专利汇可以提供PYRIDAZINONE COMPOUND AND USE THEREOF AS HERBICIDES专利检索,专利查询,专利分析的服务。并且A pyridazinone compound represented by the formula (I) have excellent effect on weed control and are useful as an active ingredient of herbicides.,下面是PYRIDAZINONE COMPOUND AND USE THEREOF AS HERBICIDES专利的具体信息内容。
The present invention relates to pyridazinone compounds and herbicides comprising thereof.
A certain type of pyridazinone compound is known in
However, said pyridazinone compound does not have enough weed controlling effect.
The subject of the present invention is to provide the compound with an excellent effect on weed control.
After extensive investigation, the present inventors discovered the pyrida zinone compounds represented by the formula (I) have an excellent effect on weed control to complete the present invention.
The present invention is as the following.
wherein in formula, R1 represents a C1-6 alkyl group or a (C1-6 alkyloxy) C1-6 alkyl group,
a group represented by formula,
or a group represented by formula,
(wherein in formula, L represents an oxygen or a sulfur atom,
a group represented by formula
or a group represented by formula,
wherein in formula,
or a group represented by formula,
wherein in formula,
wherein in formula, R7 represents a C1-6 alkyl group, R1, R2, Z1, Z2 and n have the same meaning as defined in (1).
wherein in formula, R9 represents a C1-6 alkyl group, R1, R2, Z1, Z2 and n have the same meaning as defined in (1).
In substituents represented by R1, R2, R3, R4, R5, R6, Z1 and Z2 in the formula (I) of the present invention,
a C1-6 alkyl group denotes an alkyl group with the number of carbon atoms from 1 to 6 and includes, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a sec-pentyl group, an isopentyl group, a neopentyl group, a hexyl group, an isohexyl group, etc.,
a C3-8 cycloalkyl group denotes a cycloalkyl group with the number of carbon atoms from 3 to 8 and includes, for example, a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, etc.,
a C2-6 alkenyl group denotes an alkenyl group with the number of carbon atoms from 2 to 6 and includes, for example, an allyl group, a 1-buten-3-yl group, a 3-buten-1-yl group, etc.,
a C2-6 alkynyl group denotes an alkynyl group with the number of carbon atoms from 2 to 6 and includes, for example, a propargyl group, 2-butynyl group, etc.,
a C6-10 aryl group denotes an aryl group with the number of carbon atoms from 6 to 10 and includes, for example, a phenyl group, a naphthyl group, etc.,
a (C6-10 aryl) C1-6 alkyl group denotes a C1-6 alkyl group substituted with a C6-10 aryl group and includes, for example, a benzyl group, a phenethyl group, etc.,
a C1-6 alkyloxy group denotes an alkyloxy group with the number of carbon atoms from 1 to 6 and includes, for example, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, etc., a C3-8 cycloalkyloxy group denotes a cycloalkyloxy group with the number of carbon atoms from 3 to 8 and includes, for example, a cyclopropyloxy group, a cyclopentyloxy group, etc.,
a C2-6 alkenyloxy group denotes an alkenyloxy group with the number of carbon atoms from 2 to 6 and includes, for example, a vinyloxy group, an allyloxy group, etc.,
a C2-6 alkynyloxy group denotes an alkynyloxy group with the number of carbon atoms from 2 to 6 and includes, for example, a propargyloxy group, 2-butynyloxy group, etc.,
a C6-10 aryloxy group denotes an aryloxy group with the number of carbon atoms from 6 to 10 and includes, for example, a phenoxy group, a naphthoxy group, etc.,
a (C6-10 aryl) C1-6 alkyloxy group denotes a C1-6 alkyloxy group substituted with a C6-10 aryl group and includes, for example, a benzyloxy group, a phenethyloxy group, etc.,
a C1-6 alkylamino group denotes an alkylamino group with the number of carbon atoms from 1 to 6 and includes, for example, a methylamino group, an ethylamino group, etc.,
a C2-6 alkenylamino group denotes an alkenylamino group with the number of carbon atoms from 2 to 6 and includes, for example, an allylamino group, a 3-butenylamino group, etc.,
a C6-10 arylamino group denotes an arylamino group with the number of carbon atoms from 6 to 10 and includes, for example, a phenylamino group, a naphthylamino group, etc.,
a di(C1-6 alkyl)amino group denotes an amino group substituted with two same or different C1-6 alkyl groups and includes, for example, a dimethylamino group, a diethylamino group, an N-ethyl-N-methylamino group, etc.,
a di(C2-6 alkenyl)amino group denotes an amino group substituted with two same or different C2-6 alkenyl groups and includes, for example, a diallylamino group, a di(3-butenyl)amino group, etc.,
a (C1-6 alkyl) (C6-10 aryl)amino group denotes an amino group substituted with a C1-6 alkyl group and a C6-10 aryl group and includes, for example, a methylphenyl amino group,an ethylphenyl amino group, etc.,
a C1-6 alkylthio group denotes an alkylthio group with the number of carbon atoms from 1 to 6 and includes, for example, a methylthio group, an ethylthio group, a propylthio group, an isopropylthio group, etc.,
a (C1-6 alkyloxy) C1-6 alkyl group denotes a C1-6 alkyl group substituted with a C1-6 alkyloxy group and includes, for example, a methoxyethyl group, an ethoxyethyl group, etc., and
a three- to eight-membered nitrogen containing heterocyclic ring group denotes an aromatic or alicyclic three-to eight-membered heterocyclic ring group comprising one to three nitrogen atoms as a ring member atom(s) and optionally comprising one to three oxygen and/or sulfur atom(s) as a ring member atom(s) and includes, for example, a 1-pyrazolyl group, a 2-pyridyl group, a 2-pyrimidinyl group, a 2-thiazolyl group, a pyrrolidino group, a piperidino group, a morpholino group, etc.
The group represented by R3, R4, R5 and R6 may be substituted with at least one halogen atom and such halogen atom includes, for example, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.
In the group represented by R3, R4, R5 and R6, a C3-6 cycloalkyl group, a C6-10 aryl group, an aryl moiety of a (C6-10 aryl)C1-6 alkyl group, a C3-8 cycloalkyloxy group, a C6-10 aryloxy group, an aryl moiety of a (C6-10 aryl) C1-6 alkyloxy group, an aryl moiety of a C6-10 arylamino group, an aryl moiety of a (C1-6 alkyl) (C6-10 aryl)amino group and a three- to eight-membered nitrogen containing heterocyclic ring group may be substituted with a C1-6 alkyl group and such a C1-6 alkyl group includes, for example, a methyl group, an ethyl group, a propyl group, a butyl group and the like.
Among the present compound, the compound represented by the formula (I-a), of which G is a hydrogen atom may take place in a form of tautomers represented by the formulas (I-a') and (I-a"). The compound represented by the formula (I-a) includes all of such tautomers and a mixture of any two or more of them.
The salt of the compound represented by the formula (I-a) can be also obtained, for example, by mixing the compound represented by the formula (I-a) with an inorganic base (for example, hydroxide, carbonate, hydrogen carbonate, acetate, hydride or others of an alkali metal (lithium, sodium, potassium, etc.); hydroxide, hydride or others of an alkali earth metal (magnesium, calcium, barium, etc.) or ammonia); an organic base (for example, dimethylamine, triethylamine, piperazine, pyrrolidine, piperidine, 2-phenylethylamine, benzylamine, ethanolamine, diethanolamine, pyridine, collidine, etc.) or a metal alkoxide (for example, sodium methoxide, potassium tert-butoxide, magnesium methoxide, etc.). The present invention includes agriculturally acceptable salts of the compounds represented by formula (I-a).
When the present compound has one or more asymmetric centers, the present compound takes place in a form of two or more stereoisomers (for example, enantiomers, diastereomers or the like). The present compound includes all of such stereoisomers and a mixture of any two or more of them.
When the present compound has geometric isomerism based on a double bond or the like, said compound also takes place in a form of two or more geometric isomers (for example, each isomer of E/Z- or trans/cis-isomers, each isomer of S-trans/S-cis-isomers or others). The present compound includes all of such geometric isomers and a mixture of any two or more of them.
Preferred embodiments of the present compounds include, for example, the following embodiment among the present compounds.
The pyridazinone compound in the formula (I), wherein n is an integer of 1 or more.
The pyridazinone compound in the formula (I), wherein n is 0 and Z1 is a C2-6 alkyl group.
The pyridazinone compound in the formula (I), wherein n is 1 or 2 and Z2 is bonded at a 4- and/or 6-position of the benzene ring.
The pyridazinone compound in the formula (I), wherein G is a hydrogen atom, a group represented by formula,
a group represented by formula,
or a group represented by formula,
(wherein in formula,
The pyridazinone compound in the formula (I), wherein G is a hydrogen atom, a group represented by formula,
or a group represented by formula,
(wherein in formula,
The pyridazinone compound in the formula (I), wherein R1 is a C1-3 alkyl group or a (C1-3 alkyloxy) C1-3 alkyl group.
The pyridazinone compound in the formula (I), wherein R2 is a hydrogen atom or a C1-3 alkyl group.
The pyridazinone compound in the formula (I), wherein R2 is a hydrogen atom or a methyl group.
The pyridazinone compound in the formula (I), wherein Z1 is a C1-3 alkyl group and Z2 is a C1-3 alkyl group.
The pyridazinone compound in the formula (I), wherein R1 is a C1-3 alkyl group or a (C1-3 alkyloxy) C1-3 alkyl group and R2 is a hydrogen atom or a C1-3 alkyl group.
The pyridazinone compound in the formula (I), wherein R1 is a C1-3 alkyl group or a (C1-3 alkyloxy) C1-3 alkyl group and R2 is a hydrogen atom or a methyl group.
The pyridazinone compound in the formula (I), wherein R2 is a hydrogen atom or a C1-3 alkyl group and G is a hydrogen atom, a group represented by formula,
a group represented by formula,
or a group represented by formula,
(wherein in formula, R3b, R4b, R5b and R6b denote the same as the above mentioned).
The pyridazinone compound in the formula (I), wherein R2 is a hydrogen atom or a C1-3 alkyl group and G is a hydrogen atom, a group represented by formula,
or a group represented by formula,
(wherein in formula, R3a and R4a denote the same as the above mentioned).
The pyridazinone compound in the formula (I), wherein R2 is a hydrogen atom or a methyl group, G is a hydrogen atom, a group represented by formula,
a group represented by formula,
or a group represented by formula,
(wherein in formula, R3b, R4b, R5b and R6b denote the same as the above mentioned).
The pyridazinone compound in the formula (I), wherein R2 is a hydrogen atom or a methyl group and G is a hydrogen atom, a group represented by formula,
or a group represented by formula,
(wherein in formula, R3a and R4a denote the same as the above mentioned).
The pyridazinone compound in the formula (I), wherein R1 is a C1-3 alkyl group or a (C1-3 alkyloxy) C1-3 alkyl group, R2 is a hydrogen atom or a C1-3 alkyl group and G is a hydrogen atom, a group represented by formula,
a group represented by formula,
or a group represented by formula,
(wherein in formula, R3b, R4b, R5b and R6b denote the same as the above mentioned).
The pyridazinone compound in the formula (I), wherein R1 is a C1-3 alkyl group or a (C1-3 alkyloxy)C1-3 alkyl group and R2 is a hydrogen atom or a C1-3 alkyl group and G is a hydrogen atom, a group represented by formula,
or a group represented by formula,
(wherein in formula, R3a and R4a denote the same as the above mentioned).
The pyridazinone compound in the formula (I), wherein R1 is a C1-3 alkyl group or a (C1-3 alkyloxy) C1-3 alkyl group, R2 is a hydrogen atom or a methyl group and G is a hydrogen atom, a group represented by formula,
a group represented by formula,
or a group represented by formula,
(wherein in formula, R3b, R4b, R5b and R6b denote the same as the above mentioned).
The pyridazinone compound in the formula (I), wherein R1 is a C1-3 alkyl group or a (C1-3 alkyloxy) C1-3 alkyl group, R2 is a hydrogen atom or a methyl group and G is a hydrogen atom, a group represented by formula,
or a group represented by formula,
(wherein in formula, R3a and R4a denote the same as the above mentioned.)
The pyridazinone compound in the formula (I), wherein R1 is a C1-3 alkyl group or a (C1-3 alkyloxy) C1-3 alkyl group, R2 is a hydrogen atom or C1-3 alkyl group,
n represents 0, 1 or 2 and each of Z2 may be same or different when n represents 2,
and when n represents 1 or 2, Z2 is (a) substituent (s) on 4- and/or 6-position of a benzene ring,
Z1 is a C1-6 alkyl group (preferably a C1-3 alkyl group) and
Z2 is a C1-6 alkyl group (preferably a C1-3 alkyl group).
The pyridazinone compound in the formula (I), wherein R1 is a C1-3 alkyl group or a (C1-3 alkyloxy) C1-3 alkyl group, R2 is a hydrogen atom or C1-3 alkyl group and G is a hydrogen atom, a group represented by formula,
a group represented by formula,
or a group represented by formula,
(wherein in formula, R3b, R4b, R5b and R6b denote the same as the above mentioned),
The pyridazinone compound in the formula (I), wherein R1 is a C1-3 alkyl group or a (C1-3 alkyloxy) C1-3 alkyl group, R2 is a hydrogen atom or a C1-3 alkyl group, G is a hydrogen atom, a group represented by formula,
or a group represented by formula,
(wherein in formula, R3a and R4a denote the same as the above mentioned),
The pyridazinone compound in the formula (I), wherein R1 is a C1-3 alkyl group or a (C1-3 alkyloxy) C1-3 alkyl group, R2 is a hydrogen atom or a methyl group,
n represents 0, 1 or 2 and each of Z2 may be same or different when n represents 2,
and when n represents 1 or 2, Z2 is (a) substituent (s) on 4- and/or 6-position of a benzene ring,
Z1 is a C1-6 alkyl group (preferably a C1-3 alkyl group) and
Z2 is a C1-6 alkyl group (preferably a C1-3 alkyl group).
The pyridazinone compound in the formula (I), wherein R1 is a C1-3 alkyl group or a (C1-3 alkyloxy) C1-3 alkyl group, R2 is a hydrogen atom or a methyl group, G is a hydrogen atom, a group represented by formula,
a group represented by formula,
or a group represented by formula,
(wherein in formula, R3b, R4b, R5b and R6b denote the same as the above mentioned),
The pyridazinone compound in the formula (I), wherein R1 is a C1-3 alkyl group or a (C1-3 alkyloxy) C1-3 alkyl group, R2 is a hydrogen atom or a methyl group, G is a hydrogen atom, a group represented by formula,
or a group represented by formula,
(wherein in formula, R3a and R4a denote the same as the above mentioned),
The pyridazinone compound represented by the formula (I-1),
(wherein in formula,
The pyridazinone compound in the formula (I-1), wherein R2-1 is a hydrogen atom, a methyl group or an ethyl group, G1 is a hydrogen atom, an acetyl group, a propionyl group, a methoxycarbonyl group, an ethoxycarbonyl group or a benzoyl group,
Z1-1 is a methyl group or an ethyl group,
Z2-1-1 is a methyl group or an ethyl group and
Z2-1-2 is a hydrogen atom, a methyl group or an ethyl group).
The pyridazinone compound represented by the formula (I-2),
(wherein in formula, R2-2 represents a hydrogen atom or a C1-3 alkyl group,
The pyridazinone compound in the formula (I-2), wherein R2-2 is a hydrogen atom, a methyl group or an ethyl group,
G2 is a hydrogen atom, an acetyl group, a methoxycarbonyl group or an ethoxycarbonyl group
Z2-2-1 is a hydrogen atom, a methyl group or an ethyl group and
Z2-2-2 is a hydrogen atom, a methyl group or an ethyl group).
The present compounds have an excellent weed controlling activity and can be used as an active ingredient of herbicide. Some of the present compounds have selectivity between crops and weeds. Examples of the weeds which the present compounds can control include following:
The present compound can be used for a herbicide of agricultural field such as field, paddy field, lawn, orchard and the like and non-agricultural field. Especially, it is suitable for herbicide in field. In some cases, weeds can be controlled without damage to crops by using the present compound in agricultural field where crops such as wheat, barley, soy bean, corn, cotton, rice and the like is growing.
When the present compound is used as an active ingredient of herbicides, the present compound are generally formulated in a dosage form suitable for a purpose of use by dissolving or dispersing in a proper liquid carrier or mixing with or absorbing to a proper solid carrier. Herbicides comprising the present compound are a formulated product, for example, in a form of emulsifiable concentrate, soluble concentrate, oil solution, aerosol, wettable powder, dust, less drifting dust, granule, micro granule, micro granule F, fine granule F, water dispersible granule, water soluble powder, flowable, dry flowable, jumbo tabletwhichmeansbaggedself-diffusible powder,tablets,pastes or others. Such formulation can be further prepared as needed by adding auxiliary agents, for instance, emulsifiers, dispersants, spreading agents, penetrating agents, wetting agents, binders, thickeners, preservatives, antioxidants, colorants or others according to a known method.
The liquid carrier used in formulation includes, for example, water, alcohols (for example, methanol, ethanol, 1-propanol, 2-propanol, ethylene glycol, etc.), ketones (for example, acetone, methyl ethyl ketone, etc.), ethers (for example, dioxane, tetrahydrofuran, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, etc.), aliphatichydrocarbons (for example, hexane, octane, cyclohexane, kerosene, burning oil, machine oil, etc.), aromatic hydrocarbons (for example, benzene, toluene, xylene, solvent naphtha, methylnaphthalene, etc.), halogenated hydrocarbons (for example, dichloromethane, chloroform, carbontetrachloride, etc.), acid amides (for example, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc.), esters (for example, ethyl acetate, butyl acetate, glyceryl fatty acid ester, etc.), nitriles (for example, acetonitrile, propionitrile, etc.) and the like. Two or more of such liquid carriers may be mixed in a proper ratio for use.
The solid carrier used in formulation includes plant powder (for example, soy flour, alfalfa flour, wheat flour, wood flour, etc.), mineral powder (for example, clays such as kaolin, bentonite, acid clay, clay, etc., talcs such as talc powder, pyrophillite powder, etc., silica such as diatomaceous earth, mica powder, etc.), alumina, sulfur powder, active charcoal, saccharides (for example, lactose, glucose, etc.), inorganic salts (for example, calciumcarbonate, sodiumbicarbonate, etc.), glass hollow bodies (natural vitreous materials being calcined to encapsulate air bubbles in it) and the like. Two or more of such solid carriers may be mixed in a proper ratio for use.
The amount of the liquid carrier or solid carrier used is generally 1 to 99% by weight, preferably about 10 to 99% by weight against total amount of the formulation.
Surfactants are generally used as emulsifiers, dispersants, spreading agents, penetrating agents, wetting agents or others used in formulation. Surfactants include, for example, anionic surfactants such as alkyl sulfate ester salts, alkylarylsulfonates, dialkyl sulfosuccinates, polyoxyethylene alkylaryl ether phosphate salts, lignin sulfonate, naphthalenesulfonate-formaldehyde polycondensates, etc., and nonionic surfactants such as polyoxyethylene alkyl ether, polyoxyethylene alkylaryl ether, polyoxyethylenealkyl polyoxypropylene block copolymer, sorbitol fatty acid ester and the like. Two or more of such surfactants may be used. The amount of the surfactant used is generally 0.1 to 50% by weight, preferably about 0.1 to 25% by weight against a total amount of the formulation.
Binders and thickeners include, for example, dextrin, sodium salt of carboxylmethylcellulose, polycarboxylic acid type polymers, polyvinylpyrrolidone, polyvinyl alcohol, sodium lignin sulfonate, calcium lignin sulfonate, sodium polyacrylate, gum acacia, sodium alginate, mannitol, sorbitol, bentonite type mineral matters, polyacrylic acid and derivatives thereof, white carbon, natural saccharide derivatives (for example, xanthan gum, guar gum, etc.) or others.
The content ratio of the present compound in the formulation is generally 1 to 90% by weight in the form of the emulsifiable concentrate, wettable powder, water dispersible granule, soluble concentrate, water soluble powder, flowable and the like, generally 0.01 to 10% by weight in the form of the oil miscible liquid, dust, less drifting dust and the like and generally 0.05 to 10% by weight in the form of the micro granule, micro granule F, fine granule F, granule and the like, respectively, but the concentration may appropriately be varied according to a purpose of use. The emulsifiable concentrate, wettable powder, water dispersible granule, soluble concentrate, water soluble powder, flowable or others are generally properly diluted with water or others and generally used after diluting to about 100 to 100, 000 times the concentration of the ingredient.
The method to apply the herbicides comprising the present compound as an active ingredient is similar to a conventional general application method for known agricultural chemicals and includes, for example, aerial spraying, soil broadcast, foliage application or the like.
When the herbicides comprising the present compound as an active ingredient is used as the herbicide for dry or paddy field, the amount thereof may be varied with an applied area, an applied time of year, an application method, target weed species, cultivated crop or the like, but generally in the range of 1 to 5000 g, preferably in the range of 10 to 1000 g of the present compound per one hectare of dry or paddy field.
The herbicides compris ing the present compound as an active ingredient for weed control in the dry field are generally used as a pre-emergence soil incorporation treatment agent, pre-emergence soil treatment agent or post-emergence foliage treatment agent. Such herbicides for weed control in the paddy field is generally used as a pre-emergence soil treatment agent or both foliage and soil treatment agent.
The herbicide which comprises the present compound as an active ingredient can simultaneously be applied, if necessary, with one or more kinds of other herbicides, plant growth regulators, fungicides, insecticides, acaricides, nematocides and the like. Or it can be used in combination with one or more kinds of other herbicides, plant growth regulators, fungicides, insecticides, acaricides, nematocides and the like.
Active ingredients of the other herbicide which can simultaneously be applied and/or can be used in combination with the present compound include, for example, as follows:
Active ingredients of the plant growth regulator include, for example, hymexazol, paclobutrazol, uniconazole-P, inabenfide, prohexadione-calcium and the like.
Active ingredients of the fungicide include, for example, as follows:
Active ingredients of the insecticide include, for example, as follows:
Active ingredients of the acaricide include, for example, hexythiazox, pyridaben, fenpyroximate, tebufenpyrad, chlorfenapyr, etoxazole, pyrimidifen, acequinocyl, bifenazate, spirodiclofen and the like.
Active ingredients of the nematocide include, for example, fosthiazate, cadusafos and the like.
The herbicide which contains the present compound as an active ingredient may, if necessary, be further mixed with a safener (for example, furilazole, dichlormid, benoxacor, allidochlor, isoxadifen-ethyl, fenchlorazole-ethyl, mefenpyr-diethyl, cloquintocet-mexyl, fenclorim, cyprosulfamide, cyometrinil, oxabetrinil, fluxofenim, flurazole, 1,8-naphthalic anhydride and the like), coloring agent, fertilizer (for example, urea and the like) and the like.
The present compound may be used as an active ingredient of herbicides for croplands such as a field, a rice paddy, a lawn, an orchard, or non-croplands. The present compound may control weeds without causing any crop injury to "crops" in a place cultivating the "crops" listed below.
Corn, rice, wheat, barley, rye, oats, sorghum, cotton, soybean, peanut, common buckwheat, sugar beet, rape, sunflower, sugar cane, tobacco and the like;
Solanaceae vegetables (eggplant, tomato, green pepper, red pepper, potato and the like), Cucurbitaceous vegetables (cucumber, pumpkin, zucchini, watermelon, melon and the like), Brassicaceae vegetables (Japanese radish, turnip, horseradish, kohlrabi, Chinese cabbage, cabbage, leaf mustard, broccoli, cauliflower and the like), Compositae vegetables (burdock, garland chrysanthemum, artichoke, lettuce and the like), Liliaceae vegetables (leek, onion, garlic, asparagus and the like), Umbelliferae vegetables (carrot, parsley, celery, wild parsnip and the like), Chenopodiaceae vegetables (spinach, Swiss chard and the like), Labiatae vegetables (perilla, mint, basil and the like), strawberry, sweet potato, yam, taro and the like;
ornamental flowers;
houseplants;
pomaceous fruits (apple, pear, Japanese pear, Chinese quince, quince and the like), stone fruits (peach, plum, nectarine, Japanese plum, mahaleb cherry, apricot, prune and the like), citrus (tangerine, orange, lemon, lime, grapefruit and the like), nuts (chestnut, walnut, hazel, almond, pistachio, cashew nut, macadamia nut and the like), sap fruits (blueberry, cranberry, blackberry, raspberry and the like), grape, persimmon, olive, loquat, banana, coffee, date palm, coconut palm and the like; and
teaplant, mulberry, floweringplants, roadsidetrees (ash plant, birch, American dogwood, eucalyptus, ginkgo, lilac, maple, willow oak, poplar, cercis, liquidambar, plane tree, zelkova, Thuja standishii, Abies, hemlock spruce, needle juniper, pine, Norway spruce, yew) and the like.
Crops being conferred resistance to herbicides by classic breeding technique, gene recombination technology or the like are included in such "crops". There is no crop injury to the crops, to which resistance to herbicides was given, when herbicides such as HPPD inhibitors such as isoxaflutole; ALS inhibitors such as imazethapyr, thifensulfuron-methyl; EPSP synthase inhibitors; glutamine synthetase inhibitors; acetyl CoA carboxylase inhibitors; or bromoxynil and the like; are applied.
The crops to which herbicidal resistance is given by classic breeding technique include, for example, Clearfield (registered trademark) canola with resistance to imidazolinone herbicides, STS soy bean with resistance to sulfonylurea herbicides, SR corn with resistance to acetyl CoA carboxylase inhibitors. The crops, to which the resistance to acetyl CoA carboxylase inhibitors is given, are described in, for example,
In addition, mutant acetyl CoA carboxylase conferring resistance to acetyl CoA carboxylase inhibitors is described, for example, in
The "crops" to which herbicidal resistance is conferred by gene recombination technology are known (for example, corn varieties to which resistance to glyphosate or glufosinate is added). Such corn varieties are commercially available as a product name of Roundup Ready (registered trademark) or Liberty Link (registered trademark).
The "crops" include crops to which ability to produce insecticidal toxins is given by gene recombination technology.
Such insecticidal toxins include, for example, insecticidal proteins produced from Bacillus cereus or Bacillus popilliae; δ-endotoxins such as Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1 and Cry9C produced from Bacillus thuringiensis; insecticidal proteins such as VIP1, VIP2, VIP3 and VIP3A; insecticidal proteins produced from nematode; toxins produced by animals such as a scorpion toxin, a spider toxin, a bee toxin and an insect specific nervous system toxin; Filamentous fungus toxins; Plant lectins; Agglutinins; protease inhibitors such as trypsin inhibitors, serine protease inhibitors, patatin, cystatin and papain inhibitors; ribosome inactivation proteins (RIP) such as ricins, corn-RIP, abrins, saporins, bryodin; steroid metabolism enzymes such as 3-hydroxysteroid oxidase, ecdysteroid-UDP-glucosyltransferase, cholesterol oxidase; ecdysone inhibitors; HMG-CoA reductase; ion channel inhibitors such as sodium channel or calcium channel inhibitor; Juvenile hormone esterase; diuretic hormone receptors; stilbene synthase; bibenzyl synthase; chitinase; and glucanases.
The insecticidal toxins include hybrid proteins of said insecticidal proteins, insecticidal proteins in which a part of amino acids composing the proteins is deleted or substituted. Hybrid proteins are created by putting different domains of these insecticidal proteins together by gene recombination technology. For example, Cry1Ab, in which a part of amino acid is deleted, is known as the above insecticidal protein in which a part of amino acids composing the protein is deleted.
For example, insecticidal toxins and the "crops" being given an ability to produce insecticidal toxins by gene recombination technology are described in
For example, the "crops" being given an ability to produce insecticidal toxins by gene recombination technology have resistance to attack from Coleopteran pests, Dipteran pests and/or Lepidopteran pests.
Examples of commercially available "crops" being given an ability to produce insecticidal toxins by gene recombination technology include YieldGard (registered trademark) (corn variety expressing Cry1Ab toxin), Yield Gard Rootworm (registered trademark) (corn variety expressing Cry3Bb1 toxin), YieldGard Plus (registered trademark) (corn variety expressing Cry1Ab and Cry3Bb1 toxins), Herculex I (registered trademark) (corn variety expressing Cry1Fa2 toxin and phosphinothricin N-acetyltransferase (PAT) to confer resistance to glufosinate), NuCOTN33B (registered trademark) (cotton variety expressing Cry1Ac toxin), Bollgard I (registered trademark) (cotton variety expressing Cry1Ac toxin), Bollgard II (registered trademark) (cotton variety expressing Cry1Ac and Cry2Ab toxins), VIPCOT (registered trademark) (cotton variety expressing VIP toxin), NewLeaf (registered trademark) (potato variety expressing Cry3A toxin), NatureGard (registered trademark) Agrisure (registered trademark) GT Advantage (GA21 glyphosate resistance trait), Agrisure (registered trademark) CB Advantage (Bt11 corn borer (CB) trait) and Protecta (registered trademark).
The "crops" also include crops being given an ability to produce anti-pathogen substances by gene recombination technology.
Anti-pathogen substances include, for example, PR proteins (PRPs, described in
The crops being given an ability to produce an anti-pathogen substance by gene recombination technology are described, for example, in
When the present compound is mixed with flumioxazin, the mixing ratio is preferably 0.1 to 10 by weight of flumioxazin based on 1 by weight of the present compound. The composition comprising the present compound and flumioxazin can be used for soil treatment or foliage treatment. The composition comprising the present compound and flumioxazin may control weeds without causing any crop injury in a place cultivating corn, rice, wheat, barley, rye, oats, sorghum, cotton, soybean, peanut, sugar beet, rape, sunflower, sugarcane and the like. And the composition comprising the present compound and flumioxazin may be used for croplands such as a lawn, an orchard, or non-croplands.
When the present compound is mixed with glyphosate, the mixing ratio is preferably 1 to 100 by weight of glyphosate based on 1 by weight of the present compound. The composition comprising the present compound and glyphosate can be used for foliage treatment. The composition comprising the present compound and glyphosate may control weeds without giving any crop injury in a place cultivating corn, rice, wheat, barley, rye, oats, sorghum, cotton, soy bean, peanut, sugar beet, rape, sunflower, sugarcane and the like. And the composition comprising the present compound and glyphosate may be used for croplands such as a lawn, an orchard, or non-croplands.
The present compound can be produced, for example, by following preparation methods.
Among the present compound, the compound represented by the formula (I-a), in which G is a hydrogen atom can be produced by the reaction of the compound represented by the formula (II) with a metal hydroxide,
(wherein in formula, R7 represents a C1-6 alkyl group (for example, a methyl group, an ethyl group, etc.) and R1, R2, Z1, Z2 and n denote the same as the above mentioned).
The reaction is generally carried out in a solvent. The solvent used in the reaction includes, for example, water, ethers such as tetrahydrofuran, dioxane or a mixed solvent thereof.
The metal hydroxide used in the reaction includes, for example, a hydroxide of an alkali metal such as sodium hydroxide, potassium hydroxide and the like. The amount of the metal hydroxide used in the reaction is generally 1 to 120 mole equivalents, preferably 1 to 40 mole equivalents to the compound represented by the formula (II).
The reaction temperature is generally in the range of room temperature to boiling point of the solvent, preferably at a boiling point of the solvent. The reaction may be carried out by heating in a sealed tube or a high pressure resistant closed vessel. The reaction time is generally in the range from 5 minutes to a few weeks.
The completion of the reaction may be confirmed with use of an analytical means such as thin layer chromatography, high performance liquid chromatography or the like after sampling a part of the reaction mixture. After the completion of the reaction, the compound represented by the formula (I-a) may be isolated, for example, by the following operation: addition of an acid to the reaction mixture, to which water is added to mix, followed by extraction with an organic solvent to form an organic layer, which is dried and concentrated.
Among the present compound, the compounds represented by the formula (I-b), in which G is a group except a hydrogen atom can be produced from the compound represented by the formula (I-a) and the compound represented by the formula (III),
(wherein in formula, G3 among G defined represents a group except a hydrogen atom, X represents a halogen atom (for example, a chlorine atom, a bromine atom, an iodine atom, etc.) or a group represented by the formula OG3 and R1, R2, Z1, Z2 and n denote the same as the above mentioned).
The reaction may be carried out in a solvent. The solvent used in the reaction includes, for example, aromatic hydrocarbons such as benzene, toluene, etc., ethers such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran, dimethoxyethane, etc., halogenated hydrocarbons such as dichloromethane, chloroform, 1,2-dichloroethane, etc., amides such as dimethylformamide, dimethylacetamide, etc., sulfoxides such as dimethylsulfoxide, etc., sulfones such as sulforane, etc. or a mixed solvent thereof.
The compound represented by the formula (III) used in the reaction includes, for example, carboxylic acid halides such as acetyl chloride, propionyl chloride, isobutyryl chloride, pivaloyl chloride, benzoyl chloride, cyclohexanecarbonyl chloride, etc., carboxylic acid anhydrides such as acetic anhydride, trifluoroaceticanhydride, etc., carbonate half ester halides such as methyl chloroformate, ethyl chloroformate, phenyl chloroformate, etc., carbamoyl halides such as dimethylcarbamoyl chloride, etc., sulfonyl halides such as methanesulfonyl chloride, p-toluenesulfonyl chloride, etc., sulfonic acid anhydrides such as methanesulfonic anhydride, trifluoromethanesulfonic anhydride, etc., or halogenated phosphate esters such as dimethyl chlorophosphate, etc. The amount of the compound represented by the formula (III) used in the reaction is generally one mole equivalent or more, preferably 1 to 3 mole equivalents to the compound represented by the formula (I-a).
The reaction is generally carried out in the presence of a base. The base used in the reaction includes, for example, organic bases such as triethylamine, tripropylamine, pyridine, dimethylaminopyridine, 1,8-diazabicyclo[5.4.0]-7-undecene, etc., and inorganic bases such as sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, calcium carbonate, sodium hydride, etc. The amount of the base used in the reaction is generally 0.5 to 10 mole equivalents, preferably 1 to 5 mole equivalents to the compound represented by the formula (I-a).
The reaction temperature is generally at -30 to 180°C, preferably at -10 to 50 °C. The reaction time is generally from 10 minutes to 30 hours.
The completion of the reaction may be confirmed with use of an analytical means such as thin layer chromatography, high performance liquid chromatography or the like after sampling a part of the reaction mixture. After the completion of the reaction, the compound represented by the formula (I-b) may be isolated, for example, by the following operation: mixing the reaction mixture with water followed by extraction with an organic solvent to form an organic layer, which is dried and concentrated.
The compound represented by the formula (III) is a known compound or may be produced from a known compound.
Among the present compound, the compound represented by the formula (I-a), in which G is a hydrogen atom can also be produced by the following preparation method. The compound represented by the formula (I-a) can be produced by the reaction of the compound represented by the formula (VI) with a base,
(wherein in formula, R9 represents a C1-6 alkyl group (for example, a methyl group, an ethyl group, etc.) and R1, R2, Z1, Z2 and n denote the same as the above mentioned).
The reaction is generally carried out in a solvent. The solvent used in the reaction includes, for example, aromatic hydrocarbons such as benzene, toluene, xylene, etc., ethers such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran, dimethoxyethane, etc., halogenated hydrocarbons such as dichloromethane, chloroform, 1,2-dichloroethane, etc., amides such as dimethylformamide, dimethylacetamide, etc., sulfones such as sulforane, etc., or a mixed solvent thereof.
The base used in the reaction includes, for example, metal alkoxides such as potassium tert-butoxide, etc., alkali metal hydrides such as sodium hydride, etc., and organic bases such as triethylamine, tributylamine, N,N-diisopropylethylamine, etc. The amount of the base used in the reaction is generally 1 to 10 mole equivalents, preferably 2 to 5 mole equivalents to the compound represented by the formula (VI).
The reaction temperature is generally at -60 to 180°C, preferably at -10 to 100 °C. The reaction time is generally from 10 minutes to 30 hours.
The completion of the reaction may be confirmed with use of an analytical means such as thin layer chromatography, high performance liquid chromatography or the like after sampling a part of the reaction mixture. After the completion of the reaction, the compound represented by the formula (I-a) may be isolated, for example, by the following operation: addition of an acid to the reaction mixture, to which water is added to mix, followed by extraction with an organic solvent to form an organic layer, which is dried and concentrated.
The compound represented by the formula (II) can be produced, for example, by the following preparation method,
(wherein in formula, X1 represents a leaving group (for example, a halogen atom such as a chlorine atom, a bromine atom, an iodine atom, etc.), X2 represents a halogen atom (for example, a chlorine atom, a bromine atom, an iodine atom, etc.), R8 represents a C1-6 alkyl group (for example, a methyl group, a butyl group, etc.) and R1, R2, R7, Z1, Z2 and n denote the same as the above mentioned) .
The compound represented by the formula (II) can be produced by a coupling reaction of the compound represented by the formula (IV) with an organometallic reagent represented by the formulas (V-a), (V-b) or (V-c) (generally one mole equivalent or more, preferably 1 to 3 mole equivalents to the compound represented by the formula (IV)).
When the compound represented by the formula (V-a) is used, said coupling reaction is carried out in a solvent. The solvent used in the reaction includes, for example, aromatic hydrocarbons such as benzene, toluene, etc., alcohols such as methanol, ethanol, propanol, etc., ethers such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran, dimethoxyethane, etc., ketones such as acetone, methyl ethyl ketone, etc., amides such as dimethylformamide, dimethylacetamide, etc., sulfoxides such as dimethylsulfoxide, etc., sulfones such as sulfolane, etc., water or a mixed solvent thereof.
When the compound represented by the formula (V-a) is used, said coupling reaction is carried out in the presence of a base. The base used in the reaction includes, for example, organic bases such as triethylamine, tripropylamine, pyridine, dimethylaniline, dimethylaminopyridine, 1,8-diazabicyclo[5.4.0]-7-uridecene, etc., and inorganic bases such as sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, calcium carbonate, cesium carbonate, potassium phosphate, etc. The amount of the base used in the reaction is generally 0.5 to 10 mole equivalents, preferably 1 to 5 mole equivalents to the compound represented by the formula (IV).
Furthermore, when the compound represented by the formula (V-a) is used, said coupling reaction is carried out in the presence of a catalyst. The catalyst used in the reaction includes, for example, a palladium catalyst such as tetrakis(triphenylphosphine)palladium, dichlorobis(triphenylphosphine)palladium, etc. The amount of the catalyst used in the reaction is generally 0.001 to 0.5 mole equivalent, preferably 0.01 to 0.2 mole equivalent to the compound represented by the formula (IV). When the compound represented by the formula (V-a) is used, a quaternary ammonium salt is preferably added in said coupling reaction. The quaternary ammonium salt used includes, for example, tetrabutylammonium bromide, etc.
When the compound represented by the formula (V-a) is used, a reaction temperature of said coupling reaction is generally at 20 to 180 °C, preferably at 60 to 150 °C. The reaction time is generally from 30 minutes to 100 hours.
The completion of the reaction may be confirmed with use of an analytical means such as thin layer chromatography, high performance liquid chromatography or the like after sampling a part of the reaction mixture. After the completion of the reaction, the compound represented by the formula (II) may be isolated, for example, by the following operation: mixing the reaction mixture with water, followed by extraction with an organic solvent to form an organic layer, which is dried and concentrated.
When the compound represented by the formula (V-b) is used, said coupling reaction is carried out in a solvent. The solvent used in the reaction includes, for example, aromatic hydrocarbons such as benzene, toluene, etc., ethers such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran, dimethoxyethane, etc., or a mixed solvent thereof.
When the compound represented by the formula (V-b) is used, said coupling reaction is carried out in the presence of a catalyst. The catalyst used in the reaction includes, for example, a nickel catalyst such as dichlorobis(1,3-diphenylphosphino)propanenickel, dichlorobis(triphenylphosphine)nickel, etc., and a palladium catalyst such as tetrakis(triphenylphosphine)palladium, dichlorobis(triphenylphosphine)palladium, etc. The amount of the catalyst used in the reaction is generally 0.001 to 0.5 mole equivalent, preferably 0.01 to 0.2 mole equivalent to the compound represented by the formula (IV).
When the compound represented by the formula (V-b) is used, the reaction temperature of said coupling reaction is generally at -80 to 180 °C, preferably at -30 to 150 °C. The reaction time is generally from 30 minutes to 100 hours.
The completion of the reaction may be confirmed with use of an analytical means such as thin layer chromatography, high performance liquid chromatography or others after sampling a part of the reaction mixture. After the completion of the reaction, the compound represented by the formula (II) may be isolated, for example, by the following operation: mixing the reaction mixture with water, followed by extraction with an organic solvent to form an organic layer, which is dried and concentrated.
When the compound represented by the formula (V-c) is used, said coupling reaction is carried out in a solvent. The solvent used in the reaction includes, for example, aromatic hydrocarbons such as benzene, toluene, etc., ethers such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran, dimethoxyethane, etc., halogenated hydrocarbons such as chloroform, 1,2-dichloroethane, etc., amides such as dimethylformamide, dimethylacetamide, etc., or a mixed solvent thereof.
When the compound represented by the formula (V-c) is used, said coupling reaction is carried out in the presence of a catalyst. The catalyst used in the reaction includes, for example, a palladium catalyst such as tetrakis(triphenylphosphine)palladium, dichlorobis(triphenylphosphine)palladium, etc. The amount of the catalyst used in the reaction is generally 0.001 to 0.5 mole equivalent, preferably 0.01 to 0.2 mole equivalent to the compound represented by the formula (IV).
When the compound represented by the formula (V-c) is used, the reaction temperature of said coupling reaction is generally at -80 to 180 °C, preferably at -30 to 150 °C. The reaction time is generally from 30 minutes to 100 hours.
The completion of the reaction may be confirmed with use of an analytical means such as thin layer chromatography, high performance liquid chromatography or others after sampling a part of the reaction mixture. After the completion of the reaction, the compound represented by the formula (II) may be isolated, for example, by the following operation: mixing the reaction mixture with water, followed by extraction with an organic solvent to form an organic layer, which is dried and concentrated.
The compound represented by the formula (II) can be produced, for example, by a method in accordance with the one described in
Organometallic reagents represented by the formulas (V-a), (V-b) and (V-c) are known compounds or can be produced by methods in accordance with known methods using known compounds.
The compound represented by the formula (IV) is a known compound or can be produced using known compounds. The compound can be produced, for example, by a method described in
The compound represented by the formula (VI) can be produced, for example, by a following preparation method,
(wherein in formula, X3 represents a halogen atom (for example, a chlorine atom, a bromine atom, an iodine atom, etc.) and R1, R2, R9, Z1, Z2 and n denote the same as the above mentioned).
The reaction is generally carried out in a solvent. The solvent used in the reaction includes, for example, nitriles such as acetonitrile, etc., ketones such as acetone, etc., aromatic hydrocarbons such as benzene, toluene, etc., ethers such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran, dimethoxyethane, etc., halogenated hydrocarbons such as dichloromethane, chloroform, 1,2-dichloroethane, etc., amides such as dimethylformamide, dimethylacetamide, etc., sulfones such as sulfolane, etc., or a mixed solvent thereof.
The reaction of the compound represented by the formula (VII) with the compound represented by the formula (VIII) is generally carried out in the presence of a base. The base used in the reaction includes, for example, organic bases such as triethylamine, tripropylamine, pyridine, dimethylaminopyridine, 1,8-diazabicyclo[5.4.0]-7-undecene,
1,4-diazabicyclo[2.2.2]octane, etc., and inorganic bases such as sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, calcium carbonate, sodium hydride, etc.
The amount of the compound represented by the formula (VIII) used in the reaction is generally 1 mole equivalent or more, preferably 1 to 3 mole equivalents to the compound represented by the formula (VII). The amount of a base used in the reaction is generally 0.5 to 10 mole equivalents, preferably 1 to 5 mole equivalents to the compound represented by the formula (VII).
The reaction temperature is generally at -30 to 180°C, preferably at -10 to 50 °C. The reaction time is generally from 10 minutes to 30 hours.
The completion of the reaction may be confirmed with use of an analytical means such as thin layer chromatography, high performance liquid chromatography or the like after sampling a part of the reaction mixture. After the completion of the reaction, the compound represented by the formula (VI) may be isolated, for example, by the following operation: mixing the reaction mixture with water, followed by extraction with an organic solvent to form an organic layer, which is dried and concentrated.
The compound represented by the formula (VII) can be produced by the reaction of the compound represented by the formula (IX)
(wherein in formula, Z1, Z2 and n denote the same as the above mentioned)
with a halogenation reagent (for example, thionyl chloride, thionyl bromide, phosphorous oxychloride, oxalyl chloride, etc.).
The compound represented by the formula (IX) is a known compound or can be produced from known compounds. The compound can be produced, for example, according to methods described in
The compound represented by the formula (VIII) is a known compound or can be produced from known compounds.
Each compound produced by above mentioned Preparation method 1 to 3 or Reference preparation method 1 to 2 may be isolated and/or purified by known procedures, for example, concentration, concentration under reduced pressure, extraction, transference dissolution, crystallization, re-crystallization, chromatography and the like.
Next, specific examples of the present compound are shown below.
The embodiments of the compound represented by the formula (II) include, for example, the following embodiments among the above defined the compound represented by the formula (II).
The compound in the formula (II), wherein n is an integer of 1 or more.
The compound in the formula (II), wherein n is 0 and Z1 is a C2-6 alkyl group.
The compound in the formula (II), wherein n is 1 or 2 and Z2 is (a) substituent (s) on 4- and/or 6-position of the benzene ring.
The compound in the formula (II), wherein R1 is a C1-3 alkyl group or a (C1-3 alkyloxy) C1-3 alkyl group.
The compound in the formula (II), wherein R2 is a hydrogen atom or a C1-3 alkyl group.
The compound in the formula (II), wherein R2 is a hydrogen atom or a methyl group.
The compound in the formula (II), wherein Z1 is a C1-3 alkyl group and Z2 is a C1-3 alkyl group.
The compound in the formula (II), wherein R1 is a C1-3 alkyl group or a (C1-3 alkyloxy) C1-3 alkyl group and R2 is a hydrogen atom or a methyl group.
The compound in the formula (II), wherein R1 is a C1-3 alkyl group or a (C1-3 alkyloxy) C1-3 alkyl group and R2 is a hydrogen atom or a C1-3 alkyl group,
n represents 0, 1, or 2 and each of Z2 may be same or different when n represents 2,
and when n represents 1 or 2, Z2 is (a) substituent (s) on 4- and/or 6-position of a benzene ring,
Z1 is a C1-6 alkyl group (preferably a C1-3 alkyl group) and
Z2 is a C1-6 alkyl group (preferably a C1-3 alkyl group).
The compound in the formula (II), wherein R1 is a C1-3 alkyl group or a (C1-3 alkyloxy) C1-3 alkyl group and R2 is a hydrogen atom or a methyl group,
n represents 0, 1, or 2 and each of Z2 may be same or different when n represents 2,
and when n represents 1 or 2, Z2 is (a) substituent(s) on 4- and/or 6-position of a benzene ring,
Z1 is a C1-6 alkyl group (preferably a C1-3 alkyl group) and
Z2 is a C1-6 alkyl group (preferably a C1-3 alkyl group).
The embodiments of the compound represented by the formula (VI) include, for example, the following embodiments among the above defined the compound represented by the formula (VI).
The compound in the formula (VI), wherein n is an integer of 1 or more.
The compound in the formula (VI), wherein n is 0 and Z1 is a C2-6 alkyl group.
The compound in the formula (VI), wherein n is 1 or 2 and Z2 is (a) substituent (s) on 4- and/or 6-position of the benzene ring.
The compound in the formula (VI), wherein R1 is a C1-3 alkyl group or a (C1-3 alkyloxy) C1-3 alkyl group.
The compound in the formula (VI), wherein R2 is a C1-6 alkyl group.
The compound in the formula (VI), wherein R2 is a hydrogen atom or a C1-3 alkyl group.
The compound in the formula (VI), wherein R2 is a C1-3 alkyl group.
The compound in the formula (VI), wherein R2 is a hydrogen atom or a methyl group.
The compound in the formula (VI), wherein R2 is a methyl group.
The compound in the formula (VI), wherein Z1 is a C1-3 alkyl group and Z2 is a C1-3 alkyl group.
The compound in the formula (VI), wherein R1 is a C1-3 alkyl group or a (C1-3 alkyloxy)C1-3 alkyl group and R2 is a hydrogen atom or a methyl group.
The compound in the formula (VI), wherein R1 is a C1-3 alkyl group or a (C1-3 alkyloxy) C1-3 alkyl group and R2 is a hydrogen atom or a C1-3 alkyl group,
n represents 0, 1, or 2 and each of Z2 may be same or different when n represents 2,
and when n represents 1 or 2, Z2 is (a) substituent (s) on 4- and/or 6-position of a benzene ring,
Z1 is a C1-6 alkyl group (preferably a C1-3 alkyl group) and
Z2 is a C1-6 alkyl group (preferably a C1-3 alkyl group).
The compound in the formula (VI), wherein R1 is a C1-3 alkyl group or a (C1-3 alkyloxy) C1-3 alkyl group and R2 is a hydrogen atom or a methyl group,
n represents 0, 1, or 2 and each of Z2 may be same or different when n represents 2,
and when n represents 1 or 2, Z2 is (a) substituent (s) on 4- and/or 6-position of a benzene ring,
Z1 is a C1-6 alkyl group (preferably a C1-3 alkyl group) and
Z2 is a C1-6 alkyl group (preferably a C1-3 alkyl group).
The present invention will be further illustrated by the following Examples, Reference examples, Formulation examples and Test examples: however the present invention is not limited to these examples.
In the Examples and Reference examples, room temperature means usually 10 to 30 °C. 1H-NMR means proton nuclear magnetic resonance. It is measured with tetramethyl silane as internal standard, and chemical shift (δ) is shown by ppm.
The abbreviations used in the Examples and Reference examples have the following meanings:
After 50 mL of water, 4.657 g of potassium hydroxide (content, 85%) and 5 mL of 1,4-dioxane were added to 3.193 g of 4-(2-ethylphenyl)-5-methoxy-2-methyl-3(2H)-pyridazinone (Compound II-1), the mixture was stirred and heated under reflux for 36 hours. After cooling, concentrated hydrochloric acid was added to the reaction mixture to acidify, to which 10 ml of water and 100 ml of ethyl acetate were added. The resulting mixture was filtered to remove insoluble substances and the filtrate was separate to two phase. The organic layer was washed with water and then a saturated sodium chloride aqueous solution and dried over anhydrous magnesium sulfate, and the solvent was distilled off. The solid obtained was washed with a mixed solvent of ethyl acetate and hexane (1:2) to yield 2.050 g of the title compound as colorless crystals.
The present compound which was produced according to Example 1 will be shown in Table 1.
The compound represented by the formula (I-a):
Under a nitrogen atmosphere, 13 mL of a tetrahydrofuran solution of potassium tert-butoxide (1 mol/L) was stirred at room temperature, to which a solution of 1.9 g of ethyl 2-[2-(2,6-diethyl-4-methylphenylacetyl)-2-methylhydrazono]p ropanoate (Compound VI-2) in 55 mL of toluene was added dropwise over about 1 hour. The mixture was further stirred at room temperature for 30 minutes. Then, the reaction mixture was concentrated under reduced pressure. To the residue obtained was added 30 mL of ice-water, which was extracted with tert-butyl methyl ether (20 mL x 2). To the aqueous layer was then added 1.6 g of 35% hydrochloric acid, which was extracted with ethyl acetate (20 mL x 3). The ethyl acetate extracts were combined, washed with saturated sodium chloride aqueous solution (20 mL x 2), dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue obtained was subjected to a silica gel column chromatography (ethyl acetate : hexane = 1:3 as eluent) to yield 0.76 g of a solid. The solid was washed with cold hexane and air-dried to yield 0.59 g of the title compound as white powder.
The present compound which was produced according to Example 2 will be shown in Table 2.
The compound represented by the formula (I-a):
To 0.326 g of Compound I-a-1 were added 12 mL of tetrahydrofuran and 0.40 mL of triethylamine. The mixture obtained was chilled with ice, to which 0.25 mL of benzoyl chloride was further added. The mixture was stirred for 10 minutes under cooling with ice and then at room temperature for 3 hours. 30 mL of water was added to the reaction mixture, which was extracted with 30 mL of ethyl acetate twice. The extracts were combined, washed with a saturated sodium chloride aqueous solution and dried over anhydrous magnesium sulfate, and the solvent was distilled off. The residue was subjected to a silica gel column chromatography (as eluent, ethyl acetate : hexane = 1: 2, and then 2:1) to yield 0.463 g of the title compound as colorless oil.
The present compound which was produced according to Example 3 will be shown in Table 3.
The compound represented by the formula (I-b):
A typical example of the preparation of the compound represented by the formula (II) is shown in Reference example 1.
To a mixture of 2.516 g of 4-chloro-5-methoxy-2-methyl-3(2H)-pyridazinone, 2.575 g of 2-ethylphenylboronic acid and 3.333 g of sodium carbonate were added 30 mL of 1,4-dioxane and 20 mL of water. To the mixture were added 2.417 g of tetrabutylammonium bromide and 0.657 g of tetrakis(triphenylphosphine)palladium, and then under a nitrogen atmosphere, the resulting mixture was stirred and heated under reflux for 17 hours. After cooling, 50 mL of water was added to the reaction mixture, which was extracted with 100 mL of ethyl acetate and then 30 mL of ethyl acetate. The extracts were combined, washed with a saturated sodium chloride aqueous solution and dried over anhydrous magnesium sulfate, and the solvent was distilled off. The solid obtained was washed with a mixed solvent of ethyl acetate and hexane (1:2) to yield 3.238 g of the title compound as yellow crystals.
The compound which was produced according to Reference example 1 will be shown in Table 4.
The compound represented by the formula (II):
A typical example of the preparation of the compound represented by the formula (V-a) is shown in Reference example 2.
15.5 mL of butyl lithium (1.6 mol/L solution in hexane) was placed in a reaction vessel, which was chilled in a dry ice-acetone bath. To this was added a solution of 4.412 g of 2-propylbromobenzene in 45 mL of tetrahydrofuran at -70 °C dropwise over 85 minutes under a nitrogen atmosphere. The mixture was stirred at -70 °C for 30 minutes, to which 3. 75 mL of trimethyl borate was then added at -70°C dropwise over 15 minutes. The mixture was stirred at -70 °C for one hour and then at room temperature for 18 hours. To the reaction mixture was added 33 mL of 2N hydrochloric acid dropwise over 10 minutes and then the mixture was stirred at room temperature for 4 hours. To the mixture was added 20 mL of water, which was extracted with 70 mL of ethyl acetate. The extract was washed with a saturated sodium chloride aqueous solution and dried over anhydrous magnesium sulfate, and the solvent was distilled off. The residue was subjected to a silica gel column chromatography (as eluent, ethyl acetate : hexane = 1:2, and then 2:1) to yield 1.641 g of the title compound as colorless crystals.
1H-NMR(CDCl3)δ ppm: 1.01(3H,t,J=7.4Hz), 1.69-1.79(2H,m), 3.15-3.20(2H,m), 4.0-6.0(2H,br.), 7.28-7.33(2H,m), 7.47(1H,dt,J=1.5,7.6Hz), 8.20-8.23(1H,m).
Among the compounds represented by the formula (V-a), the following ones were produced by the manner similar to Reference example 2.
2-Ethyl-6-methylphenylboronic acid
m.p. :90-91°C
1H-NMR(CDCl3)δ ppm: 1.22(3H,t,J=7.6Hz), 2.35(3H,s), 2.64(2H,q,J=7.6Hz), 4.0-5.5(2H,br.), 6.98(1H,d,J=7.7H2), 7.01(1H,d,J=7.7Hz), 7.18(1H,t,J=7.7Hz).
2,6-Diethyl-4-methylphenylboronic acid
m.p.: 111-113°C
1H-NMR(CDCl3)δ ppm: 1.23(6H,t,J=7.7Hz), 2.31(3H,s), 2.63(4H,q,J=7.7Hz), 4.0-5.0(2H,br.), 6.88(2H,s).
A typical example of the preparation of the compound represented by the formula (VI) is shown in Reference example 3.
1.5 g of potassium carbonate was added to a solution of 2.0 g of ethyl 2-(methylhydrazono)propanoate in 35 mL of acetonitrile. The mixture was stirred under cooling with ice, to which a solution of 2.6 g of 2, 6-diethyl-4-methylphenylacetyl chloride in 10 mL of acetonitrile was added dropwise over about 20 minutes. The resulting mixture was further stirred for 3.5 hours at room temperature, and then concentrated under reduced pressure. To the residue obtained was added 20 mL of ice-water, which was extracted with ethyl acetate (20 mL x 3). The extracts were combined, washed with a saturated sodium chloride aqueous solution (20 mL x 2), dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue obtained was subjected to basic alumina column chromatography (ethyl acetate : hexane = 1 : 3 as eluent) to yield 1.9 g of the title compound as white crystals.
The compound which was produced according to Reference example 3 will be shown in Table 5.
The compound represented by the formula (VI):
are mixed to yield an emulsifiable concentrate. The emulsifiable concentrate prepared is used after properly diluted with water. Compounds I-a-2 to I-a-23 and I-b-1 to I-b-23 instead of Compound I-a-1 are similarly formulated to yield the emulsifiable concentrate for each compound.
are pulverized and mixed to yield wettable powder. The wettable powder prepared is used after properly diluted with water.
are mixed, kneaded with water and palletized to yield granules.
Ten parts of Compound (I-a-12), 10 parts of any one of the compound selected from the following Group A, 4 parts of sodium laurylsulfate, 2 parts of calcium ligninsulfonate, 20 parts of synthetic hydrated silica and 54 parts of diatomaceous earth are pulverized and mixed well to give each wettable powders.
2,4-PA, MCP, MCPB, phenothiol, mecoprop, fluroxypyr, triclopyr, clomeprop, naproanilide,
2,3,6-TBA, dicamba, clopyralid, picloram, aminopyralid, quinclorac, quinmerac,
diuron, linuron, chlortoluron, isoproturon, fluometuron, isouron, tebuthiuron, methabenzthiazuron, cumyluron, daimuron, methyl-daimuron,
atrazine, ametoryn, cyanazine, simazine, propazine, simetryn, dimethametryn, prometryn, metribuzin, triaziflam,
paraquat, diquat,
bromoxynil, ioxynil,
pendimethalin, prodiamine, trifluralin,
amiprofos-methyl, butamifos, bensulide, piperophos, anilofos, glyphosate, glufosinate, bialaphos,
di-allate, tri-allate, EPTC, butylate, benthiocarb, esprocarb, molinate, dimepiperate, swep, chlorpropham, phenmedipham, phenisopham, pyributicarb, asulam,
propanil, propyzamide, bromobutide, etobenzanid,
acetochlor, alachlor, butachlor, dimethenamid, propachlor, metazachlor, metolachlor, pretilachlor, thenylchlor, pethoxamid,
acifluorfen-sodium, bifenox, oxyfluorfen, lactofen, fomesafen, chlomethoxynil, aclonifen,
oxadiazon, cinidon-ethyl, carfentrazone-ethyl, surfentrazone, flumiclorac-pentyl, flumioxazin, pyraflufen-ethyl, oxadiargyl, pentoxazone, fluthiacet-methyl, butafenacil, benzfendizone,
benzofenap, pyrazolate, pyrazoxyfen, topramezone, pyrasulfotole,
isoxaflutole, benzobicyclon, sulcotrione, mesotrione, tembotrione, tefuryltrione,
clodinafop-propargyl, cyhalofop-butyl, diclofop-methyl, fenoxaprop-ethyl, fluazifop-butyl, haloxyfop-methyl, quizalofop-ethyl, metamifop,
alloxydim-sodium, sethoxydim, butroxydim, clethodim, cloproxydim, cycloxydim, tepraloxydim, tralkoxydim, profoxydim,
chlorsulfuron, sulfometuron-methyl, metsulfuron-methyl, chlorimuron-ethyl, tribenuron-methyl, triasulfuron, bensulfuron-methyl, thifensulfuron-methyl, pyrazosulfuron-ethyl, primisulfuron-methyl, nicosulfuron, amidosulfuron, cinosulfuron, imazosulfuron, rimsulfuron, halosulfuron-methyl, prosulfuron, ethametsulfuron-methyl, triflusulfuron-methyl, flazasulfuron, cyclosulfamuron, flupyrsulfuron, sulfosulfuron, azimsulfuron, ethoxysulfuron, oxasulfuron, iodosulfuron-methyl-sodium, foramsulfuron, mesosulfuron-methyl, trifloxysulfuron, tritosulfuron,
dmazamethabenz-methyl, imazamethapyr, imazamox, imazapyr, imazaquin, imazethapyr, orthosulfamuron, flucetosulfuron,
flumetsulam, metosulam, diclosulam, florasulam, cloransulam-methyl, penoxsulam, pyroxsulam,
pyrithiobac-sodium, bispyribac-sodium, pyriminobac-methyl, pyribenzoxim, pyriftalid, pyrimisulfan,
bentazon, bromacil, terbacil, chlorthiamid, isoxaben, dinoseb, amitrole, cinmethylin, tridiphane, dalapon, diflufenzopyr-sodium, dithiopyr, thiazopyr, flucarbazone-sodium, propoxycarbazone-sodium, mefenacet, flufenacet, fentrazamide, cafenstrole, indanofan, oxaziclomefone, benfuresate, ACN, pyridate, chloridazon, nozflurazon, flurtamone, diflufenican, picolinafen, beflubutamid, clomazone, amicarbazone, pinoxaden, pyraclonil, pyroxasulfone, thiencarbazone-methyl,
furilazole, dichlormid, benoxacor, allidochlor, isoxadifen-ethyl, fenchlorazole-ethyl, mefenpyr-diethyl, cloquintocet-mexyl, fenclorim, cyprosulfamide, cyometrinil, oxabetrinil, fluxofenim, flurazole and 1,8-naphthalic anhydride.
Ten parts of Compound (I-a-13), 10 parts of any one of the compound selected from the above-mentioned Group A, 4 parts of sodium laurylsulfate, 2 parts of calcium ligninsulfonate, 20 parts of synthetic hydrated silica and 54 parts of diatomaceous earth are pulverized and mixed well to give each wettable powders.
Ten parts of Compound (I-a-14), 10 parts of any one of the compound selected from the above-mentioned Group A, 4 parts of sodium laurylsulfate, 2 parts of calcium ligninsulfonate, 20 parts of synthetic hydrated silica and 54 parts of diatomaceous earth are pulverized and mixed well to give each wettable powders.
Ten parts of Compound (I-a-15), 10 parts of any one of the compound selected from the above-mentioned Group A, 4 parts of sodium laurylsulfate, 2 parts of calcium ligninsulfonate, 20 parts of synthetic hydrated silica and 54 parts of diatomaceous earth are pulverized and mixed well to give each wettable powders.
Ten parts of Compound (I-a-16), 10 parts of any one of the compound selected from the above-mentioned Group A, 4 parts of sodium laurylsulfate, 2 parts of calcium ligninsulfonate, 20 parts of synthetic hydrated silica and 54 parts of diatomaceous earth are pulverized and mixed well to give each wettable powders.
Ten parts of Compound (I-a-17), 10 parts of any one of the compound selected from the above-mentioned Group A, 4 parts of sodium laurylsulfate, 2 parts of calcium ligninsulfonate, 20 parts of synthetic hydrated silica and 54 parts of diatomaceous earth are pulverized and mixed well to give each wettable powders.
Ten parts of Compound (I-a-18), 10 parts of any one of the compound selected from the above-mentioned Group A, 4 parts of sodium laurylsulfate, 2 parts of calcium ligninsulfonate, 20 parts of synthetic hydrated silica and 54 parts of diatomaceous earth are pulverized and mixed well to give each wettable powders.
Ten parts of Compound (I-a-19), 10 parts of any one of the compound selected from the above-mentioned Group A, 4 parts of sodium laurylsulfate, 2 parts of calcium ligninsulfonate, 20 parts of synthetic hydrated silica and 54 parts of diatomaceous earth are pulverized and mixed well to give each wettable powders .
Ten parts of Compound (I-b-12), 10 parts of any one of the compound selected from the above-mentioned Group A, 4 parts of sodium laurylsulfate, 2 parts of calcium ligninsulfonate, 20 parts of synthetic hydrated silica and 54 parts of diatomaceous earth are pulverized and mixed well to give each wettable powders.
Ten parts of Compound (I-b-14), 10 parts of any one of the compound selected from the above-mentioned Group A, 4 parts of sodium laurylsulfate, 2 parts of calcium ligninsulfonate, 20 parts of synthetic hydrated silica and 54 parts of diatomaceous earth are pulverized and mixed well to give each wettable powders.
Ten parts of Compound.(I-b-16), 10 parts of any one of the compound selected from the above-mentioned Group A. 4 parts of sodium laurylsulfate, 2 parts of calcium ligninsulfonate, 20 parts of synthetic hydrated silica and 54 parts of diatomaceous earth are pulverized and mixed well to give each wettable powders.
Ten parts of Compound (I-b-18), 10 parts of any one of the compound selected from the above-mentioned Group A, 4 parts of sodium laurylsulfate, 2 parts of calcium ligninsulfonate, 20 parts of synthetic hydrated silica and 54 parts of diatomaceous earth are pulverized and mixed well to give each wettable powders.
Ten parts of Compound (I-b-19), 10 parts of any one of the compound selected from the above-mentioned Group A, 4 parts of sodium laurylsulfate, 2 parts of calcium ligninsulfonate, 20 parts of synthetic hydrated silica and 54 parts of diatomaceous earth are pulverized and mixed well to give each wettable powders.
Ten parts of Compound (I-b-20), 10 parts of any one of the compound selected from the above-mentioned Group A, 4 parts of sodium laurylsulfate, 2 parts of calcium ligninsulfonate, 20 parts of synthetic hydrated silica and 54 parts of diatomaceous earth are pulverized and mixed well to give each wettable powders.
Ten parts of Compound (I-b-21), 10 parts of any one of the compound selected from the above-mentioned Group A, 4 parts of sodium laurylsulfate, 2 parts of calcium ligninsulfonate, 20 parts of synthetic hydrated silica and 54 parts of diatomaceous earth are pulverized and mixed well to give each wettable powders.
Ten parts of each of Compound (I-a-12), (I-a-13), (I-a-14), (I-a-15), (1-a-16), (I-a-17), (I-a-18), (I-a-19), (I-b-12), (I-b-14), (I-b-16), (I-b-18). (I-b-19), (I-b-20) or (I-b-21); 10 parts of flumioxazine: 4 parts of sodium laurylsulfate; 2 parts of calcium ligninsulfonate; 20 parts of synthetic hydrated silica and 54 parts of diatomaceous earth are pulverized and mixed well to give each wettable powders.
Five parts of each of Compound (I-a-12), (I-a-13), (I-a-14), (I-a-15), (I-a-16), (I-a-17), (I-a-18), (I-a-19), (I-b-12), (I-b-14), (I-b-16), (I-b-18), (I-b-19), (I-b-20) or (I-b-21); 25 parts of glyphosate; 4 parts of sodium laurylsulfate; 2 parts of calcium ligninsulfonate; 20 parts of synthetic hydrated silica and 44 parts of diatomaceous earth are pulverized and mixed well to give each wettable powders.
A plastic cup with a diameter of 8 cm and a depth of 6.5 cm was filled with commercially available soil, onto which seeds of Lolium multiflorum were sowed, covered with soil about 0.5 cm high and then grown in a greenhouse. When the plants were grown in first to second leaf stage, a prescribed dosage of a dilute liquid formulation comprising Compound I-a-1 was sprayed to whole plants uniformly. The dilute liquid formulation was prepared by dissolving a prescribed amount of Compound I-a-1 in a dimethylformamide solution (2%) of Tween 20 (polyoxyethylene sorbitan fatty acid ester, from MP Biomedicals, Inc.) and then diluting with deionized water. The plants after treatment with the liquid formulation were grown in a greenhouse and 20 days after the treatment, the efficacy of the compound against Lolium multiflorum was visually evaluated by rating in eleven levels from 0 to 10 (assigned as 0 for no effect and 10 for complete death while values falling in between these values were rated from 1 to 9 levels accordingly).
The other present compounds and Compound A described in
As a result, Compounds I-a-1, I-a-5, I-a-6, I-a-7, I-a-8, I-a-9, I-a-12, I-b-1, I-b-2, I-b-4, I-b-5, I-b-7, I-b-10 and I-b-11 showed the effect equal to 7 or more at a treatment dosage of 500 g/ha, whereas Compounds I-a-13, I-a-14, I-a-15, I-a-16, I-a-17, I-a-18, I-a-19, I-a-20, I-a-21, I-a-22, I-a-27, I-b-12, I-b-13, I-b-14, I-b-16, I-b-17, I-b-18, I-b-20, I-b-21, I-b-22, I-b-23 and I-b-25 showed the ef fect equal to 7 or more at a treatment dosage of 250 g/ha. By contrary, Compound A showed the effect to be 1 at a treatment dosage of 500 g/ha.
A plastic container (32 cm x 22 cm x 8 cm in height) was filled with soil sterilized by steam, onto which seeds of Apera spica-venti were sowed and covered with soil about 0.5 cm high. A prescribed dosage of a dilute liquid formulation comprising Compound I-a-1 was sprayed to the soil surface uniformly. The dilute liquid formulation was prepared by the method similar to that in Test example 1. The plants after treatment with the liquid formulation were grown in a greenhouse and three weeks after the treatment, the efficacy of the compound against Apera spica-venti was visually evaluated by rating in eleven levels from 0 to 10 similarly to Test example 1.
The other present compounds and Compound A as a comparative example were similarly tested.
As a result, Compounds I-a-1, I-a-2, I-a-4, I-a-5, I-a-6, I-a-8, I-a-9, I-a-10, I-b-1, I-b-5, I-b-6, I-b-7 and I-b-11 showed the effect equal to 8 or more at a treatment dosage of 500 g/ha, whereas Compounds I-a-12, I-a-13, I-a-14, I-a-15, I-a-16, I-a-17, I-a-18, I-a-19, I-a-20, I-a-21, I-a-22, I-a-23, I-b-13, I-b-14, I-b-16, I-b-18, I-b-19, I-b-20, I-b-21, I-b-22 and I-b-23 showed the effect equal to 8 or more at a treatment dosage of 250 g/ha. By contrary, Compound A showed the effect to be 1 at a treatment dosage of 500 g/ha.
The present compound has an excellent effect on weed control and is useful as an active ingredient of herbicides.
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