PYRIDINE DERIVATIVES AND HERBICIDAL COMPOSITION

Abstract: A pyridine derivative having the formula: wherein one of A, B, D and E is oxygen, sulfur, -SO-, -SO₂-, -NR³-, -- or = CH- with the rest being all carbon atoms: X is halogen, C₁-C₄ alkyl, C₁-C₄ alkoxy, C₁-₄ haloalkyl, C₁-C₄ haloalkoxy, C₁-C₄ alkylthio, C₁-C₄ haloalkylthio, C₁-C₄ alkoxycarbonyl, C₁-C₄ alkylthioalkyl, tetrahydro­ thiopyranyl, hydroxyl, CF₃, phenyl or pyridyl; n is an integer of from 0 to 6,; W is oxygen or sulfur; R is hydrogen, di-lower alkylimino, C₁-C₅ alkyl, C₂-C₅ alkenyl, C₂-C₅ alkynyl, C₄ or C₅ oxacycloalkyl, C₂-C₅ mono-, di- or tri-haloalkenyl, C₂-C₅ haloalkynyl, glycidyl, furfuryl, alkylthioalkyl, C₃-C₆ cy­ cloalkyl or a cation R¹ is C₁-C₄ alkyl, R² is C₁-C₄ alkyl or C₃-C₆ cycloalkyl, or R¹ and R² together with the adjacent carbon atom, form C₃-C₆ cycloalkyl; and R³ is hydrogen or C₁-C₃ alkyl.

Description: The present invention relates to a novel 2-(2-imidazolin-2-yl)pyridine-3-carboxylic acid derivative, according to claim 1 and a herbicidal composition containing said derivative. It is generally accepted that the costs for the use of a herbicide are dependent on the amount of the active ingredient required per a unit surface area, and a development of a new herbicide which is effective at a low dose, has been desired. On the other hand, with the conventional herbicides, adverse effects are sometimes given to the crop plants during the use, and researches for the compounds having high herbicidal activities at a low dose and having high selectivity as between the crop plants and unwanted weeds, have been conducted for many years. For instance, EP-A-0041623 and EP-A-0127883 disclose 2-(2-imidazolin-2-yl) pyridine-3-carboxylic acid derivatives. Furthermore EP-A-227 932 discloses (2-imidazolin-2-yl) fused heteropyridine compounds and EP-A-95 105 discloses 5,6,7,8-tetrahydroquinolines. However, these derivatives do not necessarily satisfy the above requirements. The present inventors have conducted extensive researches for many years, and have finally found that the compound of the present invention has remarkable herbicidal activities as compared with conventional herbicides, and the compound of the present invention is practically useful as having superior selectivity for crop plants particularly for leguminous plants such as soybean ( Glysine max ), peanut ( Arachis hypogaea ), alfalfa ( Medicage sativa ), French bean ( Phaseolus vulgaris ), adzuki bean ( Vigna angularis ) and pea ( Pisum sativum ). Further, it has been found that it has excellent herbicidal activities against important weeds such as morning glory ( Ipomoea spps. ), Johnsongrass ( Sorghum halepense ), velvetleaf ( Abutilon theophrasti ) and prickly sida ( Sida spinosa ), and it has a wide herbicidal spectrum including broad leaf weeds, gramineous weeds and cyperaceous weeds and has a wide range of application period ranging from soil treatment to foliage treatment. The present invention has been accomplished on the basis of these discoveries. Namely, with the compound of the present invention, the dose of the active ingredient per unit surface area can be remarkably reduced as compared with the conventional herbicides, and the phytotoxicity to the crop plants is substantially less as compared with the conventional herbicides. Thus, the economical advantage is substantial. Further, with the compound of the present invention, the danger of environmental pollution by the application of the herbicide in a substantial amount can be minimized, and adverse effects to other crop plants due to the residual effects are minimum. The present invention provides a pyridine derivative having the formula: or its optical isomers. The compound of the present invention is a novel compound not disclosed in any prior literature, and has excellent physiological activities as herbicides. The compound of the present invention is obtainable by a process which comprises (A) cyclizing a compound having the formula: wherein R¹ is a methyl group, and R² is a isopropyl group, and R is a hydrogen atom, a di-lower alkylimino group, a C₁-C₅ alkyl group (which may be substituted by C₁-C₃ alkoxy, hydroxyl, C₃-C₆ halocycloalkyl, carboxyl, lower alkoxycarbonyl, cyano, dialkylphosphonyl, halogen, benzyloxy, tri-lower alkylammonium or phenyl which may be substituted by halogen, C₁-C₄ alkyl, C₁-C₄ alkoxy or nitro), a C₂-C₅ alkenyl group (which may be substituted by C₁-C₃ alkoxy, lower alkoxycarbonyl, two C₁-C₃ alkoxy or phenyl), a C₂-C₅ alkynyl group, a C₄ or C₅ oxacycloalkyl group, a C₂-C₅ mono-, di- or tri-haloalkenyl group, a C₂-C₅ haloalkynyl group, a glycidyl group, a furfuryl group, an alkylthioalkyl group, a C₃-C₆ cycloalkyl group which may be substituted by C₁-C₃ alkyl, or a cation selected from the group consisting of an alkali metal ion, an alkaline earth metal ion, an ammonium ion or a quaternary ammonium ion; and Z is or -CN, wherein W is an oxygen atom, and if necessary, subjecting the resulting cyclized product to hydrolysis, esterification, ester exchange or conversion to an alkali metal, alkaline earth metal, ammonium or quaternary ammonium salt; or (B) reacting a compound having the formula: wherein W, R¹ and R² are as defined above, with an alcohol having the formula ROH wherein R is as defined above but other than a hydrogen atom, and if necessary, subjecting the resulting product to hydrolysis, esterification, ester exchange or conversion to an alkali metal, alkaline earth metal, ammonium or quaternary ammonium salt. Further, the present invention provides a herbicidal composition comprising a herbicidally effective amount of the pyridine derivative of the present invention or its optical isomer, and a carrier therefore. The herbicidal composition may further contain another herbicide or agricultural chemical which is commonly employed. Still further, the present invention provides a method for controlling weeds, which comprises applying to the weeds or to the locus of the weeds an effective amount of the pyridine derivative or its optical isomer. Now, the present invention will be described in detail. The compound of the present invention may be readily prepared by the following reaction. Reaction Scheme 1 wherein Z is and, W, R, R¹ and R² are as defined above. Namely, the compound of the formula II-a wherein R is a hydrogen atom and Z is is heated in an aqueous solution containing from 1 to 50% (from 1 to 10 equivalent mols) of an alkali metal hydroxide or an alkaline earth metal hydroxide, such as sodium hydroxide, potassium hydroxide or magnesium hydroxide, at a temperature of from room temperature to 100 o C, whereby a compound of the formula I wherein R is sodium, potassium, magnesium or calcium can be obtained. By neutralizing the product with a mineral acid such as hydrochloric acid or sulfuric acid, a compound of the formula I wherein R is a hydrogen atom can be obtained. Further, by treating the product with ammonia or an organic amine, a compound of the formula I wherein R is an ammonium ion or a quaternary ammonium ion can be obtained. Further, a compound of the formula I wherein R is a hydrogen atom may be esterified with an alcohol of the formula ROH wherein R is as defined above but other than a hydrogen atom, in the presence of an acid catalyst, to obtain compounds of the formula I having various R other than a hydrogen atom. Likewise, a compound of the formula I wherein R is a methyl group or an ethyl group may be obtained by treating a compound of the formula I wherein R is a hydrogen atom, with diazomethane in an inert solvent, or by treating it with methyl iodide, methyl chloride, methyl bromide, dimethyl sulfate, ethyl iodide, ethyl bromide, ethyl chloride, diethyl sulfate, triethyloxonium tetrafluoroborate or trimethyloxonium tetrafluoroborate. Further, the product may be subjected to ester exchange with an alcohol of the formula ROH where R is any one of various types as mentioned above other than a hydrogen atom, to obtain compounds of the formula I having various R other than a hydrogen atom. In a similar manner, a compound of the formula II-a wherein R is an alkali metal ion, an alkaline earth metal ion, an ammonium ion or a quaternary ammonium ion, can be cyclized directly to obtain the corresponding compound of the formula I. The starting compound of the formula II-a wherein R is a hydrogen atom can be prepared by the following method A. Method A wherein Q is -N(CH₃)₂, -N(CH₂CH₃)₂, or Z is and,, R, R¹ and R² are as defined above. Namely, the enamine compound of the formula IV can be obtained in good yield by reacting a compound of the formula III prepared in accordance with e.g. the Journal of Organic Chemistry, 36 , 2077 (1971) or Journal of the American Chemical Society, 74 , 1569 (1952), with a secondary amine (such as pyrrolidine, piperidine, morpholine, diethylamine or dimethylamine) in accordance with the method disclosed in e.g. Synthesis 368 (1978). This enamine compound of the formula IV is reacted with ethyl ethoxymethyleneoxaloacetate in a suitable solvent (such as ethanol, acetic acid or benzene), and then ammonium acetate is added and reacted thereto under heating and stirring, whereby diethyl pyridine-2,3-dicarboxylate of the formula V can be obtained in good yield. Alternatively, a compound of the formula IV' wherein A is can be prepared from a compound of the formula III wherein A is in good yield in accordance with the method disclosed in e.g. Synthesis 902 (1983). Then, the pyridine-2,3-dicarboxylic acid diester of the formula V wherein A is can be obtained in good yield by reacting the compound of the formula IV' wherein A is with an ethoxymethyleneoxaloacetic acid ester in a suitable solvent (such as diethyl ether, ethanol, acetic acid or benzene) in accordance with Journal of the American Chemical Society, 73 , 4380 (1951) or Journal of the American Chemical Society, 74 , 1489 (1952). Futhermore, the diester of the formula V wherein A is may be reduced in a suitable solvent, preferably in diethyl ether, methanol or an aqueous solvent, by using a metal hydride such as sodium borohydride, to obtain a compound of the formula V wherein A is -CH(OH)-. Still further, a compound of the formula V wherein E is -CH(OH)- can be obtained in accordance with e.g. Journal of the American Chemical Society, 76 , 1286 (1954) from a 5,6,7,8-tetrahydroquinoline derivative which can be prepared in accordance with e.g. Journal of the Chemical Society Chemical Communications, 133 (1982). These compounds of the formula V wherein A or E is -CH(OH)- may be dehydrated by using a suitable dehydrating agent, preferably sulfuric acid, a sulfate or paratoluene sulfonic acid, to obtain compounds of the formula V wherein A or E is =CH-. The diester or the formula V is treated with a water-alcohol solution containing at least two mols of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide to obtain the corresponding dicarboxylic acid of the formula VI. The dicarboxylic acid of the formula VI is then heated with acetic anhydride or trifluoroacetic anhydride at a temperature of from room temperature to the refluxing temperature, preferably at a temperature of from 60 to 100 o C, to obtain the corresponding acid anhydride of the formula VII. This acid anhydride of the formula VII is reacted with an α-aminoamide of the formula VIII in a suitable solvent (such as acetonitrile, methylene chloride, pyridine or picoline), whereby a carboxylic acid amide derivative of the formula II-a wherein R is a hydrogen atom and Z is can be obtained. In some cases, the isomer carboxylic acid amide derivative of the formula II-a' wherein R is a hydrogen atom, and Z is is produced as a by-product. wherein R is a hydrogen atom, Z is and W, R¹ and R² are as defined above. Reaction Scheme 2 wherein R is a methyl group of an ethyl group, Z is and W, R¹ and R² are as defined above. Namely, a compound of the formula I wherein R is a methyl group or an ethyl group, can be obtained by treating a compound of the formula II-a wherein R is a methyl group or an ethyl group, with e.g. phosphorus pentachloride, sodium hydride, sodium methoxide or sodium ethoxide in an inert solvent such as benzene, hexane or ethyl ether. Alternatively, a compound of the formula I wherein R is a methyl group or an ethyl group may be obtained by treating a compound of the formula II-a wherein R is a methyl group or an ethyl group, with a dehydrating condensation agent such as dicyclohexylcarbodimide or acetic anhydride in a suitable solvent, preferably in dichloroethane, dichloromethane, chloroform, carbon tetrachloride, tetrahydrofuran or acetic acid. The compound of the formula I wherein R is a methyl group or an ethyl group can be hydrolyzed to a compound of the formula I wherein R is a hydrogen atom. Further, as described with reference to Reaction Scheme 1, the compound of the formula I wherein R is a hydrogen atom can be converted to the compound of the present invention by esterification. In a similar manner, a compound of the formula II-a wherein R is other than a hydrogen atom, an alkali metal ion, an alkaline earth metal ion, an ammonium ion and the quaternary ammonium ion, can be cyclized directly to obtain the corresponding compound of the formula I. The starting compound of the formula II-a wherein R is a methyl group or an ethyl group and Z is can be prepared in accordance with the following method B. Method B-1 Method B-2 wherein R is a methyl group or an ethyl group; Z is and, W, R¹ and R² are as defined above. Namely, a half ester of the formula IX wherein R is a methyl group or an ethyl group can he prepared either by the semi-hydrolysis of the corresponding diester of the formula V wherein R is a methyl group or an ethyl group, or by the methanol or ethanol decomposition of the acid anhydride of the formula VII. The compound of the formula IX wherein R is a methyl group or an ethyl group is converted by thionyl chloride to the acid chloride or by chloroformic acid ester to an active ester, followed by the reaction with an α-aminoamide of the formula VIII to obtain a compound of the formula II-a wherein R is a methyl group or an ethyl group, and Z is Alternatively, the acid anhydride of the formula VII and the α-aminonitrile of the formula XII are reacted in an inert solvent, and after the removal of the solvent, heated in an acetic anhydride solvent in the presence of a catalytic amount of sodium acetate or potassium acetate, to obtain a compound of the formula X. Then, the compound of the formula X is treated with a strong acid such as sulfuric acid, if necessary, in a halogenated hydrocarbon solvent such as chloroform, methylene chloride or carbon tetrachloride, to obtain a compound of the formula XI wherein W is an oxygen atom. The compound of the formula XI wherein W is an oxygen atom is then treated with a methoxy or ethoxy anion in the presence of a methanol or ethanol, whereby a compound of the formula II-a wherein R is a methyl or ethyl group is obtainable. In a similar manner, a compound of the formula II-a wherein R is other than a hydrogen atom, an alkali metal ion, an alkaline earth metal ion, an ammonium ion, and a quaternary ammonium ion, can be obtained directly from the corresponding compound. Reaction Scheme 3 wherein W, R, R¹ and R² are as defined above. Namely, a compound of the formula II-b or II-c is reacted with an alcohol of the formula ROH where R may be any one of various groups as identified above other than a hydrogen atom in an inert aprotic solvent such as tetrahydrofuran or dioxane at a temperature of from about 20 to 50 o C, if necessary, in the presence of sodium hydride or an organic base such as triethylamine, as the catalyst, to obtain a compound of the formula I wherein R is other than a hydrogen atom. Otherwise, a compound of the formula II-b or II-c is reacted in an alcohol solvent of the formula ROH wherein R is any one of various groups other than a hydrogen atom at a temperature of from about 20 o C to the refluxing temperature, if necessary, with an addition of an alkali metal alkoxide such as sodium alkoxide (RONa) or potassium alkoxide (ROK), or with an addition of an organic base such as DBU (1,8-diazabicyclo[5,4,0]-7-undecene), to obtain a compound of the formula I wherein R is other than a hydrogen atom. The compound of the formula I can be converted by hydrolysis to a compound of the formula I wherein R is a hydrogen atom. Further, as described with reference to Reaction Scheme 1, the compound of the formula I wherein R is a hydrogen atom can be converted to the compound of the present invention by esterification. The starting compounds of the formulas II-b and II-c can be prepared by Method C. Method C wherein, W, R, R¹ and R² are as defined above. Namely, a compound of the formula I wherein R is a hydrogen atom is treated with a dehydrating condensation agent such as dicyclohexyl carbodiimide or acetic anhydride in a suitable solvent (such as dichloroethane, dichloromethane, tetrahydrofuran or acetic acid) to obtain a compound of the formula II-b or II-c. Otherwise, a compound of the formula XI is treated with an alkali metal hydride such as sodium hydride or with a base such as DBU (1,8-diazabicyclo[5,4,0]-7-undecene) in an aromatic hydrocarbon solvent such as benzene, toluene or xylene, to obtain a compound of the formula II-c. Reaction Scheme 4 wherein, W, Z, R, R¹ and R² are as defined above. Namely, a compound of the formula II-a wherein R is a hydrogen atom and Z is CN, is reacted with from 2 to 10 equivalent mols of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide in water with an aprotic polar solvent such as dimethylsulfoxide or in an aqueous solution of a C₁-C₄ alcohol at a temperature of from 25 to 110 o C, if necessary, with an addition of from 2 to 5 equivalent mols of an aqueous hydrogen peroxide solution having a concentration of from 30 to 90%, and then, the reaction mixture is acidified with a mineral acid such as hydrochloric acid or sulfuric acid to obtain a compound of the formula I wherein R is a hydrogen atom and W is an oxygen atom. Further, as described with respect to Reaction Scheme 1, the compound of the formula I wherein R is a hydrogen atom can be converted to the compound of the present invention by esterification. In a similar manner, a compound of the formula II-a wherein R is an alkali metal ion, an alkaline earth metal ion, an ammonium ion or a quaternary ammonium ion, can be cyclized directly to obtain the corresponding compound of the formula I. The starting compound of the formula II-a wherein R is a hydrogen atom and Z is CN, can he prepared by the following Method D. Method D wherein R is a hydrogen atom, Z is a nitrile group, W is an oxygen atom, and R¹ and R² are as defined above. Namely, a compound of the formula VII and a compound of the formula XII are reacted in a suitable solvent, preferably in diethyl ether, tetrahydrofuran, dimethoxyethane, acetonitrile or a low boiling halogenated hydrocarbon, in an inert gas stream at a temperature of from 20 to 60 o C, to obtain a compound of the formula II-a wherein R is a hydrogen atom and Z is CN. Sometimes, an isomer carboxylic acid amide derivative of the formula II-a' may be produced as a by-product. wherein R is a hydrogen atom, Z is a nitrile group, and R¹ and R² are as defined above. Synthetic Example 1 Preparation of 5.2 g (52 mmol) of tetrahydropyran-3-one and 4.25 g (59 mmol) of pyrrolidine were heated and refluxed in 100 ml of benzene for 3 hours by an aid of a Dean Stark trap. The solvent was distilled off under reduced pressure, whereby the presence of two types of enamine products was confirmed by NMR. 7.7 g (50 mmol) of the enamine products were dissolved in 150 ml of anhydrous ethanol, and 15.2 g (62 mmol) of ethyl ethoxymethylene oxaloacetate was dropwise added thereto. The mixture was stirred at room temperature for 2 hours. Then, 14.8 g (0.21 mol) of ammonium acetate was added thereto. The mixture was refluxed under heating and stirring for 1 hour. After cooling the mixture, the solvent was distilled off. The mixture was extracted with ethyl acetate, and the extract was dried. The solvent was distilled off under reduced pressure, and the residue was purified by column chromatography to obtain 3.3 g of a mixture of the above identified diester product and its isomer. From the NMR analysis, the ratio was found to be 2 : 1. NMR (δ value CDCl₃)) of the above identified compound 1.37 (t, 3H), 1.39 (t, 3H), 2.21 (dd, 2H), 3.04 (t, 2H), 4.2-4.5 (m, 2H), 4.30 (g, 2H), 4.35 (q, 2H), 7.45 (s, 1H) NMR (δ value (CDCl₃)) of the isomer 1.38 (t, 3H), 1.40 (t, 3H), 2.97 (t, 2H), 4.0 (t, 2H), 4.37 (q, 2H), 4.42 (q, 2H), 4.82 (s, 2H), 7.95 (s, 1H) Synthetic Example 2 Preparation of 3.2 g (11.4 mmol) of the mixture of two types of diesters obtained in Synthetic Example 1 was added to a solution mixture comprising 2 ml of water and 30 ml of ethanol with 1.8 g (85%, 27.5 mmol) of potassium hydroxide dissolved therein, and the mixture was stirred at 60 o C for 2 hours. After cooling, the mixture was concentrated under reduced pressure. After an addition of water, the insoluble substances were filtered off. The filtrate was acidified with hydrochloric acid, whereby crystals precipitated. The crystals were collected by filtration and dried to obtain 1.8 g of a mixture of the above identified dicarboxylic acids. From the NMR analysis, the ratio was 3 : 2. NMR of (δ value (DMSO-d₆)) 2.11 (dd, 2H), 2.95 (t, 2H), 4.22 (t, 2H), 7.37 (s, 1H), 9.2-10.1 (b, 2H) NMR of (δ value (DMSO-d₆)) 2.97 (t, 2H), 3.93 (t, 2H), 4.70 (s, 2H), 7.93 (s, 1H), 9.2-10.1 (b, 2H) Synthetic Example 3 Preparation of 1.8 g (7.9 mmol) of a mixture of the two isomers of the pyridine dicarboxylic acid prepared in Synthetic Example 2 was heated and stirred in 30 ml of acetic anhydride at 110 o C for 1 hour and 30 minutes. The mixture was cooled and concentrated under reduced pressure. Toluene was added to the residue, and the mixture was concentrated under reduced pressure to obtain 1.6 g of a mixture of the corresponding two types of two isomers of the pyridine dicarboxylic acid anhydride. The acid anhydride was dissolved in 60 ml of acetonitrile, and 1.1 g of 2-amino-2,3-dimethylbutaneamide was added thereto. The mixture was stirred at room temperature overnight. Then, the solvent was distilled off to obtain 2.7 g of a mixture of the above identified amide compounds. Pale brown crystal, m.p.: 165-173 o C (decomposed) Synthetic Example 4 Preparation of 2.7 g (7.9 mmol) of the mixture of the two isomers prepared in Synthetic Example 3 was added to 30 ml of an aqueous solution containing 1.3 g of sodium hydroxide. The mixture was heated and stirred at 80 o C for 2 hour and 30 minutes. The reaction mixture was cooled, acidified by an addition of concentrated hydrochloric acid, and extracted with chloroform. The extract was dried, and solvent was distilled off. The residue was purified by column chromatography, whereby 0.59 g (yield: 24%) of Compound No. A of the present invention and 0.18 g (yield: 7%) of Compound No. B of the present invention, were isolated respectively. Compound No. A of the present invention, White crystal, m.p.: 201-204 o C NMR (δ value (CDCl₃)): 1.91 (d, H), 2.11 (d, 3H), 1.50 (s, 3H), 1.9-2.4 (m, 1H), 2.18 (dd, 2H), 3.02 (t, 2H), 4.32 (t, 2H), 8.23 (s, 1H), 9.5-10.5 (b, 2H) Compound No. B of the present invention, White crystal, m.p.: 155-159 o C NMR (δ value (CDCl₃)): 1.92 (d, 3H), 2.12 (d, 3H), 1.52 (s, 3H), 1.95-2.4 (m, 1H), 3.07 (t, 2H), 4.03 (t, 2H), 4.82 (s, 2H), 8.75 (s, 1H), 9.2-10.2 (b, 2H) The compound which is obtainable by the above-mentioned examples 1 to 4 can be esterified by one of the above-mentioned methods in order to obtain the compound of the present invention in the form of white crystals with a melting point of from 142 to 143 o C. Test Examples. For application as herbicides, the compound of the present invention may be combined with a suitable carrier, for instance, a solid carrier such as clay, talc, bentonite or diatomaceous earth, or a liquid carrier such as water, an alcohol (such as methanol or ethanol), an aromatic hydrocarbon (such as benzene, toluene or xylene), a chlorinated hydrocarbon, an ether, a ketone, an ester (such as ethyl acetate) or an acid amide (such as dimethylformamide). If necessary, an emulsifier, a dispersant, a suspending agent, a wetting agent, an extender, a stabilizer, etc. may be added to form optional formulations such as a solution, an emulsion, a wettable powder, a dust, a granule, a flowable agent, etc. There is no particular restriction as to the content of the compound as active ingredient in these formulations. However, the content of the active ingredient is usually within a range of from 0.1 to 90.0% by weight. Further, if necessary, other types of herbicides, various insecticides, fungicides, plant growth controlling agents, assisting agents, etc. may be combined at the time of the formulation or at the time of the application of the herbicides. More specifically, the compounds of the present invention may be used in combination with the following substances: Naptalam (N-naphthylphthalamic acid), 2,4-DB (γ-(2,4-dichlorophenoxy)butyric acid), MCPB (γ-(2-methyl-4-chlorophenoxy)butyric acid), Acifluorfen-Sodium (sodium 5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitrobenzoate), Lactofen (1'-(carboethoxy)ethyl-5-[2-chloro-4-(trifluromethyl)phenoxy]-2-nitrobenzoate), fomesafen (5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitro-N-methylsulfonylbenzamide), alachlor (2-chloro-2',6'-diethyl-N-(methoxymethyl)acetanilide), metolachlor (2-chloro-2'-ethyl-6'-methyl-N-(2-methoxy-1-methylethyl)acetanilide), bentazone (3-isopropyl-(1H)-2,1,3-benzothiadiazin-4(3H)-one 2,2-dioxide), metribuzin (4-amino-6-tert-butyl-3-methylthio-1,2,4-triazin-5-(4H)-one), ethyl-2-[3-(4-chloro-6-methoxypyridmidin-2-yl) ureidosulfonyl]benzoate, imazaquim (2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)-3-quinolinic acid), 5-ethyl-2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)nicotinic acid, quizalofop-ethyl (ethyl-2-[4-(6-chloro-2-quinoxanyloxy)phenoxy]propionate), dichlofop methyl (methyl-2-[4-(2,4-dichlorophenoxy)phenoxy] propionate), fluazifop-butyl (butyl-2-[4-(5-trifluoromethyl-2-pyridyloxy)phenoxy]propionate), Sethoxydim (2-(1-ethoxyiminobutyl)-5-[2-(ethylthio)propyl]-3-hydroxycyclohex-2-enone), Fenoxaprop-ethyl (ethyl-2-[4-(6-chloro-2-benzoxazolyloxy)phenoxy]propionate), haloxyfop-methyl (methyl-2-[4-(3-chloro-5-trifluoromethyl-2-pyridyloxy)phenoxy]propionate) and toxaphene (a reaction mixture of chlorinated camphenes containing 67 - 69% chlorine). The above-mentioned other kinds of compounds to be combined with the compound of the present invention are, for instance, those disclosed in Farm Chemicals Handbook, 72nd edition (1986). The compound of the present invention can be applied for the control of various weeds not only in the agricultural and horticultural fields such as uplands, paddy fields, or orchards, but also in non-agricultural fields such as play grounds, open areas or rail road sides. The dose in its application may vary depending upon the application site, the application season, the application manner, the type of weeds to be controlled and the crop plants. However, the dose is usually within a range of from 0.005 to 10 kg per hectare as the amount of active ingredient. Now, Formulation Examples of the herbicides containing the compound of the present invention as the active ingredient, will be described. However, the formulations are not restricted to these specific Examples. In the following Formulation Examples, "parts" means "parts by weight". Solution Active ingredient: 5-75 parts, preferably 10-50 parts, more preferably 15-40 parts Liquid carrier: 25-95 parts, preferably 30-88 parts, more preferably 82-40 parts Surfactant: 1-30 parts, preferably 2-20 parts Emulsifiable concentrate Active ingredient: 1.0-50 parts, preferably 5-45 parts, more preferably 10-40 parts Surfactant: 1-30 parts, preferably 2-25 parts, more preferably 3-20 parts Liquid carrier: 20-95 parts, preferably 30-93 parts, more preferably 57-85 parts Dust Active ingredient: 0.5-10 parts Solid carrier: 90-99.5 parts Flowable agent Active ingredient: 5-75 parts, preferably 10-50 parts Water: 25-94 parts, preferably 30-90 parts Surfactant: 1-30 parts, preferably 2-20 parts Wettable powder Active ingredient: 2.5-90 parts, preferably 10-80 parts, more preferably 20-75 parts Surfactant: 0.5-20 parts, preferably 1-15 parts, more preferably 2-10 parts Solid carrier: 5-90 parts, preferably 7.5-88 parts, more preferably 16-56 parts Granule Active ingredient: 0.1-30 parts Solid carrier: 70-99.5 parts The solution and emulsifiable concentrate are prepared by dissolving the active ingredient in the respective liquid carriers containing surfactans. The wettable powder is prepared by mixing the surfactant, the solid carrier and the active ingredient and pulverizing the mixture. The dust is prepared by mixing the surfactant, the solid carrier and the active ingredient, and if necessary, pulverizing the mixture. The flowable agent is prepared by suspending or dispersing the active ingredient in an aqueous solution containing the surfactant. The granule is prepared by mixing the active ingredient and the adjuvant.

Claims: The pyridine derivative according to the following formula or its optical isomers. A herbicidal composition comprising a herbicidal effective amount of the pyridine derivative according to Claim 1 and a carrier therefore. A herbicidal composition according to Claim 2 comprising additionally as an active ingredient N-naphthylphthalamic acid, γ-(2,4-dichloro-phenoxy)butyric acid, γ-(2-methyl-4-chlorophenoxy) butyric acid, sodium 5-[2-chloro-4-(trifluoromethyl) phenoxy]-2-nitrobenzoate, 1'-(carboethoxy)ethyl-5-[2-chloro-4-(trifluoromethyl)phenoxy)-2-nitrobenzoate, 5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitro-N-methyl sulfonylbenzamide, 2-chloro-2'-6'-diethyl-N-(methoxymethyl)acetanilide, 2-chloro-2'-ethyl-6'-methyl-N-(2-methoxy-1-methylethyl)acetanilide, 3-isopropyl-(1H)-2,1,3-benzothiadiazin-4(3H)-one 2,2-dioxide, 4-amino-6-tert-butyl-3-methylthio-1,2,4-triazin-5(4H)-one, ethyl-2-[3-(4-chloro-6-methoxypyrimidin-2-yl)ureidosulfonyl]benzoate, 2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)-3-quinolinic acid, 5-ethyl-2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)-nicotinic acid, ethyl-2-[4-(6-chloro-2-quinoxanyloxy)phenoxy]propionate, methyl-2-[4-(2,4-dichlorophenoxy)phenoxy]propionate, butyl-2-[4-(5-trifluoromethyl-2-pyridyloxy)phenoxy] propionate, 2-(1-ethoxyiminobutyl)-5-[2-(ethylthio) propyl]-3-hydroxycyclohex-2-enone, ethyl-2-[4-(6-chloro-2-benzoxazolyloxy)phenoxy]propionate, methyl-2-[4-(3-chloro-5-trifluoromethyl-2-pyridyloxy) phenoxy]propionate, or a reaction mixture of chlorinated camphenes containing 67-69% chlorine (C.A.) toxaphene. A method for controlling weeds, which comprises applying to the weeds or to the locus of the weeds an effective amount of the pyridine derivative according to Claim 1.

Inventors: HATANAKA, MASATAKA, HATTORI, KENJI, IKAI, TAKASI, NAWAMAKI, TSUTOMU, NUMATA, TATSUO C/O NISSAN CHEM. IND. LTD., WATANABE, JUNICHI
Applicants: NISSAN CHEMICAL INDUSTRIES LTD.
Application year: 1986
Main classification: C07D491
IPC codes: A01N43, C07D495, C07D471, C07D401, C07D491