of broadleaf weeds, grass weeds and sedge weeds.
Preferably, the weeds are selected from at least one of descurainia sophia, shepherd's purse, chenopodium album, galium aparine, speedwell, caraway, acalypha australis, nightshade, peruvian, purslane, amaranthus retroflexus, carp intestines, barnyard grass, goosegrass, setaria viridis, crabgrass, alopecurus, jiegeng, avena avenae, bromus, moleplant seed, paspalum distichum, japanese iris lactuca and cyperus heterophyllus.
As mentioned above, a fourth aspect of the present invention provides a herbicide comprising a herbicidally effective amount of an active ingredient which is at least one of the compounds described in the first aspect.
Preferably, the active ingredient is present in the herbicide in an amount of 1 to 100 wt%, for example, 5 wt%, 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, 45 wt%, 50 wt%, 55 wt%, 60 wt%, 65 wt%, 70 wt%, 75 wt%, 80 wt%, 85 wt%, 90 wt%, 95 wt%, etc.
Preferably, the herbicide also contains auxiliary materials.
The invention has no special requirement on the types of the auxiliary materials, and the skilled in the art can select the types of the auxiliary materials according to the dosage form by combining the known application in the field of pesticides.
As mentioned above, a fifth aspect of the present invention provides the use of a compound as described in the first aspect or a herbicide as described in the fourth aspect for controlling weeds in a field planted with any one crop selected from peanut, soybean, cotton, wheat, rice and corn.
The present invention will be described in detail below by way of examples. In the following examples, the starting materials used are all common analytical grade commercial products unless otherwise specified.
Unless otherwise specified, the room temperature or the ambient temperature referred to in the following examples each represents 25. + -. 2 ℃.
Preparation example 1: preparation of Compound 1
Figure BDA0003688726440000131
2- (trifluoromethyl) nicotinic acid (0.26mol) and potassium carbonate (0.52mol) were put in a 1L eggplant-shaped bottle, and DMF (500ml) as a solvent was added thereto under stirring, followed by stirring at room temperature for 20min, methyl iodide (0.29mol) was slowly added dropwise to the reaction system, and further stirring was continued at room temperature for about 2 hours. And (3) detecting the reaction by TLC, after the reaction is finished, pouring the reaction solution into 1.2L of ice water under the stirring condition, extracting by ethyl acetate for three times, collecting an organic phase, washing the organic phase twice by saturated salt solution, drying by anhydrous sodium sulfate, filtering, collecting filtrate, and distilling under reduced pressure to remove the solvent to obtain colorless oily liquid 2- (trifluoromethyl) methyl nicotinate. The yield thereof was found to be 94%.
Adding 2- (trifluoromethyl) methyl nicotinate (0.24mol) and dichloromethane (200mL) into a 500mL eggplant-shaped bottle, adding carbamide peroxide (0.37mol) under stirring, stirring for 45min at room temperature, dropwise adding trifluoroacetic anhydride (0.37mol), continuing stirring overnight, removing the solvent by reduced pressure distillation after the reaction is finished, washing the obtained solid with petroleum ether, and performing suction filtration to obtain a white solid, namely 3- (methoxycarbonyl) -2- (trifluoromethyl) pyridine 1-oxide. The yield thereof was found to be 76%.
To a 500mL round bottom flask, 3- (methoxycarbonyl) -2- (trifluoromethyl) pyridine 1-oxide (0.18mol) and 1, 2-dichloroethane (200mL) were added and the mixture was stirred until the solid was completely dissolved. Adding phosphorus oxychloride (0.36mol) and diisopropylethylamine (0.18mol) into a system, stirring overnight at 60 ℃, supplementing phosphorus oxychloride (0.18mol) and diisopropylethylamine (0.90mmol) into the system, continuously stirring for 12 hours at 60 ℃, after the reaction is finished, pouring a reaction solution into ice water, adjusting the pH value of a water phase to 7, extracting dichloromethane for three times, purifying the reaction by column chromatography, and removing a solvent by reduced pressure distillation to obtain a solid, namely 6-chloro-2- (trifluoromethyl) methyl nicotinate. The yield thereof was found to be 72%.
To a 100mL eggplant-shaped bottle, the compound methyl 6-chloro-2- (trifluoromethyl) nicotinate (7.20mmol), lithium hydroxide monohydrate (18.00mmol), methanol as a solvent, and 20mL of water were added in this order, and the mixture was stirred at room temperature for 5 hours. After the reaction is completed, removing methanol in the system by reduced pressure distillation, adjusting the pH to 2 by 1mol/L hydrochloric acid, separating out white solid, and performing suction filtration to collect the solid, namely 6-chloro-2- (trifluoromethyl) nicotinic acid. The yield thereof was found to be 92%.
To a 100mL eggplant-shaped bottle, the compound 6-chloro-2- (trifluoromethyl) nicotinic acid (0.98mmol), N, N' -carbonyldiimidazole (1.08mmol) and 20mL of acetonitrile as a solvent were added in this order, and the mixture was stirred at 80 ℃ for 2 hours. After the reaction was completed, 1-methyl-5-aminotetrazole (1.18mmol) and 1, 8-diazabicyclo [5.4.0] undec-7-ene (1.47mmol) were added to the system and stirring was continued for 4 h. After the reaction is completed again, removing the solvent by reduced pressure distillation, dissolving residues by dichloromethane, washing the solution by 1mol/L hydrochloric acid, retaining an organic phase, continuously extracting a water phase by dichloromethane, combining the organic phases, drying, performing suction filtration to collect filtrate, performing reduced pressure distillation, removing the solvent, performing column chromatography to perform primary purification on the reaction, and performing recrystallization by methanol and diethyl ether to obtain a white solid, namely 6-chloro-N- (1-methyl-1H-tetrazol-5-yl) -2- (trifluoromethyl) nicotinamide with the yield of 86%.
Preparation example 2: preparation of Compound 2
Figure BDA0003688726440000141
To a 100mL eggplant-shaped bottle were added the intermediate 6-chloro-2- (trifluoromethyl) nicotinic acid (0.98mmol), N, N' -carbonyldiimidazole (1.08mmol) and acetonitrile (15mL) in this order, and the mixture was stirred at 80 ℃ for 2 hours. After the reaction was complete, 2-amino-5-methyl-1, 3, 4-oxadiazole (1.18mmol) and 1, 8-diazabicyclo [5.4.0] undec-7-ene (1.47mmol) were added and stirring continued at 80 ℃ for 4 h. After the reaction is finished, removing the reaction solvent by reduced pressure distillation, dissolving residues by dichloromethane, washing the solution by 1mol/L hydrochloric acid, retaining an organic phase, extracting a water phase by dichloromethane, combining the organic phases, drying, performing suction filtration to collect filtrate, removing the solvent by reduced pressure distillation, performing column chromatography to perform preliminary purification on the reaction, performing reduced pressure distillation to obtain a crude product, and further recrystallizing and purifying the crude product by methanol and ether to obtain a white solid, namely 6-chloro-N- (5-methyl-1, 3, 4-oxadiazole-2-yl) -2- (trifluoromethyl) nicotinamide, wherein the yield is 86%.
Preparation example 3: preparation of Compound 3
Figure BDA0003688726440000151
Adding 6-chloro-N- (1-methyl-1H-tetrazol-5-yl) -2- (trifluoromethyl) nicotinamide (8.00mmo), sodium methyl mercaptide (12.00mmol) and DMF (20mL) in sequence into a 100mL eggplant-shaped bottle, stirring at room temperature for 4H, after the reaction is finished, pouring the reaction liquid into 80mL ice water under stirring, extracting with ethyl acetate (3X 10mL), collecting an organic phase, washing the organic phase with saturated saline, drying, carrying out suction filtration, carrying out reduced pressure distillation, and carrying out column chromatography to obtain a white solid, namely N- (1-methyl-1H-tetrazol-5-yl) -6- (methylthio) -2- (trifluoromethyl) nicotinamide.
Preparation example 4: preparation of Compound 5
Figure BDA0003688726440000152
The compound N- (1-methyl-1H-tetrazol-5-yl) -6- (methylthio) -2- (trifluoromethyl) nicotinamide (2.00mmol), m-chloroperoxybenzoic acid (2.20mmol) and the solvent dichloromethane (20mL) were added in this order to a 100mL eggplant-shaped flask and stirred at room temperature for 2 hours. After the reaction is finished, the solvent is removed by reduced pressure distillation, and white solid, namely N- (1-methyl-1H-tetrazole-5-yl) -6- (methylthio) -2- (trifluoromethyl) nicotinamide, is obtained by column chromatography.
Preparation example 5: preparation of Compound 7
Figure BDA0003688726440000153
To a 50mL eggplant-shaped bottle were added N- (1-methyl-1H-tetrazol-5-yl) -6- (methylthio) -2- (trifluoromethyl) nicotinamide (0.90mmol), m-chloroperoxybenzoic acid (2.25mmol) and 20mL of dichloromethane as a solvent in this order, and the mixture was stirred at room temperature for 5 hours. After the reaction is finished, the solvent is removed by reduced pressure distillation and column chromatography to obtain a white solid, namely N- (1-methyl-1H-tetrazole-5-yl) -6- (methylsulfonyl) -2- (trifluoromethyl) nicotinamide.
Preparation example 6: preparation of Compound 33
Figure BDA0003688726440000154
To a 100mL eggplant-shaped bottle were added 6-chloro-N- (1-methyl-1H-tetrazol-5-yl) -2- (trifluoromethyl) nicotinamide (2.00mmol), o-cresol (4.00mmol), sodium hydroxide (4.00mmol) and 15mL of N, N-dimethylformamide in that order. Stirring for 4H at room temperature, after the reaction is finished, pouring the reaction solution into 60mL of ice water under stirring, extracting with ethyl acetate, collecting an organic phase, washing the organic phase with saturated salt water twice, drying with anhydrous sodium sulfate, and carrying out column chromatography to obtain a white solid, namely N- (1-methyl-1H-tetrazole-5-yl) -6- (o-tolyloxy) -2- (trifluoromethyl) nicotinamide.
Preparation example 7: preparation of Compound 53
Figure BDA0003688726440000161
Adding 6-chloro-N- (1-methyl-1H-tetrazol-5-yl) -2- (trifluoromethyl) nicotinamide (2.00mmol), propylamine (4.00mmol), potassium carbonate (4.00mmol) and tetrahydrofuran solution (15mL) in sequence into a 35mL closed glass tube, sealing the reaction tube, stirring overnight at 100 ℃, adding 15mL of water into the system after the reaction is finished, extracting with ethyl acetate, drying, carrying out suction filtration, collecting filtrate, and carrying out column chromatography to obtain a white solid, namely N- (1-methyl-1H-tetrazol-5-yl) -6- (propylamino) -2- (trifluoromethyl) nicotinamide.
N- (1-methyl-1H-tetrazol-5-yl) -6- (propylamino) -2- (trifluoromethyl) nicotinamide (1.80mmol) and potassium carbonate (3.6mmol) were placed in a jar, and DMF (20ml) was added as a solvent under stirring, and after stirring at room temperature for 20min, methyl iodide (2.00mmol) was slowly dropped onto the reaction system, and stirring was continued at room temperature for about 2H. And (3) detecting the reaction by TLC, after the reaction is finished, pouring the reaction solution into 80mL of ice water under the stirring condition, extracting by ethyl acetate for three times, collecting an organic phase, washing the organic phase by saturated salt solution twice, drying by anhydrous sodium sulfate, and carrying out column chromatography to obtain a white solid, namely 6- (methyl (propyl) amino) -N- (1-methyl-1H-tetrazole-5-yl) -2- (trifluoromethyl) nicotinamide.
Preparation example 8: preparation of Compound 71
Figure BDA0003688726440000162
Adding 6-chloro-N- (1-methyl-1H-tetrazol-5-yl) -2- (trifluoromethyl) nicotinamide (2.00mmol), methylamine hydrochloride (4.00mmol), potassium carbonate (4.00mmol) and tetrahydrofuran solution (15mL) in sequence into a 35mL closed glass tube, sealing the reaction tube, stirring overnight at 100 ℃, adding 15mL of water into the system after the reaction is finished, extracting with ethyl acetate, drying, carrying out suction filtration, collecting filtrate, and carrying out column chromatography to obtain a white solid, namely N- (1-methyl-1H-tetrazol-5-yl) -6- (methylamino) -2- (trifluoromethyl) nicotinamide.
N- (1-methyl-1H-tetrazol-5-yl) -6- (methylamino) -2- (trifluoromethyl) nicotinamide (1.9mmol) and ultra-dry tetrahydrofuran (20mL) were added to a 100mL eggplant-shaped flask, followed by vigorous stirring in an ice-water bath, addition of sodium hydride (3.8mmol) in portions, stirring for 30min, and addition of dimethylcarbamoyl chloride (2.8mmol) to the system. Stirring for 4H at room temperature, after the reaction is finished, slowly pouring the reaction liquid into 60mL of ice water, extracting with ethyl acetate, collecting an organic phase, drying, filtering, collecting a filtrate, distilling under reduced pressure, removing a solvent, and carrying out column chromatography to obtain white solid N- (1-methyl-1H-tetrazole-5-yl) -2- (trifluoromethyl) -6- (1,3, 3-trimethylureido) nicotinamide.
Preparation example 9: preparation of Compound 91
Figure BDA0003688726440000171
Adding 6-chloro-N- (1-methyl-1H-tetrazol-5-yl) -2- (trifluoromethyl) nicotinamide (2.00mmol), hydrazine hydrate (5.00mmol) and a solvent dioxane (50mL) into a 35mL closed glass tube in sequence, stirring for 4H at 60 ℃, extracting with ethyl acetate after the reaction is finished, washing with organic phase saturated sodium bicarbonate, washing with saturated salt water, drying, performing suction filtration to collect filtrate, and removing the solvent to obtain a solid, namely 6-hydrazino-N- (1-methyl-1H-tetrazol-5-yl) -2- (trifluoromethyl) nicotinamide.
To a 100mL eggplant-shaped bottle was added 6-hydrazino-N- (1-methyl-1H-tetrazol-5-yl) -2- (trifluoromethyl) nicotinamide (1.8mmol) and 1,1, 1-trifluoro-2, 4-pentanedione (1.9mmol), ethanol was used as a solvent, and to the system was added 1 drop of 10M hydrochloric acid, refluxed overnight, cooled and recrystallized to give N- (1-methyl-1H-tetrazol-5-yl) -6- (5-methyl-3- (trifluoromethyl) -1H-pyrazol-1-yl) -2- (trifluoromethyl) nicotinamide as a white solid.
Referring to the above preparation examples, the characterization data of some compounds of the present invention are shown in table 1, and the yield in table 1 is the yield of the last step of the reaction.
TABLE 1
Figure BDA0003688726440000172
Figure BDA0003688726440000181
Figure BDA0003688726440000191
Figure BDA0003688726440000201
Figure BDA0003688726440000211
Figure BDA0003688726440000221
Figure BDA0003688726440000231
Figure BDA0003688726440000241
Figure BDA0003688726440000251
Test example 1
This test example is intended to illustrate the herbicidal activity (expressed as growth inhibition (%)) of the compounds of the present invention.
Herbicidal activity test (potting method): the test targets are cockspur grass, green bristlegrass, crab grass, amaranth, chenopodium album and piemarker, and the post-emergence stem and leaf spraying: taking a paper cup with the inner diameter of 7cm, filling composite soil (vegetable garden soil: seedling culture medium, 1:2, v/v) to 3/4 positions, directly sowing weeds, covering soil of 0.2cm, and waiting until the leaf growing period reaches 4-5 for later use. After the compound of the invention and the aforementioned comparative compound are applied in an automatic spraying tower according to the dosage of 150g.ai/ha (g/ha), the crop leaf liquor is air-dried and then transferred into a greenhouse for culture (25 ℃, humidity 70%), and the result is investigated after 30 days.
The growth inhibition rate evaluation method is a visual method, specifically, the evaluation is performed according to the conditions shown in table 2, and the test results are shown in table 3.
TABLE 2
Figure BDA0003688726440000261
TABLE 3
Figure BDA0003688726440000262
Figure BDA0003688726440000271
From the above results, it can be seen that the compounds of the present invention have good herbicidal activity against 6 common gramineous and broadleaf weeds of Echinochloa crusgalli, Setaria viridis, crab grass, amaranth, Chenopodium quinoa and Abutilon in herbicidal activity test experiments.
In particular, some of the compounds of the present invention exhibited 100% herbicidal control against the 6 weeds tested at a rate of 150g ai/ha. Therefore, the compound has strong development and commercialization prospects.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.

Claims (10)

1. A compound having a 2-trifluoromethylpicolinamide structure, wherein the compound has a structure represented by formula (I):
Figure FDA0003688726430000011
wherein, in the formula (I),
q is a group represented by the formula (Q1) or the formula (Q2); in the formula (Q1), R 1 Is selected from C 1-6 Alkyl groups of (a); in the formula (Q2), R 2 Selected from H and C 1-6 Alkyl groups of (a);
x is absent, or X is selected from S, O, imino, C 1-6 Alkyl-substituted imino of (A), C 3-6 Cycloalkyl-substituted imino, sulfonyl, sulfoxido of (a);
r is selected from halogen, substituted or unsubstituted C 1-12 Alkyl, substituted or unsubstituted phenyl, C 3-12 Substituted or unsubstituted pyrazolyl, substituted or unsubstituted pyrazolonyl, -CONR 1 R 2 、-COR 3 、-SO 2 R 4 ；R 1 And R 2 Each independently selected from H, C 1-6 Or R is 1 And R 2 Together form a 3-8 membered ring with or without an O atom; r 3 And R 4 Each independently selected from C 1-6 Alkyl of (C) 1-6 Alkyl-substituted phenyl of (1), C 1-6 Alkyl-substituted amino of (a);
the optional substituents on R are selected from halogen and C 1-6 Alkyl, halogen substituted C 1-6 Alkyl of (C) 1-6 Alkoxy group of (C) 1-6 Alkyl-substituted phenyl, phenoxy, C 1-6 Alkyl-substituted phenoxy, halogen-substituted phenoxy, amino, -CONH 2 、C 3-6 A cycloalkyl group of (a).
2. The compound according to claim 1, wherein, in formula (I),
q is a group represented by the formula (Q1) or the formula (Q2); in the formula (Q1), R 1 Is selected from C 1-3 Alkyl groups of (a); in the formula (Q2), R 2 Selected from H and C 1-3 Alkyl groups of (a);
x is absent, or X is selected from S, O, imino, C 1-3 Alkyl-substituted imino of (A), C 3-6 Cycloalkyl-substituted imino, sulfonyl, sulfoxido of (a);
r is selected from halogen, substituted or unsubstituted C 1-10 Alkyl, substituted or unsubstituted phenyl, C 3-10 Substituted or unsubstituted pyrazolyl, substituted or unsubstituted pyrazolonyl, -CONR 1 R 2 、-COR 3 、-SO 2 R 4 ；R 1 And R 2 Each independently selected from H, C 1-6 Or R is 1 And R 2 Together form a 3-6 membered ring with or without an O atom; r 3 And R 4 Each independently selected from C 1-6 Alkyl of (C) 1-4 Alkyl-substituted phenyl of (1), C 1-4 Alkyl-substituted amino of (a);
the optional substituents on R are selected from halogen and C 1-6 Alkyl, halogen substituted C 1-6 Alkyl of (C) 1-6 Alkoxy group of (C) 1-6 Alkyl-substituted phenyl, phenoxy, C 1-6 Alkyl-substituted phenoxy, halogen-substituted phenoxy, amino, -CONH 2 、C 3-6 A cycloalkyl group of (a).
3. The compound according to claim 2, wherein, in formula (I),
q is a group represented by the formula (Q1) or the formula (Q2); in the formula (Q1), R 1 Is methyl; in the formula (Q2), R 2 Is methyl;
x is absent, or X is selected from S, O, imino, C 1-3 Alkyl-substituted imino of (A), C 3 Cycloalkyl-substituted imino, sulfonyl, sulfoxido of (a);
r is selected from halogen, substituted or unsubstituted C 1-10 Alkyl, substituted or unsubstituted phenyl, C 3-8 Substituted or unsubstituted pyrazolyl, substituted or unsubstituted pyrazolonyl, -CONR 1 R 2 、-COR 3 、-SO 2 R 4 ；R 1 And R 2 Each independently selected from H, C 1-6 Or R is 1 And R 2 Are cyclized together to form a 3-6 membered ring with or without an O atom; r 3 And R 4 Each independently selected from C 1-6 Alkyl of (C) 1-4 Alkyl-substituted phenyl of (1), C 1-4 Alkyl-substituted amino of (a);
the optional substituents on R are selected from halogen, C 1-6 Alkyl, halogen substituted C 1-6 Alkyl of (C) 1-6 Alkoxy group of (C) 1-6 Alkyl-substituted phenyl, phenoxy, C 1-6 Alkyl-substituted phenoxy, halogen-substituted phenoxy, amino, -CONH 2 、C 3-6 A cycloalkyl group of (a).
4. The compound according to any one of claims 1 to 3, wherein the compound represented by formula (I) is any one of compound 1 to compound 104:
compound 1:
Figure FDA0003688726430000031
chemical combinationAn object 2:
Figure FDA0003688726430000032
compound 3:
Figure FDA0003688726430000033
compound 4:
Figure FDA0003688726430000034
compound 5:
Figure FDA0003688726430000035
compound 6:
Figure FDA0003688726430000036
compound 7:
Figure FDA0003688726430000037
compound 8:
Figure FDA0003688726430000038
compound 9:
Figure FDA0003688726430000039
compound 10:
Figure FDA00036887264300000310
compound 11:
Figure FDA00036887264300000311
compound 12:
Figure FDA00036887264300000312
compound 13:
Figure FDA00036887264300000313
compound 14:
Figure FDA00036887264300000314
compound 15:
Figure FDA00036887264300000315
compound 16:
Figure FDA00036887264300000316
compound 17:
Figure FDA00036887264300000317
compound 18:
Figure FDA00036887264300000318
compound 19:
Figure FDA0003688726430000041
compound 20:
Figure FDA0003688726430000042
compound 21:
Figure FDA0003688726430000043
compound 22:
Figure FDA0003688726430000044
compound 23:
Figure FDA0003688726430000045
compound 24:
Figure FDA0003688726430000046
compound 25:
Figure FDA0003688726430000047
compound 26:
Figure FDA0003688726430000048
compound 27:
Figure FDA0003688726430000049
compound 28:
Figure FDA00036887264300000410
compound 29:
Figure FDA00036887264300000411
compound 30:
Figure FDA00036887264300000412
compound 31:
Figure FDA00036887264300000413
compound 32:
Figure FDA00036887264300000414
compound 33:
Figure FDA00036887264300000415
compound 34:
Figure FDA00036887264300000416
compound 35:
Figure FDA00036887264300000417
compound 36:
Figure FDA00036887264300000418
compound 37:
Figure FDA00036887264300000419
compound 38:
Figure FDA00036887264300000420
compound 39:
Figure FDA0003688726430000051
compound 40:
Figure FDA0003688726430000052
compound 41:
Figure FDA0003688726430000053
compound 42:
Figure FDA0003688726430000054
compound 43:
Figure FDA0003688726430000055
compound 44:
Figure FDA0003688726430000056
compound 45:
Figure FDA0003688726430000057
compound 46:
Figure FDA0003688726430000058
compound 47:
Figure FDA0003688726430000059
compound 48:
Figure FDA00036887264300000510
compound 49:
Figure FDA00036887264300000511
compound 50:
Figure FDA00036887264300000512
compound 51:
Figure FDA00036887264300000513
compound 52:
Figure FDA00036887264300000514
compound 53:
Figure FDA00036887264300000515
compound 54:
Figure FDA00036887264300000516
compound 55:
Figure FDA00036887264300000517
compound 56:
Figure FDA00036887264300000518
compound 57:
Figure FDA00036887264300000519
compound 58:
Figure FDA00036887264300000520
compound 59:
Figure FDA0003688726430000061
compound 60:
Figure FDA0003688726430000062
compound 61:
Figure FDA0003688726430000063
compound 62:
Figure FDA0003688726430000064
compound 63:
Figure FDA0003688726430000065
compound 64:
Figure FDA0003688726430000066
compound 65:
Figure FDA0003688726430000067
compound 66:
Figure FDA0003688726430000068
compound 67:
Figure FDA0003688726430000069
compound 68:
Figure FDA00036887264300000610
compound 69:
Figure FDA00036887264300000611
compound 70:
Figure FDA00036887264300000612
compound 71:
Figure FDA00036887264300000613
compound 72:
Figure FDA00036887264300000614
compound 73:
Figure FDA00036887264300000615
compound 74:
Figure FDA00036887264300000616
compound 75:
Figure FDA00036887264300000617
compound 76:
Figure FDA00036887264300000618
compound 77:
Figure FDA0003688726430000071
compound 78:
Figure FDA0003688726430000072
compound 79:
Figure FDA0003688726430000073
compound 80:
Figure FDA0003688726430000074
compound 81:
Figure FDA0003688726430000075
compound 82:
Figure FDA0003688726430000076
compound 83:
Figure FDA0003688726430000077
compound 84:
Figure FDA0003688726430000078
compound 85:
Figure FDA0003688726430000079
compound 86:
Figure FDA00036887264300000710
compound 87:
Figure FDA00036887264300000711
compound 88:
Figure FDA00036887264300000712
compound 89:
Figure FDA00036887264300000713
compound 90:
Figure FDA00036887264300000714
compound 91:
Figure FDA00036887264300000715
compound 92:
Figure FDA00036887264300000716
compound 93:
Figure FDA0003688726430000081
compound 94:
Figure FDA0003688726430000082
compound 95:
Figure FDA0003688726430000083
compound 96:
Figure FDA0003688726430000084
compound 97:
Figure FDA0003688726430000085
compound 98:
Figure FDA0003688726430000086
compound 99:
Figure FDA0003688726430000087
compound 100:
Figure FDA0003688726430000088
compound 101:
Figure FDA0003688726430000089
compound 102:
Figure FDA00036887264300000810
compound 103:
Figure FDA00036887264300000811
compound 104:
Figure FDA00036887264300000812
5. a process for preparing a compound containing a 2-trifluoromethylpicolinamide structure according to any one of claims 1 to 4, which comprises: carrying out a first contact reaction on a compound shown in a formula (II), a condensing agent and a compound shown in a formula (III) in the presence of a solvent;
optionally, the method further comprises: carrying out a second contact reaction on the product obtained after the first contact reaction and a raw material capable of providing a group shown by R-X-;
Figure FDA0003688726430000091
wherein, in the formula (II), the formula (III) and the raw material capable of providing the group represented by R-X-, the definition of each substituent corresponds to the same as that described in any one of claims 1 to 4.
6. The method of claim 5, wherein the conditions of the contacting comprise: the reaction temperature is 20-100 ℃; the reaction time is 2-8 h; and/or
The solvent is at least one selected from dichloromethane, trichloromethane, dichloroethane, acetonitrile, toluene, tetrahydrofuran and benzene.
7. Use of a compound according to any one of claims 1 to 4 as a herbicide for controlling weeds.
8. Use according to claim 7, wherein the weeds are selected from at least one of broadleaf weeds, grassy weeds and sedge weeds; and/or
The weeds are selected from at least one of descurainia sophia, shepherd's purse, chenopodium quinoa, abutilon, speedwell, sika-bar, acalypha australis, black nightshade, peruvian groundcherry, purslane, redroot amaranth, carp intestine, barnyard grass, eleusine indica, setaria viridis, digitaria sanguinea, alopecurus japonicus, jiejia, wild oat, bromus, moleplant seed, paspalum distichum, iris lactea and cyperus heterophyllus.
9. A herbicide, comprising a herbicidally effective amount of an active ingredient which is at least one compound of any one of claims 1 to 4.
10. Use of a compound according to any one of claims 1 to 4 or a herbicide according to claim 9 for controlling weeds in a field planted with any one crop selected from peanut, soybean, cotton, wheat, rice and corn.
CN202210657410.8A 2022-06-10 2022-06-10 Compound containing 2-trifluoromethyl picolinamide structure, preparation method and application thereof, herbicide and application thereof Pending CN114957217A (en)

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