Classifications

• • 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
  • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
  • A01N43/707—1,2,3- or 1,2,4-triazines; Hydrogenated 1,2,3- or 1,2,4-triazines

Definitions

• the present invention also relates to a method for controlling the growth of weeds in the cultivation of useful plants and the use of the novel herbicidal composition therefor.
• Patent Documents 1 to 4 and Non-Patent Documents 1 to 4 describe many compounds exhibiting herbicidal action.
• the microbial pesticide MTB-951 (Tasmart) described in Non-Patent Document 3 is a phytopathogenic imperfect bacterium, Drechslera as monoceras, and is known to exhibit a herbicidal action particularly on the fly.
• these herbicides alone may not provide a wide spectrum as desired, a weed growth control effect over a long period of time, and a sufficient effect for protecting useful plants.
• the present inventors mixed a component selected from the group consisting of a specific triazine derivative and a salt thereof with a component selected from known herbicidal compounds and the like.
• each herbicidal effect can be obtained not only additively, but also a synergistic herbicidal effect can be expressed, or phytotoxicity can be reduced synergistically.
• the herbicidal composition of the present invention can control many kinds of undesirable plants (weeds) generated in field crops, paddy fields, horticulture, turf, etc. over a long period of time, and for useful plants. It was found to have high safety. Further, the herbicidal composition of the present invention can control most of the weeds, particularly those that occur in useful plants, both before and after development, and hardly harms useful plants. As a result, the present invention was completed.
• two or more kinds of drugs consisting of [Component A] selected from the group consisting of the triazine derivative represented by the formula [I] and salts thereof and [Component B] shown below are mixed or used in combination.
• the herbicidal spectrum is expanded as compared with the range of herbicidal application of each of [Component A] and [Component B], and at the same time, the herbicidal effect is achieved at an early stage and the effect is sustained.
• safety against corn, rice, wheat, barley, grain sorghum, soybeans, cotton, sugar beet, sugarcane, turf, fruit trees, etc. is ensured once. It was found that the treatment exhibited a sufficient herbicidal effect.
• the present invention is characterized by having the following gist.
• [Component A] selected from the group consisting of triazine derivatives represented by the formula [X] described below and salts thereof, and [Component B] described below as active ingredients A herbicidal composition characterized by that.
• [Component A] (In the formula, R represents a lower alkyl group having 1 to 6 carbon atoms, and X represents a halogen atom.)
• [Component B] [Herbicide] 2,3,6-TBA (2,3,6-TBA), 2,4,5-T (2,4,5-T), 2,4-D (2,4-D), 2,4 -DB (2,4-DB), ACN (ACN), AE-F-150944 (code number), DNOC (DNOC), DSMA (DSMA), EPTC (EPTC), Krasifos (clacyfos), IR-6396 (code) Number), MCPA (MCPA), MCPA-thioethyl (MCPA-thioethyl), MCPB (MCPB), MSMA (MSMA
• herbicide composition described in any one of (1) to (3) above and having an activity as a herbicide, and at least one inert liquid carrier and / or solid carrier.
• a herbicidal composition further comprising at least one surfactant as required.
• a herbicidal composition in an amount described in any one of (1) to (5) and exhibiting activity as a herbicide; At least one inert liquid carrier and / or solid carrier; At least one surfactant as required; And the method for producing the herbicidal composition according to (4) above.
• the herbicidal composition of the present invention is [Component A] selected from the group consisting of the triazine derivative represented by the above formula [X] and one of its salts, which is one active ingredient, and the above [ The combination with at least one compound selected from component B] has a broad herbicidal spectrum. Moreover, since the herbicidal effect and the phytotoxicity mitigating effect are exhibited synergistically without being limited to the simple sum of the activities obtained with each individual component, the application rate can be reduced. Furthermore, various weeds, which are problematic in paddy fields, upland fields, non-agricultural land, etc., can be suppressed over a long period of time, and they can contribute to labor saving in cultivation and increased crop production without causing phytotoxicity to useful plants. it can.
• the herbicidal composition of the present invention has excellent herbicidal efficacy, and some exhibits excellent selectivity between crops and weeds, and is useful as an agrochemical composition in farmland, particularly as a herbicide. That is, the herbicidal composition of the present invention, the foliage treatment of the field where plants for agriculture and horticulture are grown, soil treatment, seed dressing treatment, soil mixing treatment and soil treatment before sowing, simultaneous sowing treatment, soil treatment after sowing, It has a herbicidal effect on various weeds which are problematic in the sowing simultaneous covering soil mixing treatment.
• Component A which is one active ingredient of the herbicidal composition of the present invention, is selected from the group consisting of a triazine derivative represented by the formula [X] described below and a salt thereof.
• R is, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, t-butyl group, n-pentyl group, n-hexyl group, etc.
• triazine derivative of the formula [X] used as the [component A] include the compounds represented by the formula [I] described below.
• herbicidal composition of the present invention known herbicides and plant growth regulators, which are other agrochemical active ingredients [component B] that can be mixed or used together with the triazine derivatives or salts thereof used in the present invention.
• component B agrochemical active ingredients
• Component B is a compound described in Patent Documents 1 to 4 and Non-Patent Documents 1 to 4.
• the amount ratio of the two components in the herbicidal composition of the present invention varies depending on the target scene, target crop, weed type and weed state, spraying time, spraying method, formulation type, etc., and is wide as necessary. It is possible to change the mixing ratio and application amount within the range.
• the blending ratio is generally in the range of 0.001 to 1000, preferably 0.05 to 500, particularly preferably 0.01 to 100 for [Component B] with respect to 1 of [Component A] by weight. It is desirable to blend with.
• the herbicidal composition of the present invention may be used as an active ingredient per se when used. However, the herbicidal composition in an amount exhibiting activity as a herbicidal agent and an inert liquid generally used for formulation.
• liquid carrier used in the formulation examples include carriers such as isopropyl alcohol, xylene, cyclohexane, methylnaphthalene, and water.
• solid carrier examples include talc, bentonite, clay, kaolin, diatomaceous earth, and white carbon. , Vermiculite, calcium carbonate, slaked lime, silica sand, ammonium sulfate, urea and the like.
• Surfactants used as necessary include, for example, alkylbenzene sulfonic acid metal salt, alkylnaphthalene sulfonic acid formalin condensate metal salt, alcohol sulfate ester salt, alkylaryl sulfonate, lignin sulfonate, polyoxyethylene glycol Examples include ether, polyoxyethylene alkyl aryl ether, polyoxyethylene sorbitan monoalkylate and the like.
• auxiliary agent examples include carboxymethyl cellulose, polyethylene glycol, and gum arabic.
• the herbicide composition of the present invention may be mixed with insecticides, fungicides, other herbicides, plant growth regulators, safeners, sputum microorganisms, fertilizers and the like as necessary.
• the herbicidal composition of the present invention may be applied directly, diluted to a concentration according to the purpose of use, and used by foliage application, soil application, water application, and the like.
• the herbicidal composition of the present invention may be used by mixing [Component A] and [Component B] in advance, or may be sequentially used according to the purpose.
• you may use as a formulation of a herbicidal composition.
• the amount of the active ingredient in the preparation of the herbicidal composition of the present invention is appropriately selected as necessary, but in the case of powder, fine granule or granule, 0.01 to 90% (weight), preferably 0. It is preferable to select from the range of 05 to 50% (weight). In the case of emulsions, solutions, flowables and wettable powders, it is preferable to select from the range of 1 to 90% (weight), preferably 5 to 80% (weight).
• the application rate of the herbicidal composition of the present invention varies depending on the type of active ingredient used, the target weed, the tendency to occur, the environmental conditions, the dosage form used, and the like.
• the active ingredient is selected from the range of 0.1 g to 5 kg, preferably 0.5 g to 1 kg per 10 are.
• the active ingredient concentration during use is generally selected from the range of 10 to 100,000 ppm.
• the herbicidal composition of the present invention adjusted as described above acts on a useful plant, a place where the useful plant is intended to grow or grow, or a non-agricultural land at the same time or in a divided manner. This makes it possible to control the growth of plants that are undesirable relative to useful plants.
• the useful plants include field crops, paddy field crops, horticultural crops, turf, fruit trees and the like.
• the useful plant as used in the present invention specifically includes, for example, corn, rice, wheat, barley, rye, oat, sorghum, cotton, soybean, peanut, buckwheat, sugar beet, rapeseed, sunflower, sugarcane and tobacco.
• Agricultural crops Eggplants, tomatoes, peppers, peppers, potatoes, cucurbits, pumpkins, zucchini, watermelons, melons, cruciferous vegetables (radish, turnip, horseradish, kohlrabi, Chinese cabbage, Cabbage, mustard, broccoli, cauliflower, etc.), asteraceae vegetables (burdock, shungiku, artichoke, lettuce, etc.), liliaceae vegetables (leek, onion, garlic, asparagus), seriaceae vegetables (carrot, parsley, celery, American boofish) Etc.), red crustacean vegetables (spinach, Dandelion, etc.), Lamiaceae vegetables (Perilla, mint, basil, etc.), strawberries, sweet potatoes, yam, taro, etc .; fruits (apples, pears, Japanese pears, quince, quince, etc.), nuclear fruits (peaches, Plum, Nectarine, Ume, Sweet cherry, Apricot, Prunes, etc.), Citrus (Satsuma mandarin, Orange,
• useful plants in the present invention include HPPD inhibitors such as isoxaflutol, ALS inhibitors such as imazetapyr and thifensulfuron / methyl, EPSP synthase inhibitors such as glyphosate, and glutamine synthetase inhibitors such as glufosinate.
• HPPD inhibitors such as isoxaflutol
• ALS inhibitors such as imazetapyr and thifensulfuron / methyl
• EPSP synthase inhibitors such as glyphosate
• glutamine synthetase inhibitors such as glufosinate.
• Tolerance to drugs acetyl CoA carboxylase inhibitors such as cetoxydim
• PPO inhibitors such as flumioxazin
• herbicides such as bromoxynil, dicamba and 2,4-D were conferred by classical breeding methods and gene recombination techniques Plants are also included.
• Examples of “agricultural and horticultural plants” that have been given resistance by classical breeding methods include rapeseed, wheat, sunflower, rice, and corn that are resistant to imidazolinone-based ALS-inhibiting herbicides such as imazetapil. It has already been sold under the product name>.
• SR corn and the like are examples of agricultural and horticultural plants to which resistance has been imparted to acetyl CoA carboxylase inhibitors such as trion oxime and aryloxyphenoxypropionic acid herbicides by classical breeding methods.
• acetyl-CoA carboxylase inhibitors such as trion oxime and aryloxyphenoxypropionic acid herbicides by classical breeding methods.
• Agro-horticultural plants tolerated by acetyl-CoA carboxylase inhibitors are the Proceedings of the National Academy of Sciences of the United States of America (Proc.Natl.Acad Sci. USA) 87, 7175-7179 (1990).
• a mutant acetyl CoA carboxylase resistant to an acetyl CoA carboxylase inhibitor has been reported in Weed Science 53, 728-746 (2005), etc.
• a plant resistant to an acetyl-CoA carboxylase inhibitor can be produced by introducing a mutation into the plant acetyl-CoA carboxylase or introducing a mutation associated with imparting resistance into the plant.
• a nucleic acid introduced with a base substitution mutation represented by chimera plastic technology (Gura T. 1999. Repairing the Genome's Spelling Mistakes. Science 285: 316-318) is introduced into plant cells (acetyl CoA carboxylase / herbicide). Plants that are resistant to acetyl-CoA carboxylase inhibitors / herbicides can be created by inducing site-specific amino acid substitution mutations in the target) gene.
• Examples of agricultural and horticultural plants imparted with resistance by genetic recombination technology include glyphosate-resistant corn, soybean, cotton, rapeseed, sugar beet varieties, Roundup Ready (registered trademark), Aglisher GT ( (Agriculture GT) ⁇ registered trademark> and the like.
• glyphosate-resistant corn, soybean, cotton, rapeseed, sugar beet varieties Roundup Ready (registered trademark)
• Aglisher GT (Agriculture GT) ⁇ registered trademark>
• bromoxynyl-resistant cotton by gene recombination technology is already sold under the trade name BXN.
• the above “agricultural and horticultural plants” include plants that can synthesize, for example, selective toxins known in the genus Bacillus, using genetic recombination techniques.
• insecticidal toxins expressed in such transgenic plants include insecticidal proteins derived from Bacillus cereus and Bacillus cilpopilliae; Cry1Ab derived from Bacillus cilthuringiensis , Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, etc., insecticidal proteins such as VIP1, VIP2, VIP3 or VIP3A; nematode-derived insecticidal proteins; scorpion toxin, spider toxin, bee toxin or Toxins produced by animals such as insect-specific neurotoxins; filamentous fungi toxins; plant lectins; agglutinins; protease inhibitors such as trypsin inhibitors, serine protease inhibitors, patatin, cystatins, papain inhibitors; ricin Ribosome inactivating protein (RIP) such as corn-RIP, abrin, saporin, bry
• toxins expressed in such transgenic plants insecticidal proteins such as Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, ⁇ -endotoxin proteins, VIP1, VIP2, VIP3 or VIP3A Hybrid toxins, partially defective toxins, and modified toxins are also included. Hybrid toxins are produced by new combinations of different domains of these proteins using recombinant techniques. As a toxin lacking a part, Cry1Ab lacking a part of the amino acid sequence is known. In the modified toxin, one or more amino acids of the natural toxin are substituted.
• Examples of these toxins and recombinant plants capable of synthesizing these toxins include, for example, EP-A-0374753, WO93 / 07278, WO95 / 34656, EP-A-0427529, EP-A-451878, WO03 / 052073, etc. It is described in the patent literature. Toxins contained in these recombinant plants particularly confer resistance to Coleoptera, Diptera pests, and Lepidoptera pests.
• genetically modified plants containing one or more insecticidal pest resistance genes and expressing one or more toxins are already known, and some are commercially available.
• these genetically modified plants include YieldGuard (registered trademark) (a corn variety that expresses Cry1Ab toxin), Yieldgard rootworm (registered trademark) (a corn variety that expresses Cry3Bb1 toxin), YieldGuard Plus (registered trademark) (a corn variety expressing Cry1Ab and Cry3Bb1 toxin), Herculex I (registered trademark) (phosphino for conferring resistance to Cry1Fa2 toxin and glufosinate Maize variety expressing tricine N-acetyltransferase (PAT), NuCOTN33B ⁇ registered trademark> (cotton variety expressing Cry1Ac toxin), Volga Bollgard I (registered trademark) (cotton varieties expressing Cry1Ac toxin), Volgard II (registered trademark
• the above-mentioned useful plants include those that have been given the ability to produce anti-pathogenic substances having a selective action using genetic recombination techniques.
• anti-pathogenic substances examples include PR proteins (described in PRPs, EP-A-0392225); sodium channel inhibitors, calcium channel inhibitors (virus-produced KP1, KP4, KP6 toxins, etc.) Ion channel inhibitors; stilbene synthase; bibenzyl synthase; chitinase; glucanase; peptide antibiotics, heterocyclic antibiotics, protein factors involved in plant disease resistance (called plant disease resistance genes) And the like, which are produced by microorganisms such as those described in WO 03/000906).
• PR proteins described in PRPs, EP-A-0392225
• sodium channel inhibitors calcium channel inhibitors (virus-produced KP1, KP4, KP6 toxins, etc.) Ion channel inhibitors
• stilbene synthase bibenzyl synthase
• chitinase glucanase
• peptide antibiotics heterocyclic antibiotics
• protein factors involved in plant disease resistance called plant disease resistance genes
• the above-mentioned useful plants include crops that have been provided with useful traits such as oil component modification and amino acid content enhancing traits using genetic recombination techniques. Examples include VISTIVE ⁇ (R)> (low linolenic soybean with reduced linolenic content) or high-lysine (high heel) corn (corn with increased lysine or oil content).
• the herbicidal composition of the present invention has herbicidal efficacy against various weeds.
• the weed is illustrated below, it is not limited to these examples.
• Red-tailed weeds Oenothera erythrosepala, Oenothera laciniata; Buttercup weeds: Ranunculus muricatus, Ranunculus sardous; Polygonum weeds: Polygonum convolvulus, Polygonum lapathifolium, Polygonum pensylvanicum, Polygonum persicaria, Rumex crispus, Rolix tus Weed (Polygonum pensylvanicum), Ginseng (Persicaria longiseta), Giant ginseng (Persicaria lapathifolia), Persicaria nepalensis, Polygonum aviculare; Berberidae weeds: Portulaca oleracea; Dianthus weeds: Stellaria media, Dutch easter (Cerastium glomeratum), Stell
• Hortensis Bailey Sonchus asper, Sonchus arvensis, Bidens ftondosa, Eclipta ptostrata, Bidense tipartita, Senecio madagascariensis, olop (Rudbeckia laciniata); Purple Weeds: Forget-me-nots (Myosotis arvensis), Nohara Murasaki (Myosotis arvensis), Inu Murasaki (Lithospermum officinale); Moth family weeds: Asclepias syriaca; Euphorbia weeds: Euphorbia helioscopia, Euphorbia maculata, Acalypha australis; Auricularia weeds: Geranium carolinianum, Erodium cicutarium, Dove's Foot Crane's-bill (Geranium molle), Hedgerow Crabe's-bill (Geranium pyr
• the herbicidal composition of the present invention includes corn (Zea (mays), wheat (Triticum aestivum), barley (Hordeum vulgare), rice (Oryza sativa), sorghum (Sorghum bicolor), soybean (Glycine max), cotton (Gossypium).
• sugar beet (Beta vulgaris), peanut (Arachis hypogaea), sunflower (Helianthus annuus), rapeseed (Brassica napus), buckwheat (Fagopyrum esculentum), sugarcane (Saccharum officinarum), tobacco (Nicotiana taba) It does not show any phytotoxicity that causes problems for horticultural crops such as crops, flower buds and sugar beets.
• the herbicidal composition of the present invention can effectively weed various weeds that are problematic in no-tillage cultivation such as soybean, corn, wheat and the like, and is also problematic for crops. No phytotoxicity is shown.
• the herbicidal composition of the present invention in paddy fields, for various weeds to be listed below, various sowing after sowing, soil treatment before and after transplantation, simultaneous treatment of transplantation, post-transplantation flooding treatment, foliage treatment, etc. Effective herbicidal method. Although the weed is illustrated below, it is not limited to these examples.
• Gramineae weeds Echinochloa oryzicola; Echinochloa crus-galli; Azegaya (Leptochloa chinensis), Tigosasa (Isachne globosa), Kizusuzumenohie (Paspalum distichum)
• Weeping weeds Azena (Lindernia procumbens), American Azena (Lindernia dubia), Abnome (Dopatrium junceum), Greater Abnomome (Gratiola japonica), Azepaka (Lindernia angustifolia), Kikumo (Limnophila sessiliflora) Misohidae weeds: Rotala indica, Ammannia multiflora; Weeping weeds: Elatine triandra; Cyperus weeds: Cyperus difformis, Scirpus hotarui, Matsubai (Eleocharis aci
• the herbicidal composition of the present invention does not exhibit phytotoxicity that causes problems for transplanted rice.
• the herbicidal composition of the present invention includes, for example, a land for an industrial facility such as a slope of a dike, a riverbed, a road shoulder and a slope, a railroad, a park green space, a ground, a parking lot, an airport, a factory and a storage facility, Can weed a wide range of weeds in non-agricultural lands that need to control the growth of weeds, such as fallow land or city-paid land, or in orchards, pastures, lawns, forestry areas, etc. .
• the weed is illustrated below, it is not limited to these examples.
• the herbicidal composition of the present invention can weed a wide range of weeds generated in rivers, waterways, canals, reservoirs and the like by treatment such as foliage treatment and water surface application.
• Squirrel family water hyacinth (Eichhornia crassipes); Salamanders: Azolla imbricata, Azolla japonica, Salvinia natanas; Araceae: Duckweed (Pistia stratiotes); Arynotraceae: Myriophyllum brasilensa, Myriophyllum verticillatum; Myriophyllum spicatum; Myriophyllum matogrossense; Acalyxaceae: Azolla cristata; Pokeweed family: Veronica anagallis-aquatica; Amaranthaceae: Alternanthera philoxeroides; Asteraceae: Giant sunflower (Gymnocoronis spilanth
• the triazine derivative represented by the general formula [X] or a salt thereof used in the present invention can be produced by various methods. Although the typical manufacturing method is illustrated below, it is not limited to these methods.
• the triazine derivative represented by the general formula [X] used in the present invention can be produced by a method having a reaction formula exemplified below.
• the enol ester compound of the general formula [3a] can be produced by reacting the compound of the general formula [1] with the compound of the general formula [2] in a solvent in the presence of a base.
• the amount of the compound of the general formula [2] used here may be appropriately selected from the range of 0.5 to 10 mol, preferably 1.0 to 1 with respect to 1 mol of the compound of the general formula [1]. .2 moles.
• Examples of the base that can be used in this step include organic compounds such as triethylamine, pyridine, 4-dimethylaminopyridine, N, N-dimethylaniline, and 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU).
• organic compounds such as triethylamine, pyridine, 4-dimethylaminopyridine, N, N-dimethylaniline, and 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU).
• Metal carbonates such as sodium carbonate, potassium carbonate, magnesium carbonate and calcium carbonate
• Metal hydrogen carbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate
• Metal acetates such as sodium acetate, potassium acetate, calcium acetate and magnesium acetate
• Metal carboxylates represented by: metal alkoxides such as sodium methoxide, sodium ethoxide, sodium tertiary butoxide, potassium methoxide, potassium tertiary butoxide; sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide
• Metal hydroxides such as Um
• lithium hydride, sodium hydride, potassium hydride, and metal hydrides such as calcium hydride.
• the amount of the base used may be appropriately selected from the range of 0.5 to 10 mol, preferably 1.0 to 1.2 mol, per 1 mol of the compound of the general formula [1].
• the solvent that can be used in this step is not particularly limited as long as it does not inhibit the progress of this reaction.
• nitriles such as acetonitrile, ethers such as diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, monoglyme, diglyme; dichloroethane, Halogenated hydrocarbons such as chloroform, carbon tetrachloride and tetrachloroethane; Aromatic hydrocarbons such as benzene, chlorobenzene, nitrobenzene and toluene; Amides such as N, N-dimethylformamide and N, N-dimethylacetamide; 1 Imidazolinones such as 1,3-dimethyl-2-imidazolinone; sulfur compounds such as dimethyl sulfoxide; and a mixed solvent thereof can also be used.
• the reaction temperature may be selected from the range of the boiling point of the inert solvent used from ⁇ 20 ° C., preferably 0 ° C. to 100 ° C.
• the reaction can be carried out in a two-layer system using a phase transfer catalyst such as a quaternary ammonium salt.
• the reaction time varies depending on the reaction temperature, reaction substrate, reaction amount, etc., but is usually 10 minutes to 48 hours.
• the compound of the general formula [3a], which is the target product of the reaction is collected from the reaction system by a conventional method after the completion of the reaction, and can be purified by operations such as column chromatography and recrystallization as necessary.
• the triazine derivative represented by the general formula [X] can be produced by reacting the compound of the general formula [3a] produced in Step 1 and a cyano compound in the presence of a base.
• the same bases as described in Step 1 can be mentioned.
• the amount of the base used may be appropriately selected from the range of 0.5 to 10 mol, preferably 1.0 to 1.2 mol, relative to 1 mol of the compound of the general formula [3a].
• Examples of the cyano compound that can be used in this step include potassium cyanide, sodium cyanide, acetone cyanohydrin, hydrogen cyanide, or a polymer holding hydrogen cyanide.
• the amount of the cyano compound to be used may be appropriately selected from the range of 0.01 to 1.0 mol, preferably 0.05 to 0.2 mol, per 1 mol of the compound of the general formula [3a].
• a phase transfer catalyst such as crown ether may be used.
• the reaction temperature may be selected from the range of the boiling point of the inert solvent used from ⁇ 20 ° C., preferably 0 ° C. to 100 ° C.
• the reaction time varies depending on the reaction temperature, reaction substrate, reaction amount, etc., but is usually 10 minutes to 48 hours.
• the triazine derivative represented by the general formula [X] can be produced even if the general formula [3a] produced in the step 1 is used without isolation.
• the triazine derivative represented by the general formula [X] produced in Step 2 is collected from the reaction system by a conventional method after the completion of the reaction, and can be purified by operations such as column chromatography and recrystallization as necessary. .
• the compound of the general formula [2] which is a synthetic intermediate for producing the triazine derivative represented by the general formula [X]
• the compound of the general formula [2] can be produced by a method comprising the following reaction formula.
• R, X and X 1 each have the same meaning as described above, and R 1 represents a phenyl group or an alkyl group.
• the compound of the general formula [6] can be produced by reacting the compound of the general formula [4] with diethyl ketomalonate [5].
• the amount of diethyl ketomalonate [5] used is 1.0 to 1.5 with respect to 1 mol of the compound of the general formula [4]. It may be appropriately selected from the range of moles, preferably 1.0 to 1.2 moles.
• solvents that can be used include the same solvents as those described in Step 1 of Production Method 1.
• the reaction temperature may be selected from the range of the boiling point of the inert solvent used from ⁇ 20 ° C., preferably 0 ° C. to 100 ° C.
• the reaction time varies depending on the reaction temperature, reaction substrate, reaction amount, etc., but is usually 10 minutes to 48 hours.
• the compound of general formula [8] can be produced by reacting the compound of general formula [6] with the compound of general formula [7a] or the compound of general formula [7b] under basic conditions.
• the amount of the compound of the general formula [7a] or the compound of the general formula [7b] used is 1 mol of the compound of the general formula [6]. It may be appropriately selected from the range of 1.0 to 1.5 mol, preferably 1.0 to 1.2 mol.
• Examples of the base that can be used include the same bases described in Step 1 of Production Method 1.
• the amount of the base used may be appropriately selected from the range of 0.1 to 10 mol, preferably 1.0 to 1.2 mol, per 1 mol of the general formula [6].
• solvents that can be used include the same solvents as those described in Step 1 of Production Method 1.
• the reaction temperature may be selected from the range of the boiling point of the inert solvent used from ⁇ 20 ° C., preferably 0 ° C. to 100 ° C.
• the reaction time varies depending on the reaction temperature, reaction substrate, reaction amount, etc., but is usually 10 minutes to 48 hours.
• the compound of general formula [9] can be produced by hydrolyzing the compound of general formula [8].
• the hydrolysis reaction can be performed in water, an organic solvent or a mixed solvent thereof in the presence of an acid or a base.
• bases examples include the same bases as described in Step 1 of Production Method 1.
• the amount of the base used may be appropriately selected from the range of 0.01 to 100 mol, preferably 0.1 to 10 mol, relative to 1 mol of the compound [8].
• Examples of the acid that can be used include inorganic acids such as hydrochloric acid, hydrobromic acid and sulfuric acid, and organic acids such as acetic acid and trifluoroacetic acid.
• the acid can be used in an amount of 1 mol to large excess, preferably 1 to 100 mol, per 1 mol of the compound [8].
• the solvent that can be used includes water or an organic solvent, preferably a mixed solvent of water and an organic solvent.
• the organic solvent include alcohols such as methanol or ethanol, ethers such as tetrahydrofuran, acetone or Examples thereof include ketones such as methyl isobutyl ketone, amides such as N, N-dimethylformamide and N, N-dimethylacetamide, sulfur compounds such as dimethyl sulfoxide and sulfolane, acetonitrile, and mixtures thereof.
• the amount of the solvent used is 0.01 to 100 L, preferably 0.1 to 10 L, relative to 1 mol of the compound of the formula [8].
• the reaction temperature may be selected from the range of the boiling point of the inert solvent used from ⁇ 20 ° C., preferably 0 ° C. to 100 ° C.
• the reaction time varies depending on the reaction temperature, reaction substrate, reaction amount, etc., but is usually 10 minutes to 48 hours.
• the compound of the general formula [2] can be produced by reacting the compound of the general formula [9] with an appropriate halogenating agent in a solvent or without a solvent.
• halogenating agent examples include oxalyl chloride and thionyl chloride.
• the amount of the halogenating agent to be used may be appropriately selected from the range of 0.01 to 20 mol, preferably 1 to 10 mol, relative to 1 mol of the compound of the formula [9].
• solvent examples include halogen hydrocarbons such as dichloromethane and chloroform, ethers such as diethyl ether and tetrahydrofuran, and aromatic hydrocarbons such as benzene and toluene.
• halogen hydrocarbons such as dichloromethane and chloroform
• ethers such as diethyl ether and tetrahydrofuran
• aromatic hydrocarbons such as benzene and toluene.
• the amount of the solvent used is 0.01 to 100 L, preferably 0.1 to 10 L, relative to 1 mol of the formula [9].
• the reaction temperature may be selected from the range of the boiling point of the inert solvent used from ⁇ 20 ° C., preferably 0 ° C. to 100 ° C.
• the reaction time varies depending on the reaction temperature, reaction substrate, reaction amount, etc., but is usually 10 minutes to 48 hours.
• the obtained residue was dissolved in 50 ml of acetonitrile, 0.57 g (5.64 mmol) of triethylamine and 0.03 g (0.38 mmol) of acetone cyanohydrin were added, and the mixture was heated to reflux for 30 minutes. After concentration under reduced pressure, the residue was dissolved in water and washed with ethyl acetate. The aqueous layer was acidified with citric acid, extracted with chloroform, dried over magnesium sulfate, and concentrated under reduced pressure. The obtained crystals were washed with methanol to obtain 1.08 g (yield 80%) of the desired product.
• Example 2 Wetting Agent 1 part of a triazine derivative represented by the above formula [I], 10 parts of AVH-301, 0.5 part of polyoxyethylene octylphenyl ether, ⁇ -naphthalenesulfonic acid formalin condensate sodium salt 0 5 parts, 20 parts of diatomaceous earth and 68 parts of clay were mixed and ground to obtain a wettable powder.
• a triazine derivative represented by the above formula [I] 10 parts of AVH-301, 0.5 part of polyoxyethylene octylphenyl ether, ⁇ -naphthalenesulfonic acid formalin condensate sodium salt 0 5 parts, 20 parts of diatomaceous earth and 68 parts of clay were mixed and ground to obtain a wettable powder.
• Example 3 Wetting Agent 1 part of a triazine derivative represented by the above formula [I], 10 parts of mesotrione, 0.5 part of polyoxyethylene octylphenyl ether, 0.5 part of ⁇ -naphthalenesulfonic acid formalin condensate sodium salt Then, 20 parts of diatomaceous earth and 68 parts of calcium carbonate were mixed and ground to obtain a wettable powder.
• a triazine derivative represented by the above formula [I] 10 parts of mesotrione, 0.5 part of polyoxyethylene octylphenyl ether, 0.5 part of ⁇ -naphthalenesulfonic acid formalin condensate sodium salt
• 20 parts of diatomaceous earth and 68 parts of calcium carbonate were mixed and ground to obtain a wettable powder.
• Example 4 Granule wettable powder 10 parts of triazine derivative represented by the above formula [I] and 10 parts of AVH-301, 5 parts of sodium lignin sulfonate, 1 part of polyoxyethylene alkylaryl ether, sodium polycarboxylate 3 parts, 5 parts of white carbon, 1 part of pregelatinized starch, 65 parts of calcium carbonate and 10 parts of water were added, mixed, kneaded and granulated. The obtained granular material was dried with a fluidized bed dryer to obtain a granular wettable powder.
• Example 5 Flowable agent In 62.9 parts of water, 5 parts of a triazine derivative represented by the above formula [I], 15 parts of mesotrione, 2 parts of sodium lignin sulfonate, 4 parts of polyoxyethylene alkylaryl ether ammonium sulfate, polyoxy Ethylene alkyl aryl ether 0.5 part, chitansan gum 0.1 part, bentonite 0.5 part and ethylene glycol 10 part were added, mixed with a high speed stirrer, and pulverized with a wet pulverizer to obtain a flowable agent.
• a triazine derivative represented by the above formula [I] 15 parts of mesotrione, 2 parts of sodium lignin sulfonate, 4 parts of polyoxyethylene alkylaryl ether ammonium sulfate, polyoxy Ethylene alkyl aryl ether 0.5 part, chitansan gum 0.1 part, bentonite 0.5 part and ethylene glyco
• Example 6 Granule 1 part of a triazine derivative represented by the above formula [I], 7 parts of pyraclonyl, 77 parts of a bulking agent in which talc and bentonite are mixed at a ratio of 1: 3, 10 parts of white carbon, a surfactant poly After adding 10 parts of water to 5 parts of a mixture of oxyethylene sorbitan alkylate, polyoxyethylene alkylaryl polymer and alkylaryl sulfonate, and kneading well into a paste, it was extruded through a sieve hole with a diameter of 1 mm and dried. A granule was obtained by cutting to a length of 5 to 1 mm.
• Test Example 1 an action exceeding the formal sum of herbicidal action when [Component A] and [Component B] were applied individually was observed in the combination of the present invention.
• the values observed in the study showed an effect that exceeded the expected value calculated by the following Colby equation at a suitable low dose. ⁇ See SR Colby in Weeds, 15 (1967) pp.
• Expected value (E) X + Y + Z- (XY + XZ + YZ) / 100 + XYZ / 10000
• Expected value (E) X + Y + Z + Q- (XY + YZ + ZQ + XZ + ZQ + YQ) / 100 + (XYZ + YZQ + XYQ + XZQ) / 10000 + XYZQ / 1000000 It was.
• the compound [I] in Table 2 represents a triazine derivative represented by the above formula [I]. The same applies to the following test examples.
• Example 2 Herbicidal effect test at the time of weed growing season in upland cropping 10 cm (W) x 10 cm (L) x 7 cm (H) small plastic pot filled with soil, Inobie, Enokorogusa, Ichibi, Aogatetou The seedlings were seeded at a depth of 1 cm and then covered with soil. Water was supplied from the bottom of the pot to grow 2.2 to 2.7 leaves of Inobie, 2.3 to 2.5 leaves of Enokorogusa, 1.1 leaves of Ichibi, and 0.3 to 1.1 leaves of Aogaeto. The pot was placed on an area of 800 cm 2 , and a predetermined amount of the wettable powder prepared according to Example 1 was diluted with water and sprayed.
• the index evaluation was 0 (no activity) to 100 (complete death).
• the results are shown in Tables 6, 7, 8, and 9.
• the dose is shown as the amount of active ingredient per hectare.
• Example 3 Herbicidal effect test at the time of weed growth in field crops Filled with small plastic pots of 10 cm (W) x 10 cm (L) x 7 cm (H) The seedlings were seeded to a depth of 1 cm and then covered with soil. Water was supplied from the bottom of the pot to grow 2.2 to 2.7 leaves of Inobie, 2.3 to 2.5 leaves of Enokorogusa, 1.1 leaves of Ichibi, and 0.3 to 1.1 leaves of Aogaeto. The pot was placed on an area of 800 cm 2 , and a predetermined amount of the wettable powder prepared according to Example 1 was diluted with water and sprayed.
• the index evaluation was 0 (no activity) to 100 (complete death).
• the results are shown in Tables 11, 12, 13, and 14.
• the dose is shown as the amount of active ingredient per hectare.
• Example 4 Herbicidal effect test during pre-weed treatment in upland crops 10 cm (W) x 10 cm (L) x 7 cm (H) small plastic pot filled with soil The pups were seeded to a depth of 1 cm and then covered with soil. The pot was placed on an area of 800 cm 2 , and a predetermined amount of the wettable powder prepared according to Example 1 was diluted with water and sprayed. Thereafter, it was grown by downward water supply, and the herbicidal effect was visually evaluated on the 16th day after the treatment. The index evaluation was 0 (no activity) to 100 (complete death). The results are shown in Tables 16, 17, and 18. The dose is shown as the amount of active ingredient per hectare.
• Example 5 Herbicidal effect test during pre-weed treatment in upland cropping 10 cm (W) x 10 cm (L) x 7 cm (H) small plastic pot filled with soil and 1 cm After sowing to the depth, it was covered with soil. The pot was placed on an area of 800 cm 2 , and a predetermined amount of the wettable powder prepared according to Example 1 was diluted with water and sprayed. Thereafter, the plants were grown by downward water supply, and the herbicidal effect was visually evaluated on the 8th day after the treatment. The index evaluation was 0 (no activity) to 100 (complete death). The results are shown in Table 20. The dose is shown as the amount of active ingredient per hectare.
• the index evaluation was 0 (no activity) to 100 (complete death).
• the results are shown in Tables 22, 23, 24 and 25.
• the dose is shown as the amount of active ingredient per hectare.
• Example 13 Effect of reducing phytotoxicity during pre-treatment of wheat in upland cropping 11 cm (W) x 11 cm (L) x 10 cm (H) small plastic pot filled with soil and 1 cm of wheat seeds After sowing to the depth of, it was covered with soil. The pot was placed on an area of 400 cm 2 , and a predetermined amount of the wettable powder prepared according to Example 1 was diluted with water and sprayed. Thereafter, the plants were grown by downward water supply, and the phytotoxicity to wheat was visually evaluated on the 13th day after the treatment. The index evaluation was 0 (no activity) to 100 (complete death). The results are shown in Table 43. The dose is shown as the amount of active ingredient per hectare.
• Example 14 Effect of reducing phytotoxicity during wheat growing season treatment in upland cropping 11 cm (W) x 11 cm (L) x 10 cm (H) small plastic pot filled with soil and 1 cm of wheat seeds After sowing to a depth of 5 cm, it was covered with soil.
• W weight
• L weight
• H x 10 cm
• the pot was placed on an area of 400 cm 2 , and a predetermined amount of the wettable powder prepared according to Example 1 was diluted with water and sprayed. Thereafter, it was grown by downward water supply, and the phytotoxicity to wheat was visually evaluated on the 10th day after the treatment.
• the index evaluation was 0 (no activity) to 100 (complete death).
• the results are shown in Table 45.
• the dose is shown as the amount of active ingredient per hectare.
• Example 15 Herbicidal effect test during pre-weed treatment in upland cropping 10 cm (W) x 10 cm (L) x 7 cm (H) small plastic pot filled with soil, The pups were seeded to a depth of 1 cm and then covered with soil. The pot was placed on an area of 800 cm 2 , and a predetermined amount of the wettable powder prepared according to Example 1 was diluted with water and sprayed. Thereafter, it was grown by downward water supply, and the herbicidal effect was visually evaluated on the 14th day after the treatment. The index evaluation was 0 (no activity) to 100 (complete death). The results are shown in Tables 47, 48 and 49. The dose is shown as the amount of active ingredient per hectare.
• Example 18 Test for reducing phytotoxicity during pre-treatment of corn in field crops 11 cm (W) x 11 cm (L) x 10 cm (H) small plastic pot filled with soil and 1 cm of corn seeds After sowing to the depth of, it was covered with soil. The pot was placed on an area of 400 cm 2 , and a predetermined amount of the wettable powder prepared according to Example 1 was diluted with water and sprayed. After that, it was grown by downward water supply, and the phytotoxicity to corn was visually evaluated on the 9th day after the treatment. The index evaluation was 0 (no activity) to 100 (complete death). The results are shown in Table 56. The dose is shown as the amount of active ingredient per hectare.
• Example 19 Test for reducing phytotoxicity during pre-treatment of wheat in field crops 11 cm (W) x 11 cm (L) x 10 cm (H) small plastic pot filled with soil and 1 cm of wheat seeds After sowing to the depth of, it was covered with soil. The pot was placed on an area of 400 cm 2 , and a predetermined amount of the wettable powder prepared according to Example 1 was diluted with water and sprayed. Thereafter, the plants were grown by downward water supply, and the phytotoxicity to wheat was visually evaluated on the 15th day after the treatment. The index evaluation was 0 (no activity) to 100 (complete death). The results are shown in Table 58. The dose is shown as the amount of active ingredient per hectare.
• Example 21 Test for reducing phytotoxicity during rice growing season in upland cropping 11 cm (W) x 11 cm (L) x 10 cm (H) small plastic pot filled with soil and 1 cm of rice seeds After sowing to the depth of, it was covered with soil.
• the rice was grown to the third leaf stage by supplying water from below the pot.
• the pot was placed on an area of 400 cm 2 , and a predetermined amount of the wettable powder prepared according to Example 1 was diluted with water and sprayed. After that, it was grown by downward water supply, and the chemical damage to rice was visually evaluated on the 10th day after the treatment.
• the index evaluation was 0 (no activity) to 100 (complete death).
• the results are shown in Table 62.
• the dose is shown as the amount of active ingredient per hectare.
• the water of the triazine derivative represented by the above formula [I] prepared according to Example 1 is plotted on a 2 mx 1.5 m plot.
• a predetermined amount of a Japanese medicine and atrazine liquid (AAtrex 4L ⁇ registered trademark>) was diluted with water and sprayed.
• the index evaluation was 0 (no activity) to 100 (complete death).
• the results are shown in Table 63.
• the dose is shown as the amount of active ingredient per hectare.
• the herbicidal composition of the present invention is at least one selected from [Component A] selected from the group consisting of the triazine derivative represented by the formula [X] as an active ingredient and a salt thereof, and the above [Component B].
• [Component A] selected from the group consisting of the triazine derivative represented by the formula [X] as an active ingredient and a salt thereof, and the above [Component B].
• a synergistic herbicidal effect can be achieved or It has been shown to have a broad herbicidal spectrum because it is mitigated and effective for many grass species.
• it has a wider drug treatment time range than existing herbicides, suppresses the generation of weeds over a long period of time, and safety has been confirmed for both [Component A] and [Component B]. Therefore, it does not cause phytotoxicity to useful plants, and can contribute to labor saving in cultivation and increased production of crops.

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