阅读说明：本技术 苯甲酰胺化合物及其作为除草剂的用途 (Benzamide compounds and their use as herbicides ) 是由 M·科德斯 T·齐克 T·塞茨 R·L·尼尔森 于 2018-11-28 设计创作，主要内容包括：本发明涉及式(I)的苯甲酰胺化合物、它们的N-氧化物及其盐,以及包含它们的组合物。本发明还涉及所述苯甲酰胺化合物或包含此类化合物的组合物用于控制不希望的植物的用途。此外,本发明涉及应用此类化合物的方法。在式(I)中,变量具有以下含义：R<Sup>1</Sup>是Cl或CH<Sub>3</Sub>；R<Sup>2</Sup>选自卤素、CF<Sub>3</Sub>、S-CH<Sub>3</Sub>、S(O)-CH<Sub>3</Sub>和S(O)<Sub>2</Sub>-CH<Sub>3</Sub>；R<Sup>3</Sup>选自C<Sub>1</Sub>-C<Sub>6</Sub>-烷基、C<Sub>1</Sub>-C<Sub>6</Sub>-卤代烷基和C<Sub>3</Sub>-C<Sub>10</Sub>-环烷基-Z-,其中Z是共价键或CH<Sub>2</Sub>。<Image he="233" wi="700" file="DDA0002515130680000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>(The present invention relates to benzamide compounds of formula (I), their N-oxides and salts thereof, and compositions comprising them. The invention also relates to the use of said benzamide compounds or compositions comprising such compounds for controlling undesired vegetation. Furthermore, the invention relates to methods of using such compounds. In formula (I), the variables have the following meanings: r 1 Is Cl or CH 3 ；R 2 Selected from halogen, CF 3 、S‑CH 3 、S(O)‑CH 3 And S (O) 2 ‑CH 3 ；R 3 Is selected from C 1 ‑C 6 Alkyl radical, C 1 ‑C 6 -haloalkyl and C 3 ‑C 10 -cycloalkyl-Z-, wherein Z is a covalent bond or CH 2 。)

1. A compound of the formula I,

wherein

R¹Is Cl or CH₃；

R²Selected from halogen, CF₃、S-CH₃、S(O)-CH₃And S (O)₂-CH₃；

R³Is selected from C₁-C₆Alkyl radical, C₁-C₆-haloalkyl and C₃-C₁₀-cycloalkyl-Z-, wherein Z is a covalent bond or CH₂；

Or an N-oxide or an agriculturally acceptable salt thereof.

2. The compound of claim 1, wherein R²Selected from Br, Cl and CF₃。

3. A compound according to any one of the preceding claims wherein R is³Is selected from C₁-C₆Alkyl radical, C₁-C₃-haloalkyl and C₃-C₆-a cycloalkyl group.

4. The method of claim 3Compound (I) wherein R³Is selected from C₁-C₄-alkyl, fluoro C₁-C₂-alkyl and C₃-C₄-a cycloalkyl group; is especially selected from C₁-C₃-alkyl, CH₂CF₃And a cyclopropyl group.

5. A compound according to any one of the preceding claims wherein R is²Selected from Br, Cl and CF₃(ii) a And R is³Is selected from C₁-C₃-alkyl, CH₂CF₃And a cyclopropyl group.

6. A compound according to any one of claims 1 to 3, wherein R³Is C₁-C₆-an alkyl group.

7. The compound of claim 6, wherein R³Is methyl or ethyl.

8. A compound according to any one of the preceding claims wherein R is¹Is CH₃。

9. The compound of claim 8, wherein R²Is Br.

10. The compound of any one of claims 1 to 7, wherein R¹Is Cl.

11. The compound of claim 10, wherein R²Is Br.

12. The compound of claim 10, wherein R²Is Cl.

13. A compound according to any one of the preceding claims selected from compounds of formula (I), N-oxides and agriculturally acceptable salts thereof, wherein R¹、R²And R³As defined in rows 1 to 72 of table a:

table a:

wherein C-C₃H₅Meaning cyclopropyl.

14. The compound of claim 1 selected from

4-bromo-6-fluoro-2-methyl-N- (1-methyltetrazol-5-yl) -3- [ [ methyl (2,2, 2-trifluoroethyl) carbamoyl ] amino ] benzamide,

4-bromo-6-fluoro-2-methyl-N- (1-methyltetrazol-5-yl) -3- [ [ ethyl (2,2, 2-trifluoroethyl) carbamoyl ] amino ] benzamide,

2, 4-dichloro-6-fluoro-N- (1-methyltetrazol-5-yl) -3- [ [ methyl (2,2, 2-trifluoroethyl) carbamoyl ] amino ] benzamide,

4-bromo-2-chloro-6-fluoro-N- (1-methyltetrazol-5-yl) -3- [ [ ethyl (2,2, 2-trifluoroethyl) carbamoyl ] amino ] benzamide,

n-oxides and agriculturally acceptable salts thereof.

15. A composition comprising at least one compound as claimed in any of claims 1 to 14, an N-oxide or an agriculturally acceptable salt thereof and at least one auxiliary customary for formulating crop protection compounds.

16. A combination of compounds comprising at least one compound as claimed in any of claims 1 to 14, an N-oxide or an agriculturally acceptable salt thereof and at least one further compound selected from herbicidally active compounds and safener compounds.

17. A composition comprising at least one compound as claimed in any of claims 1 to 14, an N-oxide or an agriculturally acceptable salt thereof, at least one further compound selected from herbicidally active compounds and safener compounds, and at least one auxiliary customary for formulating crop protection compounds.

18. Use of a compound as claimed in any of claims 1 to 14, an N-oxide or an agriculturally acceptable salt thereof, a composition of claim 15 or 17 or a combination of claim 16 for controlling undesirable vegetation.

19. A method of controlling undesired vegetation, which comprises allowing a herbicidally effective amount of at least one compound as claimed in any of claims 1 to 14, an N-oxide or an agriculturally acceptable salt thereof or a combination of claim 16 or a composition of claim 15 or 17 to act on plants, their seeds and/or their habitat.

The compounds of the prior art often have the problem of insufficient herbicidal activity, especially at low application rates, and/or unsatisfactory selectivity, resulting in low compatibility with crops.

It was therefore an object of the present invention to provide further benzamide compounds which have a strong herbicidal activity, especially even at low application rates, sufficiently low toxicity to humans and animals and/or high compatibility with crops. These benzamide compounds should also show a broad spectrum of activity against a large number of different undesirable plants.

These and other objects are achieved by the compounds of formula (I) as defined below and their agriculturally useful salts.

Accordingly, a first aspect of the present invention relates to compounds of formula (I),

wherein

R¹Is Cl or CH₃；

R²Selected from halogen, CF₃、S-CH₃、S(O)-CH₃And S (O)₂-CH₃；

R³Is selected from C₁-C₆Alkyl radical, C₁-C₆-haloalkyl and C₃-C₁₀-cycloalkyl-Z-, wherein Z is a covalent bond or CH₂；

N-oxides and agriculturally acceptable salts thereof.

The compounds of the invention, i.e. the compounds of formula (I) and their agriculturally useful salts, can be used, inter alia, for controlling undesirable vegetation. The present invention therefore also relates to the use of compounds of the formula (I) or their agriculturally useful salts or of compositions comprising at least one compound of the formula (I) or its agriculturally useful salt for controlling or controlling undesirable vegetation.

The invention also relates to a composition comprising at least one compound of formula (I) or a salt thereof and at least one auxiliary. The invention relates in particular to agricultural compositions comprising at least one compound of the formula (I) or an agriculturally useful salt thereof and at least one auxiliary which is customary for crop protection formulations.

The present invention also relates to a method for controlling or controlling undesired plants, which comprises allowing a herbicidally effective amount of at least one compound of the formula (I) or a salt thereof to act on the undesired plants, their seeds and/or their habitat.

Dependent on R³The compounds of formula (I) may have one or more chiral centres, in which case they exist as a mixture of enantiomers or diastereomers. By way of example only, if R³Is 1-methylpropyl (sec-butyl), the carbon atom of the propyl group bearing the methyl group is the stereogenic center. The present invention provides both the pure enantiomers or pure diastereomers of the compounds of formula (I) and mixtures thereof as well as the inventive use of the pure enantiomers or pure diastereomers of the compounds of formula (I) or mixtures thereof. Suitable compounds of formula (I) also include all possible geometric stereoisomers (cis/trans isomers) and mixtures thereof. The cis/trans isomer may exist with respect to an alkene, a carbon-nitrogen double bond, a nitrogen-sulfur double bond, or an amide group. The term "stereoisomer" includes both optical isomers, such as enantiomers or diastereomers, wherein the latter occur due to more than one chiral center in the molecule, as well as geometric isomers (cis/trans isomers).

Furthermore, the present invention relates to compounds as defined herein wherein one or more of the atoms shown in formula (I) have been replaced by its stable, preferably non-radioactive isotope (e.g. hydrogen is replaced by deuterium,¹²C quilt¹³C is substituted,¹⁴N quilt¹⁵N is substituted,¹⁶O quilt¹⁸O substitution), especially wherein at least one hydrogen atom has been replaced by a deuterium atom. Of course, the compounds of the invention contain more of the corresponding isotope than is naturally occurring and therefore always present in the compounds of formula (I).

The compounds of the invention may be amorphous or may exist in one or more different crystalline states (polymorphs) which may have different macroscopic properties such as stability or show different biological properties such as activity. The present invention includes both amorphous and crystalline compounds of formula (I), enantiomers or diastereomers thereof, mixtures of different crystalline states of the corresponding compounds of formula (I), enantiomers or diastereomers thereof, and amorphous or crystalline salts thereof.

Salts of the compounds of the present invention are preferably agriculturally acceptable salts. They may be formed in conventional manner, for example by reacting a compound of the invention with an acid if it has a basic functional group, or with a suitable base if it has an acidic functional group.

Useful agriculturally useful salts are in particular those salts of cations or acid addition salts of acids whose cations and anions, respectively, do not have any adverse effect on the herbicidal action of the compounds according to the invention. Suitable cations are especially alkali metal ions, preferably lithium, sodium and potassium ions; alkaline earth metal ions, preferably calcium, magnesium and barium ions; transition metal ions, preferably manganese, copper, zinc and iron ions; also ammonium (NH)₄ ⁺) And wherein 1 to 4 hydrogen atoms are replaced by C₁-C₄Alkyl radical, C₁-C₄Hydroxyalkyl radical, C₁-C₄Alkoxy radical, C₁-C₄alkoxy-C₁-C₄Alkyl, hydroxy-C₁-C₄alkoxy-C₁-C₄Alkyl, phenyl or benzyl substituted ammonium. Examples of substituted ammonium ions include methylammonium, isopropylammonium, dimethylammonium, diisopropylammonium, trimethylammonium, tetramethylammonium, tetraethylammonium, tetrabutylammonium, 2-hydroxyethylammonium, 2- (2-hydroxyethoxy) ethylammonium, di (2-hydroxyethyl) ammonium, benzyltrimethylammonium and benzyl-triethylammonium, and furthermoreIon, sulfonium ion, preferably tris (C)₁-C₄Alkyl) sulfonium, and sulfoxonium ions, preferably tri (C)₁-C₄Alkyl) sulfoxonium.

The anions of the useful acid addition salts are predominantly chloride, bromide, fluoride, hydrogen sulfate, dihydrogen phosphate, hydrogen phosphate, nitrate, hydrogen carbonate, hexafluorosilicate, hexafluorophosphate, benzoate and C₁-C₄The anion of an alkanoic acid, preferably formate, acetate, propionate and butyrate. They may be formed by reacting a compound of the invention with an acid of the corresponding anion, preferably hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid or nitric acid.

N-oxides of the compounds I in which the nitrogen atom, for example the ring nitrogen atom of the tetrazole ring, is in oxidized form, i.e. as the radical N⁺-O^-The compounds present. N-oxides are generally prepared by oxidation of compounds of formula I, for example with hydrogen peroxide or peroxy acids such as m-chloroperoxybenzoic acid (mCPBA), peroxyacetic acid or peroxymonosulfuric acid (peroxymonosulfuric acid).

The term "undesirable vegetation" ("weeds") is understood to include any plant that grows in a non-crop area or crop locus or in a sown and other desired crop locus, where the plant is any plant species other than the sown or desired crop (if any), including germinating seeds, emerging seedlings and formed plants thereof. Weeds in the broadest sense are plants that are considered undesirable at a particular location.

The organic moieties mentioned in the above definitions of the variables (like the term halogen) are collective terms for the individual enumeration of the group members. Prefix C_n-C_mIn each case representing the possible number of carbon atoms in the radical.

The term "halogen" denotes in each case fluorine, bromine, chlorine or iodine, especially fluorine, chlorine or bromine.

The term "alkyl" as used herein denotes in each case a straight-chain or branched alkyl (C) radical having in general from 1 to 6 carbon atoms₁-C₆Alkyl), preferably 1 to 4 carbon atoms (C)₁-C₄Alkyl), in particular 1 to 3 carbon atoms (C)₁-C₃Alkyl), in particular 1 or 2 carbon atoms (C)₁-C₂-an alkyl group). C₁-C₂-alkyl is methyl or ethyl. C₁-C₃-alkyl is methyl, ethyl, n-propyl or isopropyl. C₁-C₄Examples of-alkyl are methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl (sec-butyl), isobutyl and tert-butyl. C₁-C₄Examples of alkyl are methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl (sec-butyl), isobutyl and tert-butyl. C₁-C₆Examples of alkyl radicals other than p-C₁-C₄Alkyl group of the above-mentionedIn addition to n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 1-dimethylpropyl, 1, 2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1-dimethylbutyl, 1, 2-dimethylbutyl, 1, 3-dimethylbutyl, 2, 2-dimethylbutyl, 2, 3-dimethylbutyl, 3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1, 2-trimethylpropyl, 1,2, 2-trimethylpropyl, 1-ethyl-1-methylpropyl and 1-ethyl-2-methylpropyl.

The term "haloalkyl" as used herein denotes in each case a straight-chain or branched alkyl radical ("C") usually having from 1 to 6 carbon atoms₁-C₆-haloalkyl "), more typically a linear or branched alkyl (" C ") having 1 to 4 carbon atoms₁-C₄Haloalkyl "), preferably a linear or branched alkyl (" C ") having 1 to 3 carbon atoms₁-C₃Haloalkyl "), in particular a linear or branched alkyl (" C ") having 1 or 2 carbon atoms₁-C₂-haloalkyl "), wherein the hydrogen atoms of the group are partially or fully substituted by halogen atoms. In the present context, the term "partially or fully halogenated" means that 1 or more, for example 1,2,3,4 or 5 or all, of the hydrogen atoms of a given group are replaced by halogen atoms, in particular fluorine or chlorine. Preferred haloalkyl moieties are selected from C₁-C₄-haloalkyl, more preferably selected from C₁-C₃Haloalkyl, especially selected from C₁-C₂Haloalkyl, for example selected from halomethyl. In particular, haloalkyl is fluoroalkyl, i.e. the hydrogen atoms of the group are partially or completely replaced by fluorine atoms. Very particularly, the haloalkyl group is a fluorinated C₁-C₂-an alkyl group. Fluoromethyl is methyl in which 1,2 or 3 hydrogen atoms are replaced by fluorine atoms. Examples are fluoromethyl, difluoromethyl and trifluoromethyl. Halomethyl is methyl in which 1,2 or 3 hydrogen atoms are replaced by halogen atoms. Examples are bromomethyl, chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl and the like. Fluoro C₁-C₂Examples of-alkyl are fluoromethyl,Difluoromethyl, trifluoromethyl, 1-fluoroethyl, 2, 2-difluoroethyl, 2,2, 2-trifluoroethyl, pentafluoroethyl, and the like. C₁-C₂Examples of-haloalkyl radicals other than p-fluoro C₁-C₂And in addition to those mentioned for alkyl, chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-chloroethyl, 2, 2-dichloroethyl, 2,2, 2-trichloroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2, 2-difluoroethyl, 2, 2-dichloro-2-fluoroethyl, 1-bromoethyl and the like. Except for C₁-C₂-haloalkyl radicals other than those described, C₁-C₃Examples of the "haloalkyl" group are also a 1-fluoropropyl group, a 2-fluoropropyl group, a 3, 3-difluoropropyl group, a 3,3, 3-trifluoropropyl group, a pentafluoropropyl group, a 1,1, 1-trifluoroprop-2-yl group, a 3-chloropropyl group and the like. Except for C₁-C₂-haloalkyl radicals other than those described, C₁-C₄Examples of the "haloalkyl" group are also a 1-fluoropropyl group, a 2-fluoropropyl group, a 3, 3-difluoropropyl group, a 3,3, 3-trifluoropropyl group, a pentafluoropropyl group, a 1,1, 1-trifluoropropan-2-yl group, a 3-chloropropyl group, a 4-chlorobutyl group and the like.

The term "cycloalkyl" as used herein denotes in each case generally having from 3 to 10 carbon atoms ("C)₃-C₁₀Cycloalkyl "), preferably 3 to 7 carbon atoms (" C)₃-C₇Cycloalkyl "), in particular 3 to 6 carbon atoms (" C)₃-C₆-cycloalkyl ") or especially 3 or 4 carbon atoms (" C)₃-C₄-cycloalkyl ") groups, and monocyclic or bicyclic saturated alicyclic groups. Monocyclic radicals having 3 or 4 carbon atoms (monocyclic C)₃-C₄-cycloalkyl) include cyclopropyl and cyclobutyl. Monocyclic radicals having 3 to 6 carbon atoms (monocyclic C)₃-C₆-cycloalkyl) includes cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl. Monocyclic radicals having 3 to 7 carbon atoms (monocyclic C)₃-C₇-cycloalkyl) include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cycloheptyl. Monocyclic radicals having 3 to 10 carbon atoms (monocyclic C)₃-C₁₀Cycloalkyl) include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl and cyclodecaneAnd (4) a base. Bicyclic radicals having 7 or 8 carbon atoms (bicyclic C)₇-C₈Cycloalkyl) includes bicyclo [2.1.1]Hexyl, bicyclo [2.2.1]Heptyl, bicyclo [3.1.1]Heptyl, bicyclo [2.2.1]Heptyl, bicyclo [2.2.2]Octyl and bicyclo [3.2.1]And (4) octyl. Preferably, the term cycloalkyl denotes a monocyclic saturated alicyclic group.

The following explanations of preferred embodiments of the variables (substituents) of the compounds of formula (I) are valid both individually and preferably in combination with each other and also in combination with the stereoisomers, salts or N-oxides thereof.

The following description of preferred embodiments of the variables, where applicable, is valid both individually and preferably in combination with one another in the case of the compounds of the formula I and also in the case of the use and the process according to the invention and the compositions according to the invention.

Preferred compounds of the invention are compounds of formula (I) or stereoisomers or salts thereof, wherein the salts are agriculturally acceptable salts. Particularly preferred compounds of the invention are compounds of the formula (I) or salts thereof, especially their agriculturally useful salts.

In preferred compounds of the invention, the radical R in the formula (I)²Selected from halogen and CF₃. More preferably, the group R in formula (I)²Selected from Br, Cl and CF₃。

In a preferred embodiment of the invention, the radical R in the formula (I)³Is selected from C₁-C₆Alkyl radical, C₁-C₄Haloalkyl and Z-C₃-C₆-cycloalkyl, more preferably selected from C₁-C₆Alkyl radical, C₁-C₃-haloalkyl and C₃-C₆Cycloalkyl (i.e. Z is a bond), in particular selected from C₁-C₄-alkyl, fluoro C₁-C₂-alkyl and C₃-C₄Cycloalkyl, in particular selected from methyl, ethyl, n-propyl, isopropyl, 2,2, 2-trifluoroethyl and cyclopropyl.

In another preferred embodiment of the invention, the radical R in the formula (I)³Is C₁-C₆Alkyl, especially C₁-C₄-alkyl, especially methyl or ethyl, more especially methyl.

A first particular group 1 of embodiments relates to compounds according to the invention, wherein R¹Is methyl. In this first group of preferred embodiments, R²And R³As defined above, and in particular has the meaning as given in the expression "in particular", "preferably" or "in particular". In this first group of embodiments, wherein R¹Is methyl, R in the formula (I)²In particular from Br, Cl and CF₃，R³Preferably C₁-C₆Alkyl, especially C₁-C₄-alkyl, in particular methyl or ethyl, very particularly methyl. In this first group of embodiments, wherein R¹Is methyl, R in the formula (I)²Especially Br, and R³Is preferably C₁-C₆Alkyl, especially C₁-C₄-alkyl, in particular methyl or ethyl, and very particularly methyl.