Patent Application
20250206727
The present invention belongs to the technical field of pesticides and particularly relates to a heterocycle-substituted aromatic compound, a preparation method therefor, and a herbicidal composition and an application thereof.
Weed control is one of the most important links in the course of achieving high-efficiency agriculture. Although various herbicides are available in the market, for example, patents WO2012059050A and the like disclose the use of substituted biaryl benzenesulfonamide compounds as herbicides. However, the herbicidal properties against harmful plants and the selectivity to crops of these known compounds are not completely satisfactory. Moreover, due to the continuous expansion of the market, issues such as resistance of weeds, service life and economy of drugs, and the public's increasing attention to the environment, scientists are expected to continuously study and further develop new efficient, safe, and economical herbicide varieties with different modes of action.
The present invention provides a heterocycle-substituted aromatic compound, as well as a preparation method therefor, a herbicidal composition and an application thereof. The compound has excellent herbicidal activity against gramineous weeds, broad-leaf weeds and the like even at a low application rate and has high selectivity to crops.
The technical solution adopted in the present invention is as follows:
A heterocycle-substituted aromatic compound, as shown in the general formula I:
In one specific embodiment, Y represents halogen, halo C1-C8 alkyl, cyano, nitro, or amino.
In another specific embodiment, Y represents halogen, halo C1-C6 alkyl, cyano, nitro, or amino.
In one specific embodiment, R1, R2, R3, R4, and R5 each independently represent hydrogen, halogen, hydroxyl, mercapto, formyl, hydroxyl C1-C8 alkyl, nitro, cyano, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, C3-C8 cycloalkyl C1-C8 alkyl, C3-C8 cycloalkenyl, C3-C8 cycloalkenyl C1-C8 alkyl, —OR11, —SR11, —(SO)R11, —(SO2)R11, —(SO2)OR11, —O(SO2)R11, —N(R12)2, phenyl, or benzyl, wherein,
In another specific embodiment, R1, R2, R3, R4, and R5 each independently represent hydrogen, halogen, hydroxyl, mercapto, formyl, hydroxyl C1-C6 alkyl, nitro, cyano, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl C1-C6 alkyl, C3-C6 cycloalkenyl, C3-C6 cycloalkenyl C1-C6 alkyl, —OR11, —SR11, —(SO)R11, —(SO2)R11, —(SO2)OR11, —O(SO2)R11, —N(R12)2, phenyl, or benzyl, wherein,
In another specific embodiment, R1, R2, R3, R4, and R5 each independently represent hydrogen, halogen, hydroxyl, mercapto, formyl, hydroxyl C1-C6 alkyl, nitro, cyano, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl C1-C3 alkyl, C3-C6 cycloalkenyl, C3-C6 cycloalkenyl C1-C3 alkyl, —OR11, —SR11, —(SO)R11, —(SO2)R11, —(SO2)OR11, —O(SO2)R11, —N(R12)2, phenyl, or benzyl, wherein,
In one specific embodiment, X1 and X2 each independently represent hydrogen, halogen, nitro, cyano, thiocyanato, hydroxyl, mercapto, sulfo, formyl, haloformyl, azido, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, C3-C8 cycloalkyl C1-C8 alkyl, C3-C8 cycloalkenyl, C3-C8 cycloalkenyl C1-C8 alkyl, —PO(OR′)2, —OR″, —(CO)R″, —SR″, —(SO)R″, —(SO2)R″, —Si(R″)3, —O(CO)R″, —O—(SO2)R″, —S(CO)R″, —(SO2)OR″, —O(CO)OR″, —(CO)(CO)OR″,
—CR′═N—OH, —CR′═N—O—R″, heterocyclyl, heterocyclyl C1-C8 alkyl, aryl, aryl C1-C8 alkyl, amino, amino C1-C8 alkyl, aminocarbonyl C1-C8 alkyl, aminocarbonyloxy C1-C8 alkyl, aminothiocarbonyloxy C1-C8 alkyl, aminosulfonyl, or aminosulfonyloxy C1-C8 alkyl, wherein,
In another specific embodiment, X1 and X2 each independently represent hydrogen, halogen, nitro, cyano, thiocyanato, hydroxyl, mercapto, sulfo, formyl, haloformyl, azido, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl C1-C6 alkyl, C3-C6 cycloalkenyl, C3-C6 cycloalkenyl C1-C6 alkyl, —PO(OR′)2, —OR″, —(CO)R″, —SR″, —(SO)R″, —(SO2)R″, —Si(R″)3, —O(CO)R″, —O—(SO2)R″, —S(CO)R″, —(SO2)OR″, —O(CO)OR″, —(CO)(CO)OR″,
—CR′═N—OH, —CR′═N—O—R″, heterocyclyl, heterocyclyl C1-C6 alkyl, aryl, aryl C1-C6 alkyl, amino, amino C1-C6 alkyl, aminocarbonyl C1-C6 alkyl, aminocarbonyloxy C1-C6 alkyl, aminothiocarbonyloxy C1-C6 alkyl, aminosulfonyl, or aminosulfonyloxy C1-C6 alkyl, wherein,
In another specific embodiment, X1 and X2 each independently represent hydrogen, halogen, nitro, cyano, thiocyanato, hydroxyl, mercapto, sulfo, formyl, haloformyl, azido, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-Ce cycloalkyl, C3-C6 cycloalkyl C1-C3 alkyl, C3-Ce cycloalkenyl, C3-C6 cycloalkenyl C1-C3 alkyl, —PO(OR′)2, —OR″, —(CO)R″, —SR″, —(SO)R″, —(SO2)R″, —Si(R″)3, —O(CO)R″, —O—(SO2)R″, —S(CO)R″, —(SO2)OR″, —O(CO)OR″, —(CO)(CO)OR″,
—CR′═N—OH, —CR′═N—O—R″, heterocyclyl, heterocyclyl C1-C3 alkyl, aryl, aryl C1-C3 alkyl, amino, amino C1-C3 alkyl, aminocarbonyl C1-C3 alkyl, aminocarbonyloxy C1-C3 alkyl, aminothiocarbonyloxy C1-C3 alkyl, aminosulfonyl, or aminosulfonyloxy C1-C3 alkyl, wherein, the “C1-C6 alkyl”, “C2-C6 alkenyl”, or “C2-C6 alkynyl” is each independently unsubstituted or substituted by 1, 2, or 3 groups selected from halogen, cyano, hydroxyl, mercapto, carboxyl, —OR″, —(CO)R″, —SR″, —(SO2)R″, —O(CO)H, —O(CO)R″, —O—(SO2)R″, —(CO)OR″, —O(CO)OR″, —O(CO)(CO)OH, —O(CO)(CO)OR″, —O—(C1-C3 alkyl)-(CO)OH, and —O—(C1-C3 alkyl)-(CO)OR″;
In one specific embodiment, W3 each independently represents hydrogen, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, C3-C8 cycloalkenyl, heterocyclyl, aryl,
wherein, the “C1-C8 alkyl”, “C2-C8 alkenyl”, or “C2-C8 alkynyl” is each independently unsubstituted or substituted by at least one group selected from halogen, cyano, nitro, C3-C8 cycloalkyl, tri-C1-C8 alkylsilyl, C3-C8 cycloalkenyl, heterocyclyl, aryl,
the “C3-C8 cycloalkyl”, “tC3-C8 cycloalkenyl”, “heterocyclyl”, or “aryl” is each independently unsubstituted or substituted by at least one group selected from oxo, halogen, cyano, nitro, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, halo C1-C8 alkyl, halo C2-C8 alkenyl, halo C2-C8 alkynyl, halo C3-C8 cycloalkyl, C1-C8 alkyl-substituted C3-C8 cycloalkyl, —OR14, —SR14, —(CO)OR14, —(SO2)R14, —N(R14)2, and —O—(C1-C8 alkyl)-(CO)OR14, or two adjacent carbon atoms on the ring form a fused ring with —OCH2CH2— or —OCH2O— that is unsubstituted or substituted by halogen;
wherein, the “C1-C8 alkyl”, “C2-C8 alkenyl”, or “C2-C8 alkynyl” is each independently unsubstituted or substituted by at least one group selected from halogen, cyano, nitro, C3-C8 cycloalkyl, tri-C1-C8 alkylsilyl, C3-C8 cycloalkenyl, heterocyclyl, aryl,
the “C3-C8 cycloalkyl”, “C3-C8 cycloalkenyl”, “heterocyclyl”, or “aryl” is each independently unsubstituted or substituted by at least one group selected from oxo, halogen, cyano, nitro, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, halo C1-C8 alkyl, halo C2-C8 alkenyl, halo C2-C8 alkynyl, halo C3-C8 cycloalkyl, C1-C8 alkyl-substituted C3-C8 cycloalkyl, —OR14, —SR14, —(CO)OR14, —(SO2)R14, —N(R14)2, and —O—(C1-C8 alkyl)-(CO)OR14, or two adjacent carbon atoms on the ring form a fused ring with —OCH2CH2— or —OCH2O— that is unsubstituted or substituted by halogen;
In another specific embodiment, W3 each independently represents hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 cycloalkenyl, heterocyclyl, aryl,
wherein, the “C1-C6 alkyl”, “C2-C6 alkenyl”, or “C2-C6 alkynyl” is each independently unsubstituted or substituted by 1, 2, or 3 groups selected from halogen, cyano, nitro, C3-C6 cycloalkyl, tri-C1-C6 alkylsilyl, C3-C6 cycloalkenyl, heterocyclyl, aryl,
the “C3-C6 cycloalkyl”, “C3-C6 cycloalkenyl”, “heterocyclyl”, or “aryl” is each independently unsubstituted or substituted by 1, 2, or 3 groups selected from oxo, halogen, cyano, nitro, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, halo C1-C6 alkyl, halo C2-C6 alkenyl, halo C2-C6 alkynyl, halo C3-C6 cycloalkyl, C1-C6 alkyl-substituted C3-C6 cycloalkyl, —OR14, —SR14, —(CO)OR14, —(SO2)R14, —N(R14)2, and —O—(C1-C6 alkyl)-(CO)OR14, or two adjacent carbon atoms on the ring form a fused ring with —OCH2CH2— or —OCH2O— that is unsubstituted or substituted by halogen;
In another specific embodiment, W3 each independently represents hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 cycloalkenyl, heterocyclyl,
wherein, the “C1-C6 alkyl”, “C2-C6 alkenyl”, or “C2-C6 alkynyl” is each independently unsubstituted or substituted by 1, 2, or 3 groups selected from halogen, cyano, nitro, C3-C6 cycloalkyl, tri-C1-C6 alkylsilyl, C3-C6 cycloalkenyl, heterocyclyl, aryl,
the “C3-C6 cycloalkyl”, “C3-C6 cycloalkenyl”, “heterocyclyl”, or “aryl” is each independently unsubstituted or substituted by 1, 2, or 3 groups selected from oxo, halogen, cyano, nitro, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, halo C1-C6 alkyl, halo C2-C6 alkenyl, halo C2-C6 alkynyl, halo C3-Ce cycloalkyl, C1-C6 alkyl-substituted C3-C6 cycloalkyl, —OR14, —SR14, —(CO)OR14, —(SO2)R14, —N(R14)2, and —O—(C1-C3 alkyl)-(CO)OR14, or two adjacent carbon atoms on the ring form a fused ring with —OCH2CH2— or —OCH2O— that is unsubstituted or substituted by halogen;
In one specific embodiment, R11 each independently represents C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, C3-C8 cycloalkyl C1-C8 alkyl, C3-C8 cycloalkenyl, C3-C8 cycloalkenyl C1-C8 alkyl, phenyl, or benzyl, wherein, the “C1-C8 alkyl”, “C2-C8 alkenyl”, or “C2-C8 alkynyl” is each independently unsubstituted or substituted by halogen; the “phenyl” or “benzyl” is each independently unsubstituted or substituted by at least one group selected from halogen, cyano, nitro, C1-C8 alkyl, halo C1-C8 alkyl, C1-C8 alkoxycarbonyl, C1-C8 alkylsulfanyl, C1-C8 alkylsulfonyl, C1-C8 alkoxy, and halo C1-C8 alkoxy;
In one specific embodiment, R11 each independently represents C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl C1-C6 alkyl, C3-C6 cycloalkenyl, C3-C6 cycloalkenyl C1-C6 alkyl, phenyl, or benzyl, wherein, the “C1-C6 alkyl”, “C2-C6 alkenyl”, or “C2-C6 alkynyl” is each independently unsubstituted or substituted by halogen; the “phenyl” or “benzyl” is each independently unsubstituted or substituted by 1, 2, or 3 groups selected from halogen, cyano, nitro, C1-C6 alkyl, halo C1-C6 alkyl, C1-C6 alkoxycarbonyl, C1-C6 alkylsulfanyl, C1-C6 alkylsulfonyl, C1-C6 alkoxy, and halo C1-C6 alkoxy;
In another specific embodiment, R11 each independently represents C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl C1-C3 alkyl, C3-C6 cycloalkenyl, C3-C6 cycloalkenyl C1-C3 alkyl, phenyl, or benzyl, wherein, the “C1-C6 alkyl”, “C2-C6 alkenyl”, or “C2-C6 alkynyl” is each independently unsubstituted or substituted by halogen; the “phenyl” or “benzyl” is each independently unsubstituted or substituted by 1, 2, or 3 groups selected from halogen, cyano, nitro, C1-C6 alkyl, halo C1-C6 alkyl, C1-C6 alkoxycarbonyl, C1-C6 alkylsulfanyl, C1-C6 alkylsulfonyl, C1-C6 alkoxy, and halo C1-C6 alkoxy;
In the definitions of the compounds represented by the above-mentioned general formula and all of the structural formulas hereinafter, the technical terms used, whether used alone or used in compound words, represent the following substituent groups: an alkyl group which has more than two carbon atoms and may be linear or branched. For example, the alkyl in the compound word “-alkyl-(CO)OR11” may be —CH2—, —CH2CH2—, —CH(CH3)—, —C(CH3)2—, etc. An alkyl group is, for example, C1 alkyl: methyl; C2 alkyl: ethyl; C3 alkyl: propyl such as n-propyl or isopropyl; C4 alkyl: butyl such as n-butyl, isobutyl, tert-butyl, or 2-butyl; C5 alkyl: pentyl such as n-pentyl; C6 alkyl: hexyl such as n-hexyl, isohexyl, and 1,3-dimethylbutyl. Similarly, alkenyl is, for example, vinyl, allyl, 1-methylprop-2-en-1-yl, 2-methylprop-2-en-1-yl, but-2-en-1-yl, but-3-en-1-yl, 1-methylbut-3-en-1-yl, and 1-methylbut-2-en-1-yl. Alkynyl is, for example, ethynyl, propargyl, but-2-yn-1-yl, but-3-yn-1-yl, or 1-methylbut-3-yn-1-yl. A multiple bond may be at any position of each unsaturated group. Cycloalkyl is a saturated carbocyclic ring system having for example three to six carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl, or cyclohexyl. Similarly, cycloalkenyl is monocyclic alkenyl having for example three to six carbon ring members such as cyclopropenyl, cyclobutenyl, cyclopentenyl, and cyclohexenyl, wherein a double bond can be at any position. A halogen is fluorine, chlorine, bromine, or iodine.
Unless otherwise specified, the “aryl” of the present invention includes, but is not limited to, phenyl, naphthyl,
the “heterocyclyl” not only includes, but is not limited to, saturated or unsaturated non-aromatic cyclic groups,
etc., but also includes, but is not limited to, heteroaryl, that is an aromatic cyclic group having for example 3 to 6 ring atoms and also optionally fused with a benzo ring. One to four (for example, 1, 2, 3, or 4) heteroatoms of the ring atoms are selected from oxygen, nitrogen, and sulfur, for example
If one group is substituted by a group, this should be understood to mean that the group is substituted by one or more groups, which may be the same or different, selected from the mentioned groups. In addition, the same or different substitution characters contained in the same or different substituent groups are independently selected, which may be the same or different. This is also applicable to a ring system formed by different atoms and units. Meanwhile, the scope of the claims will exclude those compounds chemically unstable under standard conditions which are known to a person skilled in the art.
In addition, unless specifically defined, the term “substituted by at least one group” herein refers to being substituted by, for example, 1, 2, 3, 4, or 5 groups; a group (including heterocyclyl, aryl, etc.) without being specified a linking site may be linked at any position, including a site connected to C or N; if it is substituted, the substituent group may also substitute at any position as long as the valence bond theory is complied with. For example, the heteroaryl
substituted by a methyl may represent
It should be pointed out that when the carbon atom (C*) connected to X1 and X2 in Formula I
is a chiral center (i.e., when X1 and X2 are different), it is in R-configuration or S-configuration.
In the present invention, the stereochemical configuration at the position marked with * in Formula I is determined as the main (R) or (S) according to the Cahn-Ingold-Prelog system. However, the subject matter of the present invention also relates to all stereoisomers at other positions encompassed by Formula I, and mixtures thereof. Such compounds of Formula I contain, for example, one or more additional asymmetric carbon atoms or other double bonds that are not specified in Formula I. It is to be understood that the present invention comprises pure isomers and mixtures thereof of pure isomers enriched to varying degrees, wherein, the asymmetric carbon atom at the position marked with * is in R-configuration or S-configuration; or in the mixture, a compound or a compound of the same chemical structure has R-configuration or S-configuration at the position marked with *, or is present in such a proportion where the compound with R-configuration or S-configuration is predominantly present (at least 60% having R-configuration or S-configuration); meanwhile, other asymmetric carbon atoms may exist in racemic forms or may be resolved to varying degrees. As long as the stereochemical configuration at a position marked with * is eligible, possible stereoisomers defined by particular spatial forms such as enantiomers, diastereoisomers, Z- and E-isomers, are all encompassed by Formula I, and may be obtained from mixtures of stereoisomers using conventional methods, or may be prepared by stereoselective reactions in combination with the use of stereochemically pure starting materials.
The present invention also includes any keto-enol tautomeric form, a mixture and salt thereof, if various functional groups are present.
Stereoisomers are obtainable from the mixtures prepared by optical resolution. Stereoisomers may also be selectively prepared by employing stereoselective reactions and using optically active starting materials and/or auxiliaries. For optical resolution, conventional methods can often be employed (see Textbooks of Stereochemistry), such as those described below for resolving mixtures into diastereoisomers, for example, physical methods, e.g., crystallization, chromatography, particularly column chromatography and high pressure liquid chromatography, distillation methods carried out under reduced pressure as needed, extraction and other methods. Chromatographic separation on a chiral solid phase is usually adopted to separate residual mixtures of enantiomers. Suitable for a preparative amount or for use on an industrial scale are methods such as crystallization of diastereomeric salts, which can be obtained from compounds using optically active acids, and if acidic groups are present, optically active bases can be employed as needed.
A method for preparing the heterocycle-substituted aromatic compounds comprises the following steps:
The compound as shown in the general formula II can be prepared with reference to the methods set forth in WO12130798, WO1404882, WO14048882, WO18228985, WO18228986, WO19034602, WO19145245, etc.
A herbicidal composition comprises a herbicidally effective amount of at least one of the heterocycle-substituted aromatic compounds, preferably, also comprising a formulation auxiliary.
A method for controlling weeds comprises applying a herbicidally effective amount of at least one of the heterocycle-substituted aromatic compounds or the herbicidal composition to a plant or a weedy area.
At least one of the heterocycle-substituted aromatic compounds or the herbicidal composition has use in controlling weeds; preferably, the heterocycle-substituted aromatic compound is used for preventing and controlling weeds among useful crops, and the useful crops are transgenic crops or crops treated by genome editing techniques.
The compounds of Formula I of the present invention have outstanding herbicidal activity against a broad spectrum of monocotyledonous and dicotyledonous harmful plants of economic importance. The active substances of the present invention also act effectively on perennial weeds which grow from root stocks, rhizomes, or other perennial organs and are difficult to control. In this context, it is generally immaterial whether the substances are applied before sowing, before emergence, or after emergence. Representative examples of monocotyledonous and dicotyledonous weed florae which can be controlled by the compound of the present invention may be specifically mentioned, without limiting to certain species.
Examples of weed species on which the active substances act efficiently include the monocotyledons such as annual Avena, Lolium, Alopecurus, Phalaris, Echinochloa, Digitana, Setaria and Cyperus, as well as perennial Agropyron, Cynodon, Imperata and Sorghum, and perennial Cyperus.
In the case of dicotyledonous weed species, the spectrum of action extends to species such as annual Galium, Viola, Veronica, Lamium, Stellaria, Amaranthus, Sinapis, Ipomoea, Sida, Matricaria and Abutilon, as well as perennial weeds Convolvulus, Cirsium, Rumex, and Artemisia. The active substances of the present invention perform outstanding control of harmful plants such as Echinochloa, Sagittaria, Alisma, Eleocharis, Scirpus and Cyperus under the specific condition of paddy rice growing. If the compounds of the present invention are applied to soil surface prior to germination, the weed seedlings are either prevented completely from emerging, or the weeds stop growing when reaching the cotyledon stage and eventually die completely after three to four weeks. In particular, the compounds of the present invention exhibit excellent activity against Apera spica venti, Matsumurella chinense, Fallopia convolvulus, Stellaria media, Veronica hederifolia, Veronica persica, Viola tricolor, Amaranthus, Galium, and Kochia.
Although the compounds of the present invention have excellent herbicidal activity against monocotyledonous and dicotyledonous weeds, there is no damage at all to crop plants of economic importance such as wheat, barley, rye, rice, maize, sugarbeet, cotton and soybean, or the damage is negligible. In particular, the compounds have excellent compatibility with cereals such as wheat, barley, and maize, in particular wheat. Therefore, the compounds of the present invention are highly suitable for selectively controlling undesired plants in plantings for agricultural or ornamental use.
Owing to their herbicidal properties, these active substances may be employed for controlling harmful plants in plantings of genetically engineered plants that are known or to be introduced. Transgenic plants usually have advantageous traits, for example, resistance to certain pesticides, in particular to certain herbicides; resistance to plant diseases or pathogenic microorganisms of plant diseases such as certain insects or microorganisms including fungi, bacteria, or viruses. Other particular traits relate to the following conditions of the product, for example, quantity, quality, storage stability, composition, and special ingredients. Thus, it is known that the obtained transgenic plant product has an increased starch content, or modified starch quality, or a different fatty acid composition.
The compounds of Formula I of the present invention or salts thereof are preferably used in plantings of transgenic crops and ornamental plants of economic importance, for example, cereals such as wheat, barley, rye, oats, millet, rice, manioc, and maize; or in plantings of vegetable plants such as sugarbeet, cotton, soybean, rapeseed, potato, tomato, pea and the like. The compounds of Formula I are preferably used as herbicides in plantings of useful plants which are resistant, or have been made resistant by genetic engineering, against the toxic effects of the herbicides.
Conventional ways for breeding plants which have modified traits compared to known plants include, for example, conventional breeding methods and breeding of mutant strains. In other words, novel plants having improved traits may be generated with the aid of genetic engineering methods (see, e.g., EP-0221044 A, EP-0131624 A). For example, several methods have been described:
Numerous molecular biology techniques which allow the preparation of transgenic plants having modified traits are known (see, e.g., Sambrook et al., 1989, Molecular Cloning, A Laboratory Manual, 2nd edition, Cold Spring Harbor Laboratory Press, Cold Spring Harbor, N.Y.; or Winnacker, “Gene und Kone” [Genes and Clones], VCH Weinheim, 2nd edition, 1996; or Christou, “Trends in Plant Science”, 1 (1996) 423-431). In order to carry out genetic engineering manipulations, it is possible to introduce a nucleic acid molecule into a plasmid, allowing mutagenesis or a sequence change to occur by recombination of the DNA sequence. Using the above-mentioned standard processes, it is possible to, for example, substitute bases, remove partial sequences, or add natural or synthetic sequences. To link DNA fragments with each other, it is possible to attach adaptors or linkers to the fragments.
A plant cell having a gene product of reduced activity may be prepared by the following methods, for example, by expressing at least one appropriate antisense-RNA and sense-RNA to achieve a cosuppression effect, or by expressing at least one appropriately constructed ribozyme which specifically cleaves the transcripts of the above-mentioned gene product.
To this end, it is possible to employ a DNA molecule which comprises all the coding sequences of the gene product including any flanking sequence that may be present and a DNA molecule which comprises only parts of the coding sequences that must be long enough to cause an antisense effect in the cells. It is also possible to use sequences which have a high degree of homology but are not entirely identical to the coding sequences of the gene product.
When nucleic acid molecules are expressed in a plant, the synthesized protein may be localized in any desired compartment of the plant cell. However, to achieve localization in a certain compartment, it is possible, for example, to link the coding region with the DNA sequences to ensure localization in the certain location. Such sequences are known to a person skilled in the art (see, e.g., Braun et al., EMBO J., 11 (1992), 3219-3227; Wolter et al., Proc. Natl. Acad. Sci. USA, 85 (1988), 846-850; Sonnewald et al., Plant J., 1 (1991), 95-106).
The transgenic plant cells can be recombined onto a whole plant using known techniques. A transgenic plant may be of any desired plant species, i.e., a monocotyledonous and dicotyledonous plant. In this manner, it is possible to obtain transgenic plants having modified traits by overexpression, suppression, or inhibition of homologous (=natural) genes or gene sequences, or by expression of heterologous (=foreign) genes or gene sequences.
When using the active substances of the present invention in a transgenic crop, in addition to the inhibitory effect against harmful plants which can be observed in other crops, there are frequently special effects on the corresponding transgenic crop, for example, improving or broadening the spectrum of weeds which can be controlled, modifying the application amount during application, excellent combination of the drug resistance of the preferred transgenic crop and herbicide performance, as well as effects on the growth and the yield of the transgenic crop plant. The present invention therefore also provides use of the compounds as herbicides for controlling harmful plants among transgenic crop plants.
In addition, the compounds of the present invention are able to significantly regulate the growth of a crop plant. These compounds are employed for the targeted control of plant constituents and for facilitating harvesting by engaging in plant metabolism in a regulating manner, for example by provoking desiccation and stunted growth. Furthermore, they are also suitable for regulating and inhibiting undesirable plant growth without destroying the growth of crop plants. Inhibition of plant growth plays a key role in many monocotyledonous and dicotyledonous crops as it can reduce or completely prevent lodging.
The compounds of the present invention may be applied in customary formulations in the form of wettable powders, emulsifiable concentrates, sprayable solutions, dusts, or granules. The present invention therefore also provides herbicidal compositions comprising the compounds of Formula I. The compounds of Formula I may be formulated in numerous ways depending on the prevailing physical parameters in biology and/or chemistry. Examples of suitable formulation options are: wettable powders (WP), water-soluble powders (SP), water-soluble concentrates, emulsifiable concentrates (EC), emulsions such as oil-in-water and water-in-oil emulsions (EW), sprayable solutions, suspension concentrates (SC), oil dispersions (OD), oil- or water-based dispersions, oil-miscible solutions, dust powders (DP), capsule suspensions (CS), seed-dressing compositions, granules for broadcasting and soil application, spray granules, coating granules and adsorption granules, water-dispersible granules (WG), water-soluble granules (SG), ULV (Ultra-low volume) formulations, microcapsules, and waxes. These individual formulation types are known and described in the following literature, for example, Winnacker-Küchler, “Chemische Technologie” [Chemical Technology], Volume 7, C. Hauser Verlag Munich, 4th edition, 1986; Wade van Valkenburg, “Pesticide Formulations”, Marcel Dekker, N.Y., 1973; K. Martens, “Spray Drying” Handbook, 3rd edition, 1979, G. Goodwin Ltd. London.
Necessary formulation auxiliaries such as inert materials, surfactants, solvents and other additives are likewise known and described in the following documents, for example, Watkins, “Handbook of Insecticide Dust Diluents and Carriers”, 2nd edition, Dorland Books, Caldwell N.J.; H. v. Olphen, “An Introduction to Clay Colloid Chemistry”, 2nd edition, J. Wiley & Sons, N.Y.; C. Marsden, “Solvents Guide”, 2nd edition, Interscience, N.Y. 1963; “McCutcheon's Detergents and Emulsifiers Annual”, MC Publ. Corp., Ridgewood N.J.; Sisley and Wood, “Encyclopedia of Surface Active Agents”, Chem. Publ. Co. Inc., N.Y., 1964; Schönfeldt, “Grenzflüchenaktive Äthylenoxidaddkte” [Surface-active ethylene oxide adducts], Wiss. Verlagagesell., Stuttgart, 1976; Winnacker-Küchler, “Chemische Technologie” [Chemical Technology], Volume 7, C. Hauser Verlag Munich, 4th edition, 1986.
Wettable powders are uniformly dispersible in water which contain, in addition to the active substance, a diluent or inert substance, ionic and/or nonionic surfactant (wetting agent, dispersant), for example polyethoxylated alkyl phenol, polyethoxylated fatty alcohol, polyethoxylated fatty amine, fatty alcohol polyglycol ether sulfate, alkane sulfonate, alkylphenyl sulfonate, sodium lignosulfonate, sodium 2,2′-dinaphthylmethane-6,6′-disulfonats, sodium dibutylnaphthalenesulfonate, or sodium methyl oleoyl taurate. To prepare the wettable powders, the herbicidally active substance is finely ground, for example, in a customary apparatus such as hammer mill, fan mill, and air-jet mill, and mixed with formulation auxiliaries simultaneously or sequentially.
Emulsifiable concentrates are prepared by dissolving the active substance in an organic solvent, for example butanol, cyclohexanone, dimethylformamide, xylene or aromatic compounds with relatively high boiling point or hydrocarbons or mixtures of the solvents, with the addition of one or more ionic and/or nonionic surfactants (emulsifiers). Examples of emulsifiers which can be used are calcium alkylarylsulfonates such as calcium dodecylbenzene sulfonate, or nonionic emulsifiers such as fatty acid polyglycol esters, alkylaryl polyglycol ethers, fatty alcohol polyglycol ethers, propylene oxide-ethylene oxide condensation products, alkyl polyethers, sorbitan esters such as sorbitan fatty acid esters, or polyoxyethylene sorbitan esters such as polyoxyethylene sorbitan fatty acid esters.
Dusts are obtained by grinding the active substance with finely-divided solid substances, for example talc, natural clays such as kaolin, bentonite and pyrophyllite, or diatomaceous earth. Water- or oil-based suspensions may be prepared by the following methods, for example, by wet milling using a commercially customary bead mill, with or without the addition of the surfactants mentioned above in the case of another formulation type.
Emulsions such as oil-in-water emulsions (EW) may be prepared by means of stirrers, colloid mills and/or static mixers using aqueous organic solvents and, if desired, the surfactants as mentioned above in the case of another formulation type may be added.
Granules may be prepared by the following methods that either spraying the active substance onto the adsorptive and granulating with inert materials, or concentrating the active substance onto the surface of carriers such as sand and kaolinite and granulating inert materials by means of adhesive binders such polyvinyl alcohol, sodium polyacrylate, or mineral oils. Suitable active substances may also be granulated in the manner which is customary for the preparation of fertilizer granules. If desired, fertilizers may be mixed in. Water-dispersible granules are prepared by customary methods such as spray-drying, fluidized-bed granulation, disk granulation, or mixing using high-speed mixers and extrusion without solid inert materials.
For the preparation methods of granules using disk, fluidized-bed, extruder and spray, see the following processes in, for example, “Spray-Drying Handbook” 3rd edition, 1979, G. Goodwin Ltd., London; J. E. Browning, “Agglomeration”, Chemical and Engineering, 1967, pages 147 ff.; “Perry's Chemical Engineer's Handbook”, 5th edition, McGraw-Hill, New York 1973, pp. 8-57. For further details on the formulation of crop protection products, see, for example G. C. Klingman, “Weed Control as a Science”, John Wiley and Sons Inc., New York, 1961, pages 81-96 and J. D. Freyer, S. A. Evans, “Weed Control Handbook”, 5th edition, Blackwell Scientific Publications, Oxford, 1968, pages 101-103.
An agrochemical formulation generally contains from 0.1 to 99% by weight, in particular from 0.1 to 95%, of the active substance of Formula I. In a wettable powder, the concentration of the active substance is, for example, from about 10 to 99% by weight, and the remainder to 100% by weight consists of customary formulation constituents. In an emulsifiable concentrate, the concentration of the active substance may be from about 1 to 90%, preferably from 5 to 80%, by weight. A dust formulation contains from 1 to 30% by weight of the active substance, preferably from 5 to 20% by weight of the active substance in usual cases, while a sprayable solution contains from about 0.05 to 80%, preferably from 2 to 50%, by weight of the active substance. In the case of water-dispersible granules, the content of the active substance mainly depends on whether the active substance is liquid or solid and on auxiliaries, fillers, etc. that are used during granulation. In water-dispersible granules, the content of the active substance, for example, is between 1 and 95% by weight, preferably between 10 and 80% by weight.
In addition, formulations of the active substances may include tackifiers, wetting agents, dispersants, emulsifiers, penetrants, preservatives, antifreeze agents, solvents, fillers, carriers, colorants, defoamers, evaporation suppressors as well as pH and viscosity modifiers which are usually customary in all cases.
Based on these formulations, it is also possible to produce mixtures with other pesticidally active substances, for example insecticides, acaricides, herbicides and fungicides, and also with safeners, fertilizers and/or plant growth regulators, in a manner of pre-mix or tank mix.
In mixed formulations or tank-mix formulations, suitable active substances which can be mixed with the active substances of the present invention are the known substances described, for example in World Herbicide New Product Technology Handbook, China Agricultural Science and Farming Techniques Press, 2010. 9 and in the literature cited herein. For example, the herbicidally active substances mentioned below may be mixed with the compounds of Formula I (noted that the compounds are either named by the “common name” in accordance with the International Organization for Standardization (ISO) or by the chemical names, accompanied with a customary code number if appropriate): acetochlor, butachlor, alachlor, propisochlor, metolachlor, S-metolachlor, pretilachlor, propachlor, ethachlor, napropamide, napropamide-M, propanil, mefenacet, diphenamid, diflufenican, ethaprochlor, beflubutamid, bromobutide, dimethenamid, dimethenamid-P, etobenzanid, flufenacet, thenylchlor, metazachlor, isoxaben, flamprop-M-methyl, flamprop-M-propyl, allidochlor, pethoxamid, chloranocryl, cypromid, mefluidide, monalide, delachlor, prynachlor, terbuchlor, xylachlor, dimethachlor, cisanilide, trimexachlor, clomeprop, propyzamide, pentanochlor, carbetamide, benzoylprop-ethyl, cyprazole, butenachlor, tebutam, benzipram, quinonamid, dichlofluanid, naproanilide, diethatyl-ethyl, naptalam, flufenacet, EL-177, benzadox, chlorthiamid, chlorophthalimide, isocarbamide, picolinafen, atrazine, simazine, prometryn, cyanatryn, simetryn, ametryn, propazine, dipropetryn, SSH-108, terbutryn, terbuthylazine, triaziflam, cyprazine, proglinazine, trietazine, prometon, simeton, aziprotryne, desmetryn, dimethametryn, procyazine, mesoprazine, sebuthylazine, secbumeton, terbumeton, methoprotryne, cyanatryn, ipazine, chlorazine, atraton, pendimethalin, eglinazine-ethyl, cyanuric acid, indaziflam, chlorsulfuron, metsulfuron-methyl, bensulfuron-methyl, chlorimuron-ethyl, tibenuron-methyl, thifensulfuron-methyl, pyrazosulfuron-ethyl, mesosulfuron, iodosulfuron-methyl sodium, foramsulfuron, cinosulfuron, triasulfuron, sulfometuron methyl, nicosulfuron, ethametsulfuron-methyl, amidosulfuron, ethoxysulfuron, cyclosulfamuron, rimsulfuron, azimsulfuron, flazasulfuron, monosulfuron, monosulfuron-ester, flucarbazone-sodium, flupyrsulfuron-methyl, halosulfuron-methyl, oxasulfuron, imazosulfuron, primisulfuron, propoxycarbazone, prosulfuron, sulfosulfuron, trifloxysulfuron, triflusulfuron-methyl, tritosulfuron, sodium metsulfuron methyl, flucetosulfuron, HNPC-C9908, orthosulfamuron, propyrisulfuron, metazosulfuron, acifluorfen, fomesafen, lactofen, fluoroglycofen, oxyfluorfen, chlomitrofen, acionifen, ethoxyfen-ethyl, bifenox, nitrofluorfen, chlomethoxyfen, fluorodifen, fluoronitrofen, furyloxyfen, nitrofen, TOPE, DMNP, PPG1013, AKH-7088, halosafen, chlortoluron, isoproturon, linuron, diuron, dymron, fluometuron, benzthiazuron, methabenzthiazuron, cumyluron, ethidimuron, isouron, tebuthiuron, buturon, chlorbromuron, methyldymron, phenobenzuron, SK-85, metobromuron, metoxuron, monolinuron, monuron, siduron, fenuron, fluothiuron, neburon, chloroxuron, noruron, isonoruron, cycluron, thiazfluron, tebuthiuron, difenoxuron, parafluron, methylamine tribunil, karbutilate, trimeturon, dimefuron, monisouron, anisuron, methiuron, chloreturon, tetrafluron, phenmedipham, phenmedipham-ethyl, desmedipham, asulam, terbucarb, barban, propham, chlorpropham, rowmate, swep, chlorbufam, carboxazole, chlorprocarb, fenasulam, BCPC, CPPC, carbasulam, butylate, benthiocarb, vemolate, molinate, triallate, dimepiperate, esprocarb, pyributicarb, cycloate, di-allate, EPTC, ethiolate, orbencarb, pebulate, prosulfocarb, tiocarbazil, CDEC, dimexano, isopolinate, methiobencarb, 2,4-D-butyl, MCPA-sodium, 2,4-D-isooctyl, MCPA-isooctyl, 2,4-D-sodium, 2,4-D-dimethylammonium, MCPA-thioethyl, MCPA, dichlorprop, salts of dichlorprop-P, 2,4-DB, mecoprop, salts of mecoprop, MCPB, 2,4,5-T, fenoprop, 2,4,5-TB, MCPA-ammonium, dicamba, erbon, chlorfenac, disul, 2,3,6-TBA, chloramben, methoxy-2,3,6-TBA, diclofop-methyl, fluazifop-butyl, fluazifop-P-butyl, haloxyfop-methyl, haloxyfop-P, quizalofop-ethyl, quizalofop-P-ethyl, fenoxaprop-ethyl, fenoxaprop-P-ethyl, propaquizafop, cyhalofop-butyl, metamifop, clodinafop-propargyl, fenthiaprop-ethyl, chlorazifop-propargyl, poppenate-methyl, trifopsime, isoxapyrfop, paraquat, diquat, oryzalin, ethalfluralin, isopropalin, nitralin, profluralin, prodinamine, benfluralin, fluchloraline, dinitramina, dipropalin, chlomidine, methalpropalin, dinoprop, glyphosate, anilofos, glufosinate ammonium, amiprophos-methyl, sulphosate, piperophos, bialaphos, bensulide, butamifos, fosamine-ammonium, 2,4-DEP, H-9201, DMPA, imazapyr, imazethapyr, imazaquin, imazamox, imazamox-ammonium, imazapic, imazamethabenz-methyl, fluroxypyr, fluroxypyr-isooctyl ester, clopyralid, picloram, trichlopyr, dithiopyr, haloxydine, pyriclor, thiazopyr, fluridone, aminopyralid, diflufenzopyr, triclopyr-butotyl, cliodinate, sethoxydim, clethodim, cycloxydim, alloxydim, profoxydim, butroxydim, tralkoxydim, tepraloxydim, buthidazole, metribuzin, hexazinone, metamitron, ethiozin, ametridione, amibuzin, bromoxynil, bromoxynil octanoate, ioxynil octanoate, ioxynil, dichlobenil, diphenylacetonitrile, pyraclonil, chloroxynil, iodobonil, flumetsulam, florasulam, penoxsulam, metosulam, cloransulam-methyl, diclosulam, pyroxsulam, benzofluor, bispyribac, pyribenzoxim, pyriftalid, pyriminobac-methyl, pyrithiobac-sodium, benzobicylon, mesotrione, sulcotrione, tembotrione, tefuryttrione, bicyclopyrone, ketospiradox, isoxaflutole, isoxachlortole, fenoxasulfone, methiozolin, fluazolate, pyraflufen-ethyl, pyrazolynate, difenzoquat, pyrazoxyfen, benzofenap, nipyraclofen, pyrasulfotole, topramezone, pyroxasulfone, cafenstrole, flupoxam, amitrole, amicarbazone, azafenidin, carfentrazone, sulfentrazone, bencarbazone, benzfendizone, butafenacil, bromacil, isocil, lenacil, terbacil, flupropacil, cinidon-ethyl, flumiclorac, flumioxazin, flumipropyn, MK-129, flumezin, (sodium)pentachlorophenol, dinoseb, dinoterb, dinoterb acetate, dinosam, DNOC, chloronitrophene, medinoterb acetate, dinofenate, oxadiargyl, oxadiazon, pentoxazone, profluazol, fluthiacet-methyl, fentrazamide, flufenpyr-ethyl, pyrazon, brompyrazon, metflurazon, kusakira, dimidazon, oxapyrazon, norflurazon, pyridafol, quinclorac, quinmerac, bentazone, pyridate, oxaziclomefone, benazolin-ethyl, clomazone, cinmethylin, pyribambenz-isopropyl, pyribambenz-propyl, indanofan, sodium chlorate, dalapon, trichloroacetic acid, monochloroacetic acid, hexachloroacetone, flupropanate, cyperquat, bromofenoxim, epronaz, methazole, flurtamone, benfuresate, ethofumesate, tioclorim, chlorthal, fluorochlordone, tavron, acrolein, bentranil, tridiphane, chlorfenprop-methyl, thidiazimin, phenisopham, busoxinone, methoxyphenone, saflufenacil, clacyfos, chloropon, alorac, diethamquat, etnipromid, iprymidam, ipfencarbazone, thiencarbazone-methyl, pyrimisulfan, chlorflurazole, tripropindan, suiglycapin, prosulfalin, cambendichlor, aminocyclopyrachlor, rodethanil, benoxacor, fenclorim, flurazole, fenchlorazole, cloquintocet-mexyl, oxabetrinil, MG191, cyometrinil, DKA-24, mefenpyr-diethyl, furilazole, fluxofenim, isoxadifen-ethyl, dichlormid, halauxifen-methyl, DOW848, UBH-509, D489, LS 82-556, KPP-300, NC-324, NC-330, KH-218, DPX-N8189, SC-0744, DOWCO535, DK-8910, V-53482, PP-600, MBH-001, KIH-9201, ET751, KIH-6127, and KIH-2023.
For use, the commercially available formulations are, if needed, diluted in customary manners, for example diluted with water in the cases of wettable powders, emulsifiable concentrates, dispersions, and water-dispersible granules. For products in the form of dusts, granules for soil application, or solutions for broadcasting and spray, usually no further dilution with inert materials is required prior to use. The required application amount of the compounds of Formula I varies with the external conditions such as temperature, humidity, the nature of the used herbicide and the like. It may have a large variation range, for example, between 0.001 and 1.0 kg a.i./ha, or more active substances, but preferably between 0.005 and 750 g a.i./ha, in particular between 0.005 and 250 g a.i./ha.
The following examples are used to illustrate the present invention and should not be construed as limiting the present invention in any way. The scope of rights claimed by the present invention is described in the Claims.
In view of the economy and diversity of the compounds, some compounds were preferably synthesized. Among the many synthesized compounds, selected ones are listed in Table 1 below. The specific compound structures and corresponding compound information are as set forth in Tables 1-2. The compounds in Table 1 are only to better illustrate the present invention but do not limit the present invention. For a person skilled in the art, it should not be understood that the scope of the above-mentioned subject matters of the present invention is limited to the following compounds.
1H NMR of Compounds
1H NMR
1H NMR (300 MHz, Chloroform-d) δ 8.89 (s, 1H), 8.09 (s, 1H), 7.97 (d, J = 7.2 Hz, 1H), 7.41 (d, J = 9.3 Hz, 1H), 1.95 (s,
1H NMR (300 MHz, Chloroform-d) δ 8.87 (s, 1H), 8.08 (s, 1H), 7.95 (d, J = 7.2 Hz, 1H), 7.62 (d, J = 9.3 Hz, 1H), 6.31 (s,
1H NMR (300 MHz, Chloroform-d) δ 8.53-8.49 (m, 1H), 7.94 (d, J = 7.5 Hz, 1H), 7.69-7.66 (m, 1H), 7.38 (d, J = 9.0 Hz,
1H NMR (300 MHz, Chloroform-d) δ 8.62 (d, J = 4.8 Hz, 1H), 8.13-8.04 (m, 1H), 7.55 (t, J = 5.2 Hz, 1H), 7.45-7.35 (m,
1H NMR (300 MHz, DMSO-d6) δ 8.66 (d, J = 2.1 Hz, 1H), 8.00 (d, J = 2.1 Hz, 1H), 7.92 (d, J = 7.5 Hz, 1H), 7.41 (d, J = 9.0
1H NMR (300 MHz, Chloroform-d) δ 8.84 (t, J = 1.9, Hz, 1H), 8.13 (d, J = 7.3 Hz, 1H), 7.79 (d, J = 8.9 Hz, 1H), 7.42 (d, J =
1H NMR (300 MHz, Chloroform-d) δ 8.48 (d, J = 2.4 Hz, 1H), 8.06 (d, J = 7.5 Hz, 1H), 7.42-7.31 (m, 2H), 3.84 (s, 3H),
1H NMR (300 MHz, Chloroform-d) δ 8.62 (d, J = 6.9 Hz, 1H), 7.95 (d, J = 7.5 Hz, 1H), 7.84 (d, J = 8.1 Hz, 1H), 7.41-7.30
1H NMR (300 MHz, Chloroform-d) δ 8.87 (s, 1H), 8.08 (s, 1H), 7.93 (d, J = 7.2 Hz, 1H), 7.61 (d, J = 9.3 Hz, 1H), 3.85 (s,
1H NMR (300 MHz, Chloroform-d) δ 8.01-7.92 (m, 1H), 8.01-7.92 (m, 2H), 7.39 (d, J = 9.3 Hz, 1H), 3.84 (s, 3H), 2.07-
1H NMR (300 MHz, DMSO-d6) δ 8.76 (s, 1H), 8.47-8.44 (m, 1H), 8.01-7.81 (m, 2H), 3.76 (s, 3H), 1.87 (s, 3H).
1H NMR (300 MHz, Chloroform-d) δ 8.46-8.41 (m, 1H), 7.93 (d, J = 7.5 Hz, 1H), 7.67-7.63 (m, 1H), 7.36 (d, J = 9.0 Hz,
1H NMR (300 MHz, Chloroform-d) δ 8.53 (s, 1H), 8.07 (d, J = 7.2 Hz, 1H), 7.58 (d, J = 9.0 Hz, 1H), 7.38 (d, J = 9.3 Hz,
1H NMR (300 MHz, Chloroform-d) δ 8.52 (d, J = 2.4 Hz, 1H), 7.92 (d, J = 7.5 Hz, 1H), 7.65-7.61 (m, 1H), 7.38 (d, J = 9.3
1H NMR (300 MHz, Chloroform-d) δ 8.88 (s, 1H), 8.09 (s, 1H), 7.97 (d, J = 7.0 Hz, 1H), 7.41 (d, J = 9.0 Hz, 1H), 3.84 (s,
1H NMR (300 MHz, Chloroform-d) δ 8.55 (s, 1H), 8.08 (d, J = 7.5 Hz, 1H), 7.64-7.56 (m, 1H), 7.39 (d, J = 9.3 Hz, 1H),
1H NMR (300 MHz, Chloroform-d) δ 8.88 (s, 1H), 8.08 (s, 1H), 7.96 (d, J = 7.5 Hz, 1H), 7.40 (d, J = 9.0 Hz, 1H), 3.83 (s,
1H NMR (300 MHz, Chloroform-d) δ 8.91 (s, 1H), 8.19 (d, J = 7.5 Hz, 1H), 7.85 (d, J = 9.0 Hz, 1H), 7.48 (d, J = 9.6 Hz,
1H NMR (300 MHz, Chloroform-d) δ 8.89 (s, 1H), 8.08 (s, 1H), 7.96 (d, J = 7.2 Hz, 1H), 7.41 (d, J = 9.3 Hz, 1H), 3.83 (s,
1H NMR (300 MHz, Chloroform-d) δ 8.56-8.53 (s, 1H), 8.04 (d, J = 7.2 Hz, 1H), 7.62-7.56 (m, 1H), 7.38 (d, J = 9.3 Hz,
1H NMR (300 MHz, Chloroform-d) δ 8.99 (s, 1H), 8.63 (d, J = 8.1 Hz, 1H), 8.04-7.94 (m, 2H), 7.42 (d, J = 10.8 Hz, 1H),
1H NMR (300 MHz, Chloroform-d) δ 7.82-7.79 (m, 2H), 7.62 (d, J = 8.7 Hz, 1H), 7.49-7.37 (m, 2H), 6.28 (s, 1H), 4.31 (q, J =
1H NMR (300 MHz, Chloroform-d) δ 8.87 (s, 1H), 8.08 (s, 1H), 7.96 (d, J = 7.2 Hz, 1H), 7.62 (d, J = 9.3 Hz, 1H), 6.29 (s,
1H NMR (300 MHz, DMSO-d6) δ 9.09 (d, J = 2.1, 1H), 8.68 (d, J = 2.1 Hz, 1H), 8.02 (d, J = 7.5 Hz, 1H), 7.98 (d, J = 9.6
1H NMR (300 MHz, Chloroform-d) δ 8.99 (s, 1H), 8.59 (d, J = 8.1 Hz, 1H), 8.04-7.93 (m, 2H), 7.41 (d, J = 10.5 Hz, 1H),
1H NMR (300 MHz, Chloroform-d) δ 8.83-8.77 (m, 1H), 7.93 (d, J = 7.5 Hz, 1H), 7.89-7.84 (m, 1H), 7.38 (d, J = 9.3 Hz,
1H NMR (300 MHz, Chloroform-d) δ 8.54 (d, J = 2.1 Hz, 1H), 8.08 (d, J = 7.5 Hz, 1H), 7.59 (dd, J = 8.7, 2.1 Hz, 1H), 7.39
1H NMR (300 MHz, Chloroform-d) δ 8.38 (s, 1H), 8.08 (d, J = 7.2 Hz, 1H), 7.38-7.33 (m, 2H), 4.28 (q, J = 6.9 Hz, 2H),
1H NMR (300 MHz, Chloroform-d) δ 8.58 (s, 1H), 7.99 (d, J = 7.2 Hz, 1H), 7.47 (s, 1H), 7.34 (d, J = 9.3 Hz, 1H), 4.28 (q, J =
1H NMR (300 MHz, Chloroform-d) δ 8.83 (s, 1H), 8.13 (d, J = 7.2 Hz, 1H), 7.79 (d, J = 9.0 Hz, 1H), 7.42 (d, J = 9.3 Hz,
1H NMR (300 MHz, Chloroform-d) δ 8.51 (d, J = 2.4 Hz, 1H), 7.92 (d, J = 7.5 Hz, 1H), 7.67-7.58 (m, 1H), 7.37 (d, J = 9.3
1H NMR (300 MHz, DMSO-d6) δ 9.10 (s, 1H), 8.71 (s, 1H), 8.01 (d, J = 9.0 Hz, 1H), 7.99 (d, J = 7.0 Hz, 1H), 4.22 (q, J =
1H NMR (300 MHz, Chloroform-d) δ 8.51 (s, 1H), 7.92 (d, J = 7.2 Hz, 1H), 7.86 (s, 1H), 7.36 (d, J = 9.3 Hz, 1H), 4.28 (q, J =
1H NMR (300 MHz, Chloroform-d) δ 8.89 (s, 1H), 8.11 (s, 1H), 8.04 (d, J = 6.0 Hz, 1H), 7.66 (d, J = 9.0 Hz, 1H), 4.30 (q, J =
1H NMR (300 MHz, Chloroform-d) δ 8.91 (s, 1H), 8.09 (s, 1H), 8.12 (d, J = 6.6 Hz, 1H), 7.75 (d, J = 9.0 Hz, 1H), 4.27 (q, J =
1H NMR (300 MHz, Chloroform-d) δ 8.84 (s, 1H), 8.13 (d, J = 7.2 Hz, 1H), 7.79 (d, J = 8.7 Hz, 1H), 7.42 (d, J = 9.3 Hz,
1H NMR (300 MHz, Chloroform-d) δ 8.89 (s, 1H), 8.09 (s, 1H), 7.96 (d, J = 7.2 Hz, 1H), 7.45 (d, J = 9.3 Hz, 1H), 4.42 (q, J =
1H NMR (300 MHz, Chloroform-d) δ 8.85 (s, 1H), 8.07 (s, 1H), 7.82 (d, J = 7.2 Hz, 1H), 7.38 (d, J = 9.0 Hz, 1H), 4.36-4.20
1H NMR (300 MHz, Chloroform-d) δ 8.88 (s, 1H), 8.09 (s, 1H), 7.97 (d, J = 7.2 Hz, 1H), 7.41 (d, J = 9.0 Hz, 1H), 2.92 (q, J =
1H NMR (300 MHz, Chloroform-d) δ 8.87 (s, 1H), 8.08 (s, 1H), 7.96 (d, J = 7.5 Hz, 1H), 7.40 (d, J = 9.3 Hz, 1H), 4.19 (t, J =
1H NMR (300 MHz, Chloroform-d) δ 8.51 (s, 1H), 7.92 (d, J = 7.2 Hz, 1H), 7.86 (s, 1H), 7.36 (d, J = 9.3 Hz, 1H), 4.18 (t, J =
1H NMR (300 MHz, Chloroform-d) δ 8.88 (d, J = 2.1 Hz, 1H), 8.08 (d, J = 2.1 Hz, 1H), 7.97 (d, J = 7.5 Hz, 1H), 7.40 (d, J =
1H NMR (300 MHz, Chloroform-d) δ 8.58 (s, 1H), 8.08 (s, 1H), 7.96 (d, J = 7.2 Hz, 1H), 7.40 (d, J = 9.3 Hz, 1H), 4.22 (t, J =
1H NMR (300 MHz, Chloroform-d) δ 8.87 (s, 1H), 8.08 (s, 1H), 7.96 (d, J = 7.2 Hz, 1H), 7.40 (d, J = 9.3 Hz, 1H), 6.00-5.84
1H NMR (300 MHz, Chloroform-d) δ 8.88 (s, 1H), 8.08 (s, 1H), 7.96 (d, J = 7.2 Hz, 1H), 7.40 (d, J = 9.3 Hz, 1H), 5.37-5.30
1H NMR (300 MHz, Chloroform-d) δ 8.88 (s, 1H), 8.09 (s, 1H), 7.97 (d, J = 7.2 Hz, 1H), 7.41 (d, J = 9.3 Hz, 1H), 4.81 (s,
1H NMR (300 MHz, Chloroform-d) δ 8.87 (s, 1H), 8.08 (s, 1H), 7.96 (d, J = 8.1 Hz, 1H), 7.41 (d, J = 9.3 Hz, 1H), 4.74-4.69
1H NMR (300 MHz, Chloroform-d) δ 8.87 (s, 1H), 8.08 (s, 1H), 7.96 (d, J = 7.2 Hz, 1H), 7.41 (d, J = 9.3 Hz, 1H), 6.20-5.80
1H NMR (300 MHz, Chloroform-d) δ 8.87 (s, 1H), 8.08 (s, 1H), 7.97 (d, J = 7.2 Hz, 1H), 7.41 (d, J = 9.3 Hz, 1H), 4.60 (t, J =
1H NMR (300 MHz, Chloroform-d) δ 8.87 (s, 1H), 8.08 (s, 1H), 7.96 (d, J = 7.2 Hz, 1H), 7.40 (d, J = 9.3 Hz, 1H), 4.47-4.42
1H NMR (300 MHz, Chloroform-d) δ 8.89 (s, 1H), 8.08 (s, 1H), 7.96 (d, J = 7.2 Hz, 1H), 7.41 (d, J = 9.3 Hz, 1H), 5.82-5.68
1H NMR (300 MHz, Chloroform-d) δ 8.87 (s, 1H), 8.08 (s, 1H), 7.97 (d, J = 7.5 Hz, 1H), 7.41 (d, J = 9.6 Hz, 1H), 5.28 (s,
1H NMR (300 MHz, Chloroform-d) δ 8.87 (s, 1H), 8.08 (s, 1H), 7.97 (d, J = 7.2 Hz, 1H), 7.41 (d, J = 9.3 Hz, 1H), 5.36 (s,
1H NMR (300 MHz, Chloroform-d) δ 8.88 (s, 1H), 8.08 (s, 1H), 7.97 (d, J = 7.5 Hz, 1H), 7.40 (d, J = 9.3 Hz, 1H), 4.41-4.34
1H NMR (300 MHz, Chloroform-d) δ 8.58 (s, 1H), 7.94 (d, J = 7.2 Hz, 1H), 7.86 (s, 1H), 7.37 (d, J = 9.3 Hz, 1H), 4.36 (t, J =
1H NMR (300 MHz, DMSO-d6) δ 9.10 (d, J = 2.1 Hz, 1H), 8.70 (d, J = 2.1 Hz, 1H), 8.03 (d, J = 7.5 Hz, 1H), 8.00 (d, J = 9.3
1H NMR (300 MHz, Chloroform-d) δ 8.90 (s, 1H), 8.11 (s, 1H), 8.00 (d, J = 7.2 Hz, 1H), 7.44 (d, J = 9.3 Hz, 1H), 4.35 (t, J =
1H NMR (300 MHz, DMSO-d6) δ 9.10 (d, J = 2.1 Hz, 1H), 8.69 (d, J = 2.1 Hz, 1H), 8.02 (d, J = 7.5 Hz, 1H), 8.00 (d, J = 9.6
1H NMR (300 MHz, Chloroform-d) δ 8.82 (s, 1H), 8.08 (s, 1H), 7.97 (d, J = 7.2 Hz, 1H), 7.42 (d, J = 9.3 Hz, 1H), 5.51-5.40
1H NMR (300 MHz, DMSO-d6) δ 8.87 (s, 1H), 8.08-8.07 (m, 1H), 7.98 (d, J = 7.5 Hz, 1H), 7.41 (d, J = 9.3 Hz, 1H), 4.07-
1H NMR (300 MHz, Chloroform-d) δ 8.88 (s, 1H), 8.09 (s, 1H), 7.97 (d, J = 7.2 Hz, 1H), 7.41 (d, J = 9.0 Hz, 1H), 5.36-5.21
1H NMR (300 MHz, Chloroform-d) δ 8.87 (d, J = 1.2 Hz, 1H), 8.08 (d, J = 1.2 Hz, 1H), 7.92 (d, J = 7.5 Hz, 1H), 7.42-7.27
1H NMR (300 MHz, Chloroform-d) δ 8.87 (s, 1H), 8.08 (s, 1H), 7.97 (d, J = 7.2 Hz, 1H), 7.40 (d, J = 9.0 Hz, 1H), 2.06 (s,
1H NMR (300 MHz, Chloroform-d) δ 8.87 (s, 1H), 8.09 (s, 1H), 7.98 (d, J = 7.2 Hz, 1H), 7.40 (d, J = 9.0 Hz, 1H), 2.19 (s,
1H NMR (300 MHz, Chloroform-d) δ 8.87 (s, 1H), 8.09 (s, 1H), 7.98 (d, J = 7.2 Hz, 1H), 7.40 (d, J = 9.0 Hz, 1H), 4.09 (s,
1H NMR (300 MHz, Chloroform-d) δ 8.82 (s, 1H), 8.08 (s, 1H), 7.97 (d, J = 7.2 Hz, 1H), 7.42 (d, J = 9.3 Hz, 1H), 5.51-5.40
1H NMR (300 MHz, Chloroform-d) δ 8.89 (s, 1H), 8.09 (s, 1H), 7.99 (d, J = 7.2 Hz, 1H), 7.93 (d, J = 9.0 Hz, 1H), 7.55 (d, J =
1H NMR (300 MHz, Chloroform-d) δ 8.86 (s, 1H), 8.35 (s, 1H), 8.05 (s, 1H), 7.83 (d, J = 7.2 Hz, 1H), 7.32 (d, J = 9.0, 1H),
1H NMR (300 MHz, Chloroform-d) δ 8.87 (s, 1H), 8.08 (s, 1H), 7.98 (d, J = 7.2 Hz, 1H), 7.41 (d, J = 9.0 Hz, 1H), 2.59-2.53
1H NMR (300 MHz, Chloroform-d) δ 8.89 (s, 1H), 8.09 (s, 1H), 7.76 (d, J = 7.2 Hz, 1H), 7.59-7.54 (m, 2H), 7.51-7.42 (m,
1H NMR (300 MHz, Chloroform-d) δ 8.87 (s, 1H), 8.08 (s, 1H), 8.03 (d, J = 7.2 Hz, 1H), 7.40 (d, J = 9.0 Hz, 1H), 5.99 (s,
1H NMR (300 MHz, Chloroform-d) δ 8.87 (s, 1H), 8.08 (s, 1H), 7.98 (d, J = 7.5 Hz, 1H), 7.40 (d, J = 9.0 Hz, 1H), 2.00 (s,
Several methods for preparing the compounds of the present invention are illustrated in detail in the following solutions and examples. Raw materials can be purchased on the market or can be prepared by methods known in literature or as shown in the detailed description. A person skilled in the art should understand that other synthetic routes may also be used to synthesize the compounds of the present invention. Although the specific raw materials and conditions in the synthetic routes have been illustrated below, they may be easily replaced with other similar raw materials and conditions. Various isomers and the like of the compounds resulted from these modifications or variants of the preparation methods of the present invention are all included in the scope of the present invention. In addition, the preparation methods as described below can be further modified according to the disclosure of the present invention using conventional chemical methods well known to a person skilled in the art. For example, the protection for an appropriate group during the reaction, etc.
The examples of the methods provided below are used to enhance further understanding of the preparation method of the present invention. The specific substances, types and conditions used are determined to further illustrate the present invention and are not intended to limit its reasonable scope. Reagents used in the synthesis of the compounds shown in the following tables are either commercially available or can be easily prepared by a person skilled in the art.
Examples of representative compounds are as follows. The synthesis methods of other compounds are similar and will not be described in detail here.
Compound 5-1 was obtained by referring to the preparation method for Compound 6-7. A 100-mL single-necked flask was added in with Compound 5-1 (0.2 g, 0.51 mmol, 1.0 eq), methyl pyruvate (0.15 g, 1.51 mmol, 3 eq), and 10 mL of toluene in sequence. The reaction solution was stirred at room temperature for 10 min. Then triethylamine (0.05 g, 0.51 mmol, 1 eq) was added dropwise into the reaction solution which was continued with stirring and reacting at room temperature for 8 h. The LCMS detected that the reaction of the raw materials was essentially complete with the formation of a major new peak. The solvent was rotary-evaporated and 20 mL of water and ethyl acetate (20 mL*3) was added for extraction. The organic phase was washed with saturated saline solution (20 mL*3), concentrated, then stirred and purified through a silica gel column to obtain Compound 5 (0.04 g, 18% yield, colorless oily matter).
(1) Compound 6-1 (8.3 g, 38 mmol) was dissolved in 200 mL of acetonitrile, added with bis(pinacolato)diborane 6-2 (48 g, 1.90 mol), and then slowly added dropwise with tert-butyl nitrite (7.8 g, 76 mmol). The system was heated to 60° C. and reacted for 12 h. The LCMS detected disappearance of the raw materials. The reaction solution was concentrated to obtain the crude product which was then extracted with water and ethyl acetate. The organic phase was dried, concentrated, stirred and purified through a silica gel column to obtain Compound 6-3 (4.8 g, 14.7 mmol) with a yield of 39%.
(2) Compound 6-4 (0.2 g, 1.00 mmol), borate 6-3 (0.49 g, 1.50 mmol), and potassium carbonate (0.41 g, 3.00 mmol) were added into a clean flask, added with 20 mL of 1,4-dioxane and 2 mL of water, and then protected by nitrogen and evacuated for 2-3 times. After evacuation, the system was added with 1,1′-bis(diphenylphosphino)ferrocene-palladium(II)dichloride dichloromethane complex (44.74 mg, 54.79 umol), evacuated again, heated to 100° C. and stayed overnight. Upon the completion of the reaction detected by In-Process Control, the solution was treated by decompressing distillation to dry the solvent, washed with water, and extracted for 2-3 times with EA. The EA phase was then washed for 2-3 times with saturated saline solution and added with anhydrous sodium sulfate for drying. The sample was added with silica gel, stirred, and purified by normal phase chromatography to obtain Compound 6-5 (300 mg, 0.82 mmol).
(3) Compound 6-5 (0.3 g, 0.82 mmol) and hydroxylamine hydrochloride (0.28 g, 4.1 mmol) were added in a clean flask, added with a mixed solvent of ethanol and water (10 mL:2 mL), and stirred for 3 h at 80° C. Upon the completion of the reaction detected by In-Process Control, the sample was directly stirred and purified by normal phase chromatography to obtain Compound 6-6 (270 mg, 0.80 mmol).
(4) Compound 6-6 (0.27 g, 0.80 mmol) and NCS (0.32 g, 2.4 mmol) were added in a clean flask, added with 10 mL of DMF for dissolution, and stirred at 40° C. for 3 h. Upon the completion of the reaction detected by In-Process Control, the sample was washed with water, and then added with EA for extraction (extracted 3 times with suitable amount of EA). Next, the EA phase was washed twice with saturated saline solution and spin-dried to obtain the white solid 6-7 (290 mg, 0.78 mmol).
(5) A 100-mL single-necked flask was added in with Compound 6-7 (0.2 g, 0.54 mmol, 1.0 eq), methyl pyruvate (0.17 g, 1.62 mmol, 3 eq), and 10 mL of toluene in sequence. The reaction solution was stirred at room temperature for 10 min. Then triethylamine (0.06 g, 0.54 mmol, 1 eq) was added dropwise into the reaction solution which was continued with stirring and reacting at room temperature for 8 h. The LCMS detected that the reaction of the raw materials was essentially complete with the formation of a major new peak. The solvent was rotary-evaporated and 20 mL of water and ethyl acetate (20 mL*3) was added for extraction. The organic phase was washed with saturated saline solution (20 mL*3), concentrated, then stirred and purified through a silica gel column to obtain Compound 6 (0.05 g, 23% yield, pale yellow oily matter).
Compound 11-1 was obtained by referring to the preparation method for Compound 6-7. Then at room temperature, Compound 11-1 (1.0 eq) and triethylamine (3.0 eq) were added to 10 mL of THF, finally added with methyl pyruvate (1.5 eq), and stirred at room temperature for 1 h. The LCMS detected that the reaction of the raw materials was essentially complete. The reaction solution was added with silica gel, concentrated, stirred, and purified by normal phase chromatography to obtain Compound 11.
A 100-mL single-necked flask was added in with Compound 15-1 (0.3 g, 0.78 mmol, 1.0 eq), methyl pyruvate (0.24 g, 2.32 mmol, 3 eq), and 10 mL of toluene in sequence. The reaction solution was stirred at room temperature for 10 min. Then triethylamine (0.08 g, 0.78 mmol, 1 eq) was added dropwise into the reaction solution which was continued with stirring and reacting at room temperature for 8 h. The LCMS detected that the reaction of the raw materials was essentially complete with the formation of a major new peak. The solvent was rotary-evaporated and 20 mL of water and ethyl acetate (20 mL*3) was added for extraction. The organic phase was washed with saturated saline solution (20 mL*3), concentrated, then stirred and purified through a silica gel column to obtain Compound 15 (0.06 g, 25% yield, pale yellow oily matter).
Compound 6-7 (0.15 g, 0.41 mmol) and methyl 2-oxobutyrate (0.19 g, 1.64 mmol) were dissolved in 15 mL of toluene and stirred in ice-water bath until the temperature dropped to zero. Triethylamine (50 mg, 0.49 mmol) was dissolved in toluene and was added dropwise into the system in ice-water bath. After the addition, the ice-water bath was removed and the system stayed at room temperature overnight. Upon the completion of the reaction detected by in-process control, the sample was directly stirred and purified by normal phase chromatography to obtain Compound 19 (35 mg, 0.08 mmol).
300 mg of Compound 23-1 was dissolved in 10 mL of toluene, added with ethyl glyoxalate (350 mg, 4 eq) in ice bath, and stirred evenly. The system was added with 2 mL of toluene solution of triethylamine (100 mg, 1.2 eq), then warmed to room temperature and stirred overnight. The disappearance of the raw materials was detected with the generation of the product which went through post-treatment and normal phase purification to result in 180 mg of Compound 23 (50% yield).
(1) 300 mg of Compound 15 was dissolved in 10 mL of 1,4-dioxane, added with 3 eq of hydrobromic acid, and reacted at 80° C. for 3 h. The LC-MS detected the completion of the reaction. The solvent was removed by decompressing concentration. The system was added with appropriate amount of water and extracted three times with ethyl acetate. The organic phases were combined, washed with saturated saline solution for three times, dried over anhydrous sodium sulfate, and spin-dried to obtain 240 mg of the crude product 114-1 (92% yield) for direct use in the next step.
(2) 240 mg of Compound 114-1 was dissolved in 10 mL of DMF, added with 2 eq of anhydrous potassium carbonate, added dropwise with 1.5 eq of 1-bromo-3-methoxypropane at room temperature, and reacted for 2 h at room temperature. The LC-MS detected the completion of the reaction. The system was added with appropriate amount of water and extracted three times with ethyl acetate. The organic phases were combined, washed three times with 5% saline solution, and dried over anhydrous sodium sulfate. The petroleum ether/ethyl acetate system was used for separation and purification. The fractions that meet the purity requirements were spin-dried to obtain 60 mg of the pure product, i.e., Compound 114 (21% yield).
The activity level criteria for plant damage (i.e., growth control rate) are as follows:
The above growth control rates are fresh weight control rates.
Monocotyledonous and dicotyledonous weed seeds (Descurainia sophia, Capsella bursa-pastoris, Abutilon theophrasti, Galium spurium, Stellaria media, Lithospermum arvense, Rorippa indica, Alopecurus aequalis, Alopecurus japonicus, Eleusine indica, Beckmannia syzigachne, Sclerochloa dura, Erigeron canadensis, Phleum paniculatum, Veronica polita, Bromus japonicus, Aegilops tauschii, Phalaris arundinacea, Amaranthus retrofexus, Chenopodium, Commelina communis, Cichorium endivia, Convolvulus arvensis, Cirsium arvense, Solanum nigrum, Acalypha australis, Digitaria sanguinalis, Echinochloa crus-galli, Setaria viridis, Setaa pumila, Lepochloa chinensis, Monochona vaginalis, Sagitta trifolia, Schoenoplectiella juncoides, Cypenus rotundus, Cyperus ira, Cyperus difformis, Fimbristylis, Portulaca oleracea, Xanthium sibiricum, Ipomoea nil, Eschenbachia japonica, etc.) and major crop seeds (wheat, maize, paddy rice, soybean, cotton, oilseed rape, millet, sorghum, potato, sesame, castor plant, etc.) were placed in plastic pots filled with soil and then covered with 0.5-2 cm of soil to allow them to grow in a favorable greenhouse environment. Two weeks after sowing, the test plants were treated at the stage of 2-3 leaves. The test compounds of the present invention were individually dissolved with acetone, then added with Tween® 80, with 1.5 L/ha of methyl oleate emulsifiable concentrate as a synergist, diluted into solutions of certain concentrations using certain amount of water, and sprayed to the plants using a spray tower. After drug application, the experimental results on weeds were collected after 3 weeks of cultivation in a greenhouse. The compounds were applied at 500, 250, 125,860, 15, and 7.5 g a.i./ha in triplicate, and the results were averaged. Representative data are listed in Table 3.
Echinochloa
Amaranthus
Veronica
Abutilon
Digitaria
Setaria
crus-galli
retroflexus
polita
theophrasti
sanguinalis
viridis
Monocotyledonous and dicotyledonous weed seeds as well as major crop seeds (wheat, maize, paddy rice, soybean, cotton, oilseed rape, millet, sorghum) were placed in plastic pots filled with soil and then covered with 0.5-2 cm of soil. The test compounds of the present invention were individually dissolved with acetone, then added with Tween® 80, diluted with certain amount of water to obtain solutions of certain concentrations, and sprayed immediately after sowing. After drug application, the experimental results were observed after 4 weeks of cultivation in a greenhouse, showing that most of the drugs of the present invention exhibited outstanding effects at the dose of 250 g a.i./ha., especially on weeds such as Echinochloa crus-galli, Digitada sanguinalis, Abutilon theophrasti, etc., and many of the compounds had great selectivity to maize, wheat, paddy rice, and soybean.
Meanwhile, it has been found by experimentations on major weeds in wheat fields and paddy rice fields that the compounds of the present invention generally have good weed control effects; in particular, it has been noticed that the compounds have extremely high activity on broad-leaf weeds and Cyperaceae that are resistant to ALS inhibitors, for example, Sagittaria trifolia, Schoenoplectiella juncoides, Cyperus difformis, Descurainia sophia, Capsella bursa-pastoris, Leptospermum arvense, Galium spurium, Cyperus rotundus, etc., which have excellent commercial values.
Meanwhile, it has been found by extensive experimentations that many of the compounds of the present invention and compositions thereof have good selectivity to gramineae grasses such as zoysia grass, bermuda grass, tall fescue, bluegrass, ryegrass, seashore paspalum, etc., and can prevent or eliminate many key gramineous weeds and broad-leaf weeds. The experiments on sugarcane, soybean, cotton, oil sunflower, potato, fruit trees, vegetables and the like using different drug application methods also demonstrated excellent selectivity and commercial values.
| Number | Date | Country | Kind |
|---|---|---|---|
| 202210517156.1 | May 2022 | CN | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/CN2023/093936 | 5/12/2023 | WO |
