HERBICIDAL PYRIDINE DERIVATIVES AND THEIR SALTS OF 3-(AMINOOXOACETYL)-2-(2-IMIDAZOLIN-2-YL)

Abstract: The present invention relates to a new 3-(aminooxoacetyl)-2-(2-imidazolin-2-yl)pyridine and their salts, having a herbicidal activity, which is described in the structure of general formula (I) wherein, R<1> is C1 - C4 alkyl; R<2> is C1 - C4 alkyl, C3 - C5 cycloalkyl or C1 - C4 alkyl optionally substituted with 1 - 4 fluorine; R<3> is hydrogen, C1 - C3 alkyl, C1 - C3 alkyl optionally substituted with substituents contained in the following group I, C2 - C4 alkenyl or C2 - C4 alkynyl; R<4> is the same as R<3>; or phenyl, benzyl, pyridyl, furanyl, thiophenyl, benzofuranyl, dihydrobenzofuranyl, benzothiophenyl, dihydrobenzothiophenyl, indolyl, indolinyl, optionally substituted with 0-3 same or different substituents selected from the substituents contained in group II; and when taken together, connecting R<3> and R<4>, a 3-7 membered ring may be formed, in which may contain 0-3 double bonds or 0-3 O, N, SOn (n=0-2); W is O or S; X is hydrogen, C1 - C4 alkyl, C1 - C4 alkoxy, C1 - C4 alkoxyalkyl, or halogen; Y, Z are each hydrogen, halogen, C1 - C6 alkyl, C1 - C6 alkoxy, C1 - C6 alkoxyalkyl, C1 - C6 alkylthio, phenoxy, C1 - C6 haloalkyl, C1 - C6 alkylamino, C1 - C6 alkylsulfonyl or phenyl optionally substituted with one C1 - C4 alkyl, C1 - C4 alkoxy or halogen; and when taken together, a 5-6 membered ring may be formed in which may contain O, N, S double bonds or -(CH2)n-(n=0-4); A is hydrogen or -COR<5> (where R<5> is hydrogen, methyl or CH2Cl); when A is hydrogen, tautomeric isomer may exist; group I contains hydroxy, alkoxy, haloalkoxy, cyano, -CO2R<6> (where R<6> is hydrogen, alkyl, alkenyl, or alkynyl), alkylthio, alkylsulfonyl, phenylthio, phenylsulfonyl, haloalkylthio, alkenoxy, alkoxy, -NR<6>R<7> (where R<6>, R<7> are each hydrogen, alkyl, alkenyl or alkynyl or R<6>, R<7> may form a ring), phenyl, or phenoxy; group II contains group I substituents, halogen, nitro, haloalkyl, alkoxyalkyl, alkyl, alkenyl, alkynyl, alkylthioalkyl, -COR<8> (where R<8> is hydrogen, alkyl or phenyl), -CO2R<9> (where R<9> is hydrogen or alkyl), -SO3R<10> (where R<10> is hydrogen or alkyl), -SO2NR<6>R<7>, -CONR<6>R<7> (R<6>, R<7> are the same as above), or ( alpha ) (where n, m are an integer of 1-3, D is a single bond or double bond, O2, S, SO2, NCH3).

Description: HERBICIDAL PYRIDINE DERIVATIVES AND THEIR SALTS OF 3- (AMINOOXOACETYL) -2- (2-IMIDAZOLIN-2-YL) TECHNICAL FIELD The present invention relates to a novel 3- (aminooxoacetyl) -2- (2-imidazolin-2-yl)pyridine and their salts, having a herbicidal activity. BACKGROUND ART The imidazolinone herbicides, a potent class, have publicly known and until recently, British patent No.2,174,395 discloses the compounds having the following formula (A) . (A herein : R 1 is C j, - C 4 alkyl ; R 2 is C x - C 4 alkyl or C 3 - C 6 cycloalkyl ; B is C0 2 R 3 , CONHR 6 , CHO, CH 2 0H, C0CH 3 , COC 6 H 5 , CN, CH 3 , CH=N0H, CH 2 C00H, CONHOH, CHROH, CH 2 CH 2 C00H, JCO H, COOCH" (wherein, R 3 is hydrogen, dialkylimino, substituted alkyl, alkenyl or cation, R 6 is hydrogen, hydroxy or alkenyl) A is hydrogen, COR 4 , S0 2 R 5 , etc. The above patent introduces many a herbicidal compounds, but they have recognized a disadvantage in that except for soybean, such compounds failed to exert an effective selectivity of herbicidal activity as herbicide. Also, such i idazolinone compounds are specified in the following patents, say, German Patent No. 2,833,274, U.S. Patent No.4, 824, 66/4, 851, 021/4,824,474, European Patent No. 41,623/298,029/322,616. However, the current situation is that the undesirable vegetation should be controlled so as to improve the growth of useful crops such as corn, rice, cotton, wheat, and soybean. The failure to check the weed growth in such useful crops may bring about significant losses to farmers and to consumer as well. Thus, the continuous research to develop more effective products should be required for a good harvest. DETAILED DESCRIPTION OF THE INVENTION The present invention relates to novel compounds demonstrating a herbicidal activity and to agriculturally suitable compositions thereof, and a method of their uses as general and/or selective preemergent and/or postemergent herbicides or plant growth regulants. More specifically, said compounds demonstrating a herbicidal activity are 3- (aminooxoacetyl)-2- (2-imidazolin- 2-yl)pyridine having a following stucture of general formula(I) . wherein, R 1 is λ - C 4 alkyl; R 2 is C x - C 4 alkyl, C 3 - C 5 cycloalkyl or C x - C 4 alkyl optionally substituted with 1 - 4 fluorine; R 3 is hydrogen, C x - C 3 alkyl, C x - C 3 alkyl optionally substituted with substituents contained in the following group I, C 2 - C 4 alkenyl or C 2 - C 4 alkynyl ; R 4 is the same as R 3 ; or phenyl, benzyl, pyridyl, furanyl, thiophenyl, benzofuranyl, dihydrobenzofuranyl, benzothiophenyl, dihydrobenzothiophenyl, indolyl, indolinyl, optionally substituted with 0-3 same or different substituents selected from the substituents contained in group II ; and when taken together, connecting R 3 and R 4 , a 3-7 membered ring may be formed, which may contain 0-3 double bonds or 0-3 0, N, SOn(n=0-2); W is 0 or S; X is hydrogen, C τ - C 4 alkyl, τ - C 4 alkoxy, C x - C 4 alkoxyalkyl, or halogen; Y, Z are each hydrogen, halogen, C x - C 6 alkyl, C x - C 6 alkoxy, C x - C 6 alkoxyalkyl, C x - C 6 alkylthio, phenoxy, C x - C 6 haloalkyl, , - C 6 alk lamino, C, - C 6 alkylsulfonyl or phenyl optionally substituted with one C : - C 4 alkyl, C x - C 4 alkoxy or halogen; and when taken together, a 5-6 membered ring may be formed in which may contain 0,N,S, double bonds or- (CH 2 )n- (n=0-4) ; A is hydrogen or -COR 5 (where R 5 is hydrogen, methyl or CH 2 C1) ; when A is hydrogen, tautomeric isomer may exist; Group I contains hydroxy, alkoxy, haloalkoxy, cyano, -COR 6 (where R 6 is hydrogen, alkyl, alkenyl, or alkynyl) , alkylthio, alkylsulfonyl, phenylthio, phenylsulfonyl, haloalkylthio, alkenoxy, alkoxy, -NR 6 R 7 (where R 6 , R 7 are each hydrogen, alkyl, alkenyl or alkynyl or R 6 , R 7 may form a ring) , phenyl, or phenoxy ; Group II contains group I substituents, halogen, nitro, haloalkyl, alkoxyalkyl, alkyl, alkenyl, alkynyl, alkylthioalkyl, -COR 8 (where R 8 is hydrogen, alkyl or phenyl) -C0 2 R 9 (where R 9 is hydrogen or alkyl), -S0 3 R 10 (where R 10 is hydrogen or alkyl), -S0 2 NR 6 R 7 ,-C0NR 6 R 7 (R 6 , R 7 are the same as above) , or (where n, m are an integer of 1-3, D is a single bond or double bond, 0, S, S0 2 , NCH 3 ) . A preferred group of 3-(aminooxoacetyl) -2- (2-imidazolin- 2-yl)pyridine compounds having the formula shown as above (I), wherein R 1 is methyl, R 2 is methyl, ethyl, isopropyl or cyclopropyl; W is oxygen; A is hydrogen, X is hydrogen, Y, Z is each hydrogen, Cj - C 6 alkyl or C x - C 6 alkoxy, and when Y and Z are taken together, YZ is -(CH 2 ) 4 , -CH=CH-CH=CH-, or -0(CH 2 ) 3 -, and R 3 is hydrogen or C τ - C 2 alkyl, R 4 is C τ - C 2 alkyl optionally substituted with 0-2 substituents selected from halogen, hydroxy, alkoxy, alkylthio, amino, phenyl, phenoxy ; C 2 - C 6 alkenyl, C 2 - C 6 alkynyl, or phenyl optionally substituted with 0-3 same or different selected from substituents contained in the above group II, when taken together, connecting R 3 and R 4 , a 3-7 membered ring may be formed, which may contain 0-3 double bonds or 0-3 0, N, SOn(n=0-2) ; A more preferred group of 3- (aminooxoacetyl)-2- (2- imidazolin-2-yl)pyridines, wherein A and X is each hydrogen, Y is hydrogen, C x - C 2 alkyl or C x - C 2 alkoxy, Z is hydrogen, R 1 is methyl, R 2 is isopropyl, R 3 is methyl or ethyl, R 4 is benzyl, phenyl, or phenyl substituted with 1-3 substituents selected from C 2 - C 6 alkyl, phenoxy, C x - C 6 alkoxy, halogen, haloalkyl, C x - C 6 alkylthio, C - C 6 alkylsulfone C, - C 6 dialkylamino, or those where -NR 3 R 4 is Among the definitions according to the present invention, the following terms have the following meanings : a) "Alkyl" used either alone or in compound words such as "alkylthio" or "haloalkyl", etc. denotes straight chain, or branched alkyls within six carbon atoms. b) "Alkenyl" denotes straight chain or branched alkenes within six carbon atoms. c) "Alkynyl" denotes straight chain or branched alkynes within six carbon atom. d) "Alkoxy" denotes groups of 0-alkyls defined as above. e) "Halogen" denotes either alone or in compound words such as haloalkyl denotes fluorine, chlorine, or bromine. As a useful herbicide, said 3- (aminooxoacetyl) -2- (2- imidazolin-2-yl) pyridine compounds and their salts of the present invention may be used in cultivating soybean, corn, wheat, barley, rice, and cotton. The salts of said compounds can be prepared as an acid-addition salt or an alkali, alkaline earth metal or quaternary amine salts. Compounds of the present invention can be prepared by reactions as described in hereinbelow. The compounds of general formula(I) can be obtained by acylating the compounds of formula(II), when neither of R 3 or R 4 is hydrogen, can be prepared as shown in Reaction(1) U ) From the above reaction(1), BuLi and LDA are preferably used as a strong base, possibly at the temperature of -78 ~ -30 °C. The synthesis method in the compound of said general formula(II) is publicly known, and its synthesis is available by Korea Patent Publication No. 85-1817 and Germany Patent DE No.2,833,274/3,121,736. If R 3 is hydrogen, the manufacture of said compound should be preferably made available by protecting this functional group under the following reaction(2) . When there is a substituent of hydroxy having active hydrogen in R 3 or R 4 from the above reaction, the systhesis is made available by protecting the substituent under the reaction (1) or reaction (2) . Also, the novel compound of the present invention may be synthesized by the following reaction(3), wherein n = the fixed number of 1 ~ 6, R 3 is hydrogen or has a substituent of hydroxy. If R 3 and R 4 is each hydrogen, the manufacture of said compound should be preferably made available by protecting the amino functional group under the following reaction (4) . Meantime, the manufacture of general formula(III) used in said reaction(1) may be made available by reacting with oxalic acid ester and amine as do in the following reaction(5) . O O R 3 0 O R EtO-C-C-Olit I . HN-R 4 ElO-C --CC--NN-R 4 (5) (III) Also, the manufacture of said general formula (IV) and (V) may be made available by the following reaction (6) and (7) The manufacture of said general formula (VI) may be made available by the existing method, and the manufacture of said general formula(VIII) may be made available by the following reaction(8). The compounds of said general formula(I) of the present invention specify the following materials: . 3- (N-methyl-N-3-fluorophenyl-aminooxoacetyl) -2- (4- isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl) -5-methyl- pyridine . 3-(N-methyl-N-3-chloro-4-methoxyphenyl-aminooxoacetyl) -2- (4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl) -5-methyl- pyridine 3-(N-methyl-N-3,5-dimethylphenyl-aminooxoacetyl) -2- (4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)-5-methyl- pyridine 3-(N-methyl-N-4-n-butylphenyl-aminooxoacetyl) -2- (4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl) -5-methyl- pyridine 3-(N-methyl-N-4-t-butylphenyl-aminooxoacetyl) -2- (4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl) -5-methyl- pyridine 3- (N-methyl-N-4-phenoxyphenyl-aminooxoacetyl) -2- (4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)-5-methyl- pyridine 3-(N-methyl-N-3-chlorophenyl-aminooxoacetyl) -2-(4- isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl) -5-methyl- pyridine 3- (N-methyl-N-4-cyclohexylphenyl-aminooxoacetyl) -2- (4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)-5-methyl- pyridine 3-(N-methyl-N-4-dimethylaminophenyl-aminooxoacetyl)-2- (4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)-5-methyl- pyridine 3-(N-methyl-N-3-trifluoromethylphenyl-aminooxoacetyl)-2- (4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)-5-methyl- pyridine 3-(N-methyl-N-3,4-dichlorophenyl-aminooxoacetyl) -2- (4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)-5-methyl- pyridine 3-(N-methyl-N-4-trifluoromethylphenyl-aminooxoacetyl)-2- (4-isopropyl-4-methyl-5-oxό-2-imidazolin-2-yl) -5-methyl- pyridine . 3- (N-methyl-N-3-methylphenyl-aminooxoacetyl)-2- (4- isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl) -5-methyl- pyridine The above-manufactured compounds of said general formula(I) are used, in various forms of solutions and powders having herbicidal compositions, to the soil containing plant's leaf or plant-breeding part. The dosage forms available are wettable powder, flow concentrates, emulsifiable concentrates, and granules. According to the present invention, the wettable powder is homogeneously dispersed in water; in addition to the active composition, diluent, and non-toxic material, said wettable agent is manufactured by the following materials: polyoxyethylated alkylphenols, polyoxyethylated fatty alcols, alkyl or alkylphenyl sulfonates. The dispersing agent includes sodium lignin sulfonate, sodium 2,2'-dinaphthylmethane-6, 6' disulfonate, sodium dibutyl naphthalene sulfonate, or sodium oleil-methyltauride. Such agents are manufactured by the existing method by pulverizing and mixing the ingredients. The flow concentrates may be manufactured by mixing/melting the active ingredients into non-toxic organic solvent (e.g., butanol, cyclohexanol, DMF, xylene, or high boiling aromatics, or hydrocarbons) , together with any one or more emulsifiers. As an usable emulsifier, calcium alkylsulfonates includes calcium dodesylbenzenesulfonate or non-ionic emulsifier includes fatty acid polyglycolesters, alkyl- aryl polyglycolethers, fatty alcol polyglycolethers, propyleneoxide, ethyleneoxide polymers, fattyalcohol, propyleneoxide ethyleneoxide polymers, alkylpolyglocolethers, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, or polyoxyethylene sorbitol esters. Also, a powdering agent may be manufactured by pulvering the active ingredient with talc of micro- pulverized solid and natural clay(e.g., kaolin, bentonite, pyrophilite, or siliceous earth) . And a granular agent may be manufactured either by spraying the active ingredient on inactive adsorbent in granular form or by adsorbing the active flow concentrates on the surface of intermediates, say, sand, kaolinites. The usable adsorbent includes pol vinyl alcol, sodium polyacrylate or mineral oils. The herbicides of general formula(I) in the present invention may be manufactured by the existing method of fertilizer-granule agent, and if necessary, they may also be manufactured by the mixture of fertilizer. The preparations containing aforementioned active ingredients may , if necessary, contain wettable agents, dispersing agents, emulsifiers, impregnating agents, solvents, fillers, intermediates, etc. For the actual appication, the flow concentrates in a commercial form may be used by appropriate dilution. For example, the wettable powder or emulsifiable concentrates is used by dilution, while powdering/granular/ spraying solution, inactive materials, are not diluted. Also, the flowable liquid is composed of the following: active ingredient of 30 ~ 50 wt %, gelator of 1 ~ 3 wt %, dispersing agent of 1 ~ 5 wt %, alcohol of 0.1 ~ 3 wt %, and water of 40 ~ 60 wt %. The prevailing method of manufacturing the flowable liquid is based upon the following formula: in proportion to the active ingredient of about 40 wt %, gelator(e.g., bentonite) of about 2 wt %, dispersing agent (e.g., lignosulfate) , polyethylene alcohol of 1 wt %, and water of 54 wt %. Also, the prevailing method of manufacturing the concentrated emulsifying liquids is based upon the following formula: after dissolving the active ingredient of about 5 ~ 25 wt % into N-methylpyrrolidone, isoporone, butylcellosolve, methylacetate in about 65 ~ 90 wt %, some non-ionic surfactant (e.g., alkyloxy polyethoxy alcohol) of about 5 ~ 10 wt % is dispersed into said liquids. When said concentrated liquids are used, they are dispersed into water to make the spraying solution. In case the compounds of the present invention are to be used as the herbicide containing a soil-treating agent, they may be used by manufacturing a granular agent; to manufacture said agent, the active ingredient is dissolved into some solvent (e.g., methylene chloride and N- methylpyrrolidone) and said formed solution is sprayed to granular carries such as powder of corn stalk, sand, attapulgite, and kaolin. In general, the above manufactured granular agent contains the active ingredient of about 3 ~ 20 wt % and the granular carrier of about 97 -80 wt %. Meantime, the compounds of general formula(I) of the present invention are the most effective herbicide in controlling one-year weed, perenial plant, mono- or bi- cotyledonous plant. Also, said compounds is quite effective in eliminating the weeds growing in the dry/humid soil areas only. They are used as underwater herbicides and if said compounds, in a ratio of about 0.06 ~ 10 kg/ha, are given to plant's leaves, s.oil, or the breeding parts such as tuber, rhizome, or ladix, the plant may be eliminated successfully and effectively. Moreover, surprisingly, it is found that various kinds of compounds of general formula(I) demonstrate their selective herbicidal effect according to the kinds of plant eliminated, when they are given to plant's leaves, or soil, in a low ratio. It is also noted that said compounds may be widely used as pre-emergent or as post-emergent. However, it does not mean that said compounds of general formula(I) are non-selective. Especially, certain compounds are selective in soybean, wheat, barley, corn, rice, and cotton, while other compounds are said to be effective as growth-inhibitors against plant. As above, the novel compounds of the present invention may be used not only as effective herbicides, but also as growth-modulators for inhibiting the plant's growth. The applicable amount of said compounds is decided based upon various considerable factors. For example, the following factors should be considered: kinds of plants, controlled type of weeds, climate, weather, dosage forms, applicable methods, quantity of leaf. A low amount is preferably used in the following cases; a) soil having less content of organic material b) the transformation in plant growth or short- term duration should be required. The following Examples illustrate ways in which the principle of this invention has been applied, but are not to be construed as limiting its scope. Common Name acetochlor bromacil clethodim acifluofen bromoxynil clomazone acrolein butachlor cloproxydim alachlor buthidazole clopyralid ametryn butralin CMA amitrole butylate cyanazine AMS cacodylic acid cycloate asulam CDAA cycluron atrazine CDEC cyperquat barban chloramben cyprazine benefin chlorbromuron cyprazole bensulfuron methyl chlorimuron ethyl cypromid bensulide chloroxuron dalapon bentazon chlorporpham dazomet benzofluor chlorsulfuron DCPA benzoylprop chloroluron desmediphan bifenox cimmethylin desmetryn EXAMPLE 1 :3-(N,N-dimethylaminooxoacetyl)-2- (4- isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl) -5-methyl pyridine To a stirred solution of 2.5 g (0.011 mole) of 2-(5- isopropyl-5-methyl-4-oxo-2-imidazolin-2-yl)-5-methyl pyridine in 100 ml of dry tetrahydrofuran cooled to -70°C under the presence of nitrogen was added dropwise a 9.68 ml of 2.5 molar n-butyllithium, thereby temperature was maintained below -65°C. The solution was stirred at -70°C for 3 hours and a solution 1.96 g of N,N-dimethyl oxamic acid methyl ester(0.015 mole) in 10 ml of anhydrous tetrahydrofuran was added dropwise while maintaining the temperature below -65°C. After stirring another hour at -70°C, the solution was poured into water and extracted with methylene chloride. The combined organic phases were dried over magnesium sulfate, and evaporated under reduced pressure. Trituration of the residue with diethyl ether affored a crude solid which was recrystallized from a mixture of diethyl ether and methylene chloride to yield 1.67 g of a white solid (m.p=180-182°C) . EXAMPLE 2: Preparation of 2-(4-isopropyl-4-methyl-5-oxo-2- imidazolin-2-yl)-5-methy1-3-(N-methyl-N-phenyl amino oxo acetyl)pyridine To a stirred solution of 2.5 g(0.011 mole) of 2-(5- isopropyl-5-methyl-4-oxo-2-imidazolin-2-yl)-5-methyl pyridine in 100ml of anhydrous tetrahydrofuran cooled to -70°C under the presence of nitrogen was added dropwise a 9.68 ml of 2.5 molar n-butyllithium, thus maintaining temperature below -65°C. The solution was stirred at -70°C for 3 hr and a solution 1.96 g of N-methyl-N-phenyl oxamic acid methyl ester(3.4 g, 0.016 mole) in 10 ml of anhydrous tetrahydrofuran was added dropwise while maintaining temperature below -65°C. After stirring another hour at -70°C, the solution was poured into water and extracted with methylene chloride. The combined organic phases were dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure to give crude product. The crude product was purified by column chromatography to produce 1.76 g of pale yellow solid( m.p. = 153 ~ 156°C) . EXAMPLE 3: Preparation of 2-(4-isopropyl-4-methyl-5-oxo-2- imidazolin-2-yl)-5-methyl-3- (N-methyl-N-phenyl amino oxo acetyl)pyridine To a stirred solution containing 3.0g(0.13 mole)-2- (5-isopropyl-5-methyl-4-oxo-2-imidazolin-2-yl)-5-methyl pyridine in 100ml dry THF at -70°C under nitrogen was added dropwise 12.48ml of 2.5 molar n-butyllithium in hexane without allowing the temperature to rise above -65°C. The solution was stirred at -70°C for 3 hours and a solution 2.58 g of 3-methyloxazolin-2,4,5-trione(0.02 mole) in 10 ml dry THF was added dropwise while maintaining the temperature below -65°C. After stirring another hour at -70°C, the reaction mixture was allowed to attain room temperature. Reaction mixture was poured into water, the pH was adjusted to 7 with 5N H 2 S0 4 and extracted with methylene chloride. The combined organic phases were dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure to give crude product. The crude product was purified by column chromatography to afford 1.27 g of pale yellow solid(m.p.=174-178°C) . The Synthesis of using following compounds based upon said Examples 1 - 3 was conducted : A-l - A-39 compound as shown in the following general formular (I-A) , B-l - B-81 compound as shown in the following general formula (I-B) , C-l - C-34 compound as shown in the following general formula(I-C) , and D-l - D-6 compound as shown in the following general formular(I-D) The herbicidal activity of said compound was measured in the greenhouse test. Table 25 Table 27 28 32 34 35 37 Table 4 Comp . No. K NO. R 3 -N-R 4 m.p. (°C) -l Me-N-Me 178-180 D-2 150-154 3-3 - 177-179 D- N ' ~CH3 189-191 D-5 169-171 E>-6 163-166 Example 4: Post-emergence herbicidal evaluation of test compounds The post-emergence herbicidal activity of the compounds of the invention is demonstrated by the following tests, wherein a variety of monocotyledonous and dicotyledonous plants are treated with test compounds dispersed in aqueous acetone mixtures. In the tests, seedling plants are grown in jiffy flats for two weeks. The test compounds are dispersed in 50/50 acetone/water mixtures containing 0.5% TWEEN(TM) 20, a polyoxyethylene sorbitan monolaurate surfactant, in sufficient quantity to provide the equivalent of about 0.06 kg of 10 kg per hectare of active compound when applied to the plants through a spray nozzle operating at 40 psi for a predetermined time. After spraying, the plants are placed on greenhouse benches and are cared for in the usual manner, commensurate with conventional greenhouse practices. From 2 to 4 weeks after treatment, the seedling plants, are examined and rated according to the rating system provied below. The data obtained are recorded in table 6 below. [Rating System ] Rating System % Difference in Growth No effect 0 Possible effect 1 - 10 Slight effect 1 - 25 Moderate effect 26 - 40 Definite injury 41 - 60 Herbicidal effect 61 - 75 Good herbicidal effect 76 - 90 Approaching complete kill 91 - 99 Complete kill 100 In most cases the data are a single test, but in several instances, they are average values obtained from more than one test. Table 5. Test to evaluate herbicidal activity (Testgroup I : UPLAND SPECIES) Abbr. Scieutific Name Plamts applied LYPES Lycopersicon esculentum MILL.Tomato TRZAW Triticum aestivum L, Wheat GLXMX Glycine max(L.) MERR. Soybean ZEAMX Zea mays L. Corn DACGL Dactylis glomerata L, Orchardgrass AMAVI Amaranthus viridis L, Pigweed DIGSA Digitaria sanguinalis (L.) Large SCOP. crabgrass RUMJA Rumex japonicus HOUTT. Dock AESIN Aeschyno ene indica L. Indian jointvetch CAGHE Calystegia japonica CHOISY Bindweed POLHY Polygonum hydropiper L, Smartweed (Test group II : PADDY SPECIES) Abbr. Sciemtific Name Plamts applied ORYSA Oryza sativa L, Rice ECHOR Echinochloa crus-galli P. Barnyardgrass Beauv. var. oryzicola OHWI CYPDI Cyperus difformis L. Umbrellaplant ANEKE Aneilema keisak HASSK. Dayflower EXAMPLE 5: Pre-emergence herbicidal evaluation of test compounds The pre-emergence herbicidal activity of the compounds of the invention is examplified by the following tests in which the seeds of a variety of monocotyledonos and dicotyledonous plants are seperated mixed with potting soil in separated pint cups. After planting, the cups are sprayed with the selected aqueous acetone solution containing test compound in sufficient quantity to provide the equivalent of about o.06 to 10 kg per hectare of test compound per cup. The treated cups are then placed on greenhouse benches, watered and cared for in accordance with conventional greenhouse procedures. From 2 to 4 weeks after treatment, the tests are terminated and each cup is examined and rated according to the rating system set forth above. The herbicidal proficiency of the active ingredients of the present invention is evident from the test results which are recorded in Table 6 below. Table 6 below is represented pre-and post-emerergence herbicidal evaluation [PRIMARY SCREENING (Herbicide) ] of test compounds. PLANT RESPONSE SCREENING (Herbicide) Table 6, U P L A N D M E E S P E C I E S PADDY HEED SPECIES KSC CHEH. TYPE kg/ha NO. REF. LYPES TRZAM GLXHX ZEAHX DACGL AHAVI DIGSA RUHJA POLHY AESIN CAGHE ORYSA ECHUR CYPDI ANEKE PRE .25 00 60 IC 70 70 30 90 20 70 50 80 60 35 90 25 (A-2) POST .25 100 90 70 100 70 100 100 60 95 70 100 70 i30 60 30 PRE .25 100 90 60 60 65 90 100 40 90 50 65 70 20 90 70 (A-3) POST .25 100 85 30 65 70 80 80 65 70 75 30 90 70 50 70 PRE .25 90 70 15 60 65 90 80 20 80 70 90 70 70 60 40 (A- ) POST .25 100 90 85 100 80 100 100 70 90 90 100 90 90 80 70 PRE .25 90 80 10 40 70 90 100 40 30 70 90 100 70 90 45 (A-5) POST .25 100 100 100 100 100 100 100 95 100 95 100 90 90 70 100 PRE .25 100 "JO 70 30 70 90 100 70 85 70 95 100 90 90 70 (A-β) POST .25 100 100 90 100 100 100 100 70 100 90 100 90 100 100 90 CD CD t o t CD •JO c* CM —• to r»» -O <=) tO CM c_> 10 cs f. *. CD CD CD CD C"s —- CD <_D CD C3 CM CO M r-t rs. —. PLANT RESPONSE SCREENING (Herbicide) U P L N D U E E D S E C I E S PADDY UEED SPECIES KSC CHEH. TYPE kg/ha NO. REF. LYPES TRZAU GLXHX ZEAHX DACGL AHAVI DIGSA RUHJA POLHY AESIN CAGHE HRYSA ECHOR CYPDI ANEKE PRE ΛC 100 95 90 100 90 100 100 90 95 90 ;oo 85 ICO 100 90 (A-12) POST .25 100 100 35 100 100 100 100 90 100 90 100 100 90 95 90 PRE .25 100 70 25 20 35 100 70 60 95 50 70 15 10 70 0 (A-13) POST .25 90 65 40 0 0 100 25 10 70 10 70 65 15, 0 0 PRE .25 100 90 85 90 30 100 100 90 100 70 90 60 70 90 90 (A-14) POST .25 100 80 80 30 75 90 30 70 90 75 95 95 100 75 95 PRE .25 90 70 20 0 30 70 65 10 0 30 55 10 65 0 (A-15) POST ΛC ._.J 100 100 75 100 100 100 35 10 70 60 100 80 65 65 25 PRE .25 30 70 30 0 20 70 60 10 15 30 60 0 65 30 (A-16) POST .25 90 100 65 70 65 100 70 10 70 65 100 90 60 55 60 CD CD CD CD tO Cf « CD CD CD CM CM CD CD —. -O Cl rs CD CD to CD CD CD CK CD O <=> t Cts tO O CD CD CD CD CD CD CD tO o t CD CD CD tO CD CD CO CD CD CD c CD CD tO CO CO CD O CD CD W) β CD CO O ^ CT* *» f *» - ι* * » si CD CD CD CD ( Λ CD CD OD r * . r--. r- s© so r CD CD to CD CD O Nθ t to to CD CD SO => co co co co to CJ —. C9 CD CD CD CD CD CD CD CD to CD CD O O r-. tO t PLANT RESPONSE SCREENING (Herbicide) U P L A N D H E E D S P E C I E S PADDY UEED SPECIES XSC CHEH. TYPE kg/ha NO. REF. • LYPES TRZAU GLXHX ZEAHX DACGL AHAVI DIGSA RUHJA POLHY AESIN CAGHE DRYSA ECHUR CϊPDI AfiEKE PRE .25 100 100 75 90 90 90 100 60 100 100 35 20 65 65 (A-23) POST .25 100 100 30 65 70 100 100 20 90 100 70 90 100 60 PRE .25 100 100 35 90 100 90 100 80 95 90 70 15 65 70 (A-24) POST .25 100 100 90 70 100 100 100 15 00 100 H) 100 90 60 PRE .25 85 35 0 10 70 30 100 60 0 80 (A-25) POST .25 90 15 0 10 30 90 .90 35 0 90 65 60 100 20 PRE .25 90 55 15 10 55 100 60 40 85 20 70 20 10 20 10 (A-26) POST .25 90 '. 20 0 10 70 15 20 75 10 60 7 30 0 15 PRE .25 100 95 30 100 90 100 100 95 95 95 95 70 50 30 75 (A-27) P05! .25 100 100 i.O 100 65 100 80 70 90 >ι) 100 70 100 40 90 PRE .25 100 90 85 90 30 100 100 00 90 90 100 60 30 70 40 (A-28) POST .25 100 «0 30 '»0 75 100 75 70 100 90 100 90 90 60 100 49 *Λ 2 S S 8 2 S S? S? 2 £ _§ ϋ? 2 2; 5 R 55 2 s o CD o «o o o O s s? C9 D .. OB s C .S? Q PRE .25 70 40 10 0 0 65 0 0 30 20 10 0 (A-30 ) POST .25 100 90 70 30 70 100 65 30 85 100 60 70 90 PRE .25 100 100 30 90 90 1 00 100 70 100 100 100 30 35 80 70 (A-31 ) POST .25 100 100 90 55^ 90 00 70 30 90 100 90 100 100 60 PRE .25 100 90 35 90 80 100 100 50 90 95 { A J ) POST .25 100 100 90 100 90 100 100 70 100 100 65 100 100 90 PRE .25 100 90 65 flc 85 100 100 25 30 80 90 35 20 70 20 (A-33 ) POST .25 100 100 30 100 100 100 70 70 90 100 90 100 100 100 PLANT RESPONSE SCREENING (Herbicide) U P A N D E E D S P C I E S PADDY HEED SPECIES use CHEH. TYPE kg/ha HO. REF. LYPES TRZAU GLXHX ZEAHX DACGL AHAVI DIGSA RUHJA POLHY AESIN CAGHE ORYSA ECHOR CYPDI ANEKE PRE .25 90 65 50 40 60 100 50 15 65 40 90 30 10 30 0 (A-34) POST .25 100 70 60 10 40 100 25 25 60 70 60 60 60 80 PRE .25 80 65 15 50 100 70 30 40 70 0 0 0 (A-35) POST .25 100 100 30 15 60 100 60 40 90 50 30 80 50 30 30 PRE .25 70 70 20 10 35 10 75 20 15 30 30 0 10 0 (A-36) 8 OST .25 90 100 50 10 25 100 30 10 70 20 70 100 30 10 10 PRE .25 80 35 5 0 20 )0 15 0 65 0 80 0 0 0 0 (A-37) POST .25 90 60 50 0 20 100 15 10 75 20 90 10 20 0 0 PRE .25 100 100 70 70 90 100 100 90 90 75 100 60 • 60 20 70 (A-38) POST .25 100 100 70 65 80 100 65 .00 70 100 100 100 100 90 PRE .25 90 100 90 75 80 100 100 70 80 70 POST .25 70 60 40 10 20 100 30 10 10 70 10 0 0 20 PRIMARY SCREENING (Herbicide) U P L A N D U EE D S P E C I E S PADDY UEED SPECIES sc CHEH. TYPE kg/ha - -r NO. REF. LYPES TRZAU GLXHX ZEAHX DACGL AHAVI DIGSA RUHJA POLHY AESIN CAGHE ORYSA ECHUR CYPDI ANEXE PRE .5 IOO 30 0 0 60 70 100 55 80 20 80 70 70 90 90 (B-l) ' • - .25 80 0 0 0 40 60 70 30 80 0 80 40 50 70 10 .125 70 0 0 0 0 0 65 0 30 0 10 0 0 70 0 .06 70 0 0 0 0 0 10 0 10 0 0 0 0 60 0 POST .5 90 40 5 0 80 70 90 10 30 55 60 70 60 50 30 .25 80 5 0 0 60 50 65 0 50 10 40 50 60 20 10 .125 70 0 0 0 10 20 20 0 10 0 10 50 15 0 0 .06 40 0 0 0 0 10 0 0 0 0 0 20 0 0 0 CD CD CD 'CD to CD CD CD O — ff- CD CD CD α CD CD CD CD CD CD C o* o CD α : CD CD CD CD CD _ _. o- CO CD CD CD CD CD C . '¬ o» O. O o» co CD to CD . rs CO O to t CD CO CD CD CD CD CD CD t CD CD CD CO to to CD CD 0 ι_D CN ON Cts CD CD CD CD CD CD OO — ■ <=J <_D O- - CD CD to OO CD OO CD CD O CD C O* O CD o to . —• «r to CD CD CD CD CD O CD CO —• PLANT RESPONSE SCREENING (Herbicide) U P L A N D H E E D S P E C I E S PADDY UEED SPECIES XSC CHEH. TYPE kg/ha NO. REF. LYPES TRZAU GLXHX ZEAHX DACGL AHAVI DIGSA RUHJA POLHY AESIN CAGHE ORYSA ECHOR CYPDI ANEXE PRE .25 100 80 25 30 90 90 ' 100 70 90 50 90 100 95 90 60 (B-7) POST .25 100 90 60 80 90 90 100 70 90 90 100 90 100 90 50 PRE .25 100 90 40 65 90 90 100 60 90 60 100 100 95 90 90 (B-8) POST .25 100 70 80 70 100 90 100 70 90 85 100 90 100 90 60 PRE .25 100 90 0 70 80 90 100 70 80 65 100 100 100 90 85 (B-9) POST .25 100 90 65 60 90 100 100 70 90 80 100 90 100 95 70 PRE .25 90 40 10 30 90 100 100 90 40 70 100 60 90 60 (B-IO) POST .25 100 70 25 30 100 100 90 80 100 65 90 90 85 90 30 PRE .25 100 80 50 30 70 90 100 80 90 50 90 90 20 90 60 (B-ll) POST .25 100 90 55 60 80 90 100 80 80 80 100 100 100 90 70 PRE .25 100 65 10 10 100 95 100 90 90 70 80 90 90 90 10 (B-12) POST .25 100 60 40 45 90 100 100 90 100 90 100 100 100 100 65 PRE .25 100 70 65 75 70 80 95 40 80 60 95 90 70 90 50 (B-13) POST .25 100 60 30 70 90 90 100 50 90 65 100 70 100 60 20 PRE .25 100 90 60 60 80 90 100 90 90 90 100 100 90 100 25 (B-14) POST .25 100 90 50 80 90 100 100 90 90 90 100 100 100 30 8 < PRE .25 100 90 35 90 100 100 100 95 75 90 100 100 95 7 (B-15) POST .25 100 75 60 90 100 100 100 90 100 80 100 100 100 100 5 PRE .25 90 30 10 10 90 90 100 70 90 10 70 100 85 95 3 (B-16) POST .25 100 30 30 10 70 100 70 60 80 40 90 100 100 80 4 PRE .5 100 90 70 100 95 90 100 90 90 90 100 100 100 100 80 (B-17) .25 100 90 50 65 90 90 100 90 90 80 100 100 100 90 90 .125 100 70 10 20 80 90 100 90 90 70 100 85 70 90 80 .06 90 30 0 0 70 85 90 80 80 35 90 50 65 70 35 .03 90 15 0 0 60 70 80 70 70 10 60 30 20 10 10 POST .5 100 100 90 90 100 100 100 90 100 100 100 90 100 100 65 .25 100 70 15 5 100 100 100 80 85 85 100 90 90 100 65 .125 90 35 10 0 60 100 100 65 70 55 100 70 80 100 55 .06 70 10 0 0 25 30 60 10 50 10 90 10 25 70 20 .03 65 10 0 0 0 20 50 0 40 0 55 0 0 20 0 PRE .25 80 50 15 0 70 90 100 85 0 65 60 30 90 10 (B-18) POST .25 90 10 10 0 70 0 100 80 100 25 70 70 70 70 15 PRE .25 100 60 10 25 90 95 100 90 30 90 70 60 90 20 (B-19) POST .25 100 60 20 50 100 100 100 90 100 90 100 100 90 90 40 —. PRE .25 80 0 0 0 65 90 95 50 0 70 70 70 90 10 (B-20) POST .25 100 65 20 20 100 100 100 90 100 70 100 70 80 90 60 PRE .25 80 0 0 0 60 70 90 30 0 65 50 0 70 20 (B-21) POST .25 100 15 20 0 50 90 100 20 90 25 100 70 70 70 0 PRIMARY SCREENING (Herbicide) U P L A N D U E E D S P E C I E S PADDY UEED SPECIES XSC CHEH. TYPE kg/ha NO. REF. LYPES TRZAU GLXHX ZEAHX DACGL AHAVI DIGSA RUHJA POLHY AESIN CAGHE ORYSA ECHOR CYPDI ANEXE PRE .25 100 80 65 65 90 100 100 100 90 100 100 80 90 70 (B-22) .125 100 70 30 30 90 100 100 100 75 100 70 20 90 60 .06 90 4ϋ 10 0 80 100 100 70 55 80 60 50 20 .03 90 10 0 0 70 100 90 70 15 70 0 50 0 30 .015 70 0 0 0 35 85 >0 20 0 70 0 0 0 0 .25 100 70 50 40 90 100 100 90 80 90 100 40 90 100 .12 90 60 20 20 90 100 100 80 70 80 100 20 90 80 .06 90 30 0 0 80 90 100 65 30 70 90 0 βO 70 .03 80 10 0 0 70 90 100 SO 0 60 80 0 80 10 POST .25 100 50 10 40 100 100 100 80 80 95 100 100 65 .12 100 50 0 0 90 100 95 60 65 90 80 90 20 .06 0 0 0 75 100 60 40 30 SO 65 SO 0 .03 0 0 0 30 95 10 20 20 20 20 50 0 CD CD OO CD O CD SO CD ON CD _ CD tO — ©N -. o σ< es o CD CD OO CO CD O o t lO CO -N. NO CD CO CM CD CO o • O CNJ CD CD Λ CO so tO CD NO O CD CD CD CD CD CD CD _-4 t —4 CO CD O) O CD CD CD CD OO so CD CD to <_D CD to — O so Γ CO CM to CD CD to t CD tO CD - to CM _ ON CO 3D -O CD CD I CD CD ^T CM CD CD CD CD CD O O CD CO CO — CO t CD o CD CD CD CD CD CD CD CD to CD CD CD CD CD CD CO ro — rs, to t_D I— CD CD CD CD CD CD CD O —H OD OD tN. --_ι tO tO CD ΓN. CD CD CD CD CD O C O CD CD CD -_-. __■ _ —_ CD CD CD CD CD CD to —4 CO —• CO CD CD CD e» CD CD fN. -__■ —« CD CD O t CD CD SO . to CM to CM CO CO PLANT RESPONSE SCREENING (Herbicide) U P L A N D H E E D S P E C I E S PADDY UEED SPECIES XSC CHEH. TYPE kg/ha T - NO. REF. LYPES TRZAU GLXHX ZEAHX DACGL AHAVI DIGSA RUHJA POLHY AESIN CAGHE ORYSA ECHOR CYPDI ANEXE PRE .25 100 85 30 80 100 100 100 90 90 85 100 90 85 100 30 (B-29) POST .25 100 75 30 25 100 100 100 100 90 100 100 100 100 €0 PRE .25 100 90 30 40 100 100 100 90 100 80 90 (B-30) .125 90 30 0 0 90 100 100 70 80 40 90 .06 90 15 0 0 60 60 40 60 70 0 25 .03 65 0 0 0 10 50 0 0 25 ύ 25 O CD Ot *χ Q to —T CD CD CD CD CD CD —4 . —- CO O I - , SO C3 CD CD CD tO CD 4* CM O CO SO CD CD CD CD lO lO O- OO CO CO IN. CD CD OS CO CD CD CS_ CD CD ^ —■ CD CD CD CD CD t CD ^- t SO r CD CD CD CD CD CD CD ' CD CD • CD PRIMARY SCREENING (Herbicide) U P L A N D U E E D S P E C I E S PADDY HEED SPECIES XSC CHEH. TYPE kg/ha - - - HO. REF. LYPES TRZAU GLXHX ZEAHX DACGL AHAVI DIGSA RUHJA POLHY AESIN CAGHE ORfSA ECHUR CYPGI ANEXE PRE .25 100 60 40 50 100 100 100 80 90 90 100 50 100 30 (B-32) .125 90 40 30 10 80 90 100 70 40 70 100 40 100 0 .06 90 10 10 0 70 90 100 65 20 60 90 0 80 0 .03 80 0 0 0 70 80 80 60 0 10 80 0 70 0 POST .25 100 60 35 0 100 100 100 80 75 100 100 100 100 20 .125 90 20 10 0 80 100 90 40 50 90 60 50 85 20 .06 70 0 0 0 70 100 . 80 30 60 10 40 (00 20 .03 50 0 0 0 20 85 0 30 0 40 0 0 50 0 t CM CD CD O to CD to o CD OO tO tO • D to CD tO CD CD C_D CD CD CD CD " - CD O CM CD CD CD CD CD CD CD CD cr- co CD CD CD • CD CD CD CD o CD CD SO CM 67 CD CD CD CD to CD CD CD CO —4 CD CD PRE .25 100 10 10 0 90 100 100 90 90 70 80 100 80 100 60 (B-39) POST .25 90 10 80 100 80 70 0 100 90 100 100 20 PRE .25 90 10 0 0 70 100 90 65 90 20 75 15 20 10 10 (B-40) POST .25 90 0 0 0 60 20 60 30 75 20 70 70 65 0 15 PRE .25 100 80 65 55 80 100 100 70 90 100 100 100 100 100 70 (B-41) POST .25 100 70 35 10 100 100 100 90 100 85 100 100 100 100 60 PRE .25 100 90 40 60 90 100 100 90 100 80 100 100 100 100 60 (B-42) POST .25 100 50 35 25 100 100 100 90 100 70 100 90 100 90 70 PLANT RESPONSE SCREENING (Herbicide) U P L A N D U E E D S P E C I E S PADDY HEED SPECIES XSC CHEH. TYPE kg/ha - - NO. REF. LYPES TRZAU GLXHX ZEAHX DACGL AHAVI DIGSA RUHJA POLHY AESIN CAGHE ORYSA ECHOR CYPDI ANEX PRE .25 100 70 30 95 100 100 100 90 100 100 100 100 90 (B-43) POST .25 100 65 15 0 80 75 100 75 70 100 90 90. 90 60 PRE .25 100 65 40 50 90 100 100 80 70 90 100 50 100 60 (B- 4) .125 90 20 10 5 80 90 90 70 0 60 100 0 100 40 .06 80 10 0 0 70 70 60 70 0 30 100 0 100 10 .03 65 0 0 0 40 70 55 60 0 0 100 0 100 0 BECA POST .25 95 20 20 10 95 100 60 70 50 95 100 95 95 55 B A .125 90 10 0 0 90 95 60 50 60 80 75 20 90 1 .06 75 0 0 0 50 90 65 30 40 50 50 60 0 .03 60 0 0 0 20 70 40 20 20 50 40 50 0 PRE .25 100 60 45 30 100 100 100 100 90 90 100 100 90 70 (B-45) POST .25 100 60 25 30 100 100 100 70 80 100 100 100 100 60 PRE .25 100 85 55 90 100 100 100 90 90 100 (B-46) POST .25 100 60 20 10 100 100 100 90 90 100 90 100 100 6 PRE .25 90 60 15 15 90 90 100 75 80 90 (B-47) POST .25 100 30 10 100 100 100 90 80 100 90 100 100 9 PRE .25 90 70 10 90 95 100 70 100 70 90 90 100 100 7 (B-48) POST .25 100 60 35 0 100 100 100 90 100 90 100 90 100 100 3 -— PRE .25 80 0 0 0 60 100 100 70 75 10 70 100 90 90 50 (B-49) POST .25 70 35 0 0 60 100 35 35 30 80 60 50 70 60 PRE .25 90 70 30 30 80 90 100 60 95 75 95 100 90 90 40 (B-50) POST .25 100 60 15 0 100 100 100 80 95 90 100 80 70 100 30 PRE .25 100 90 50 60 80 100 100 50 100 90 95 100 90 90 70 (B-51) POST .25 100 65 30 20 100 100 100 90 100 90 100 100 100 100 60 PRIMARY SCREENING (Herbicide) U P L A N D H E E D S P E C I E S PADDY UEED SPECIES XSC CHEH. TYPE kg/ha - NO. REF. LYPES TRZAU GLXHX ZEAHX DACGL AHAVI DIGSA RUHJA POLHY AESIN CAGHE ORYSA ECHOR CYPDI AN PRE .25 80 20 10 0 80 100 100 100 40 50 100 70 100 70 (B-52) . . . .125 80 10 0 0 70 80 70 50 0 40 100 0 80 30 .06 70 10 0 0 70 80 60 50 0 20 100 0 70 0 .03 60 0 0 0 65 65 30 40 0 10 100 0 70 0 POST .25 100 30 30 30 100 100 100 90 70 100 0 95 100 60 .125 20 20 0 0 10 20 0 0 0 0 0 0 0 0 .06 0 0 0 0 0 0 0 0 0 0 0 0 0 0 .03 0 0 0 0 0 0 0 0 0 0 0 0 0 0 PRE .25 100 70 60 75 100 100 100 100 90 90 (B-53) POST .25 100 40 30 0 100 100 100 90 65 100 90 100 100 80 CD CO S IO CD CD CD O CD CD CD CD —4 » OS —4 ro SO CD CO tO CD to to t <• -4 CD CD CD ιr_ CD CD CD CO —• O IN. —I CD CD CD to oo CD CD CD to CD IN. -_»• CM CD NO CJ CD CD CD CD CD CD CD CD CD CD CD CD CD CD tO -_-ι -__• --4 — • -—• —ι I — CD CD CD CD CD to CD CD eo so CM OS SO CD CD CD CD CD CD OD CO CO CO o to CD CD CD CD CD CD CD to CD CD CD . O t ro ■ CD c? CD CD CD to CO OS so CD CD CD CD CD CD CD to to CD D CO CO ro CM CD CM CD CD —• CD CD to CM O CD CD CD CD to t CM CD to CM CD CD CD CD CD CD CD CD CD CD < CD ___ι CO ON O to C^i PRE .25 100 65 15 10 70 100 100 70 80 40 90 100 60 90 15 (B-63) POST .25 100 45 10 0 70 100 70 70 55 100 100 100 100 60 PRE .25 100 85 50 65 90 100 100 70 100 100 100 100 100 100 80 (B-64) POST .25 100 60 55 55 100 100 100 100 100 90 100 90 100 100 40 PRE .25 100 90 60 65 90 90 100 70 100 90 100 100 100 100 30 (B-65) POST .25 100 80 55 45 100 100 100 100 100 100 100 100 100 100 30 PRE .25 100 70 30 40 90 100 100 65 100 90 90 100 100 100 80 (B-66) POST .25 100 80 60 50 100 100 100 100 100 90 100 100 100 100 85 PRE .25 90 85 45 60 90 100 100 80 100 80 90 100 100 100 85 (B-67) .06 85 20 10 0 55 90 100 20 100 60 70 70 65 70 30 POST .25 100 70 60 35 100 100 100 100 100 100 100 100 100 100 35 .06 90 30 0 0 90 100 90 90 90 40 100 60 70 100 10 O O lO " OS o SO —4 N * o oo to O. so PLANT RESPONSE SCREENING (Herbicide) U P L A N D U E E D S P E C I E S PADDY UEED SPECIES XSC CHEH. TYPE kg/ha HO. REF. LYPES TRZAU GLXHX ZEAHX DACGL AHAVI DIGSA RUHJA POLHY AESIN CAGHE ORYSA ECHUR CYPDI ANEXE PRE .25 40 10 0 0 15 25 40 20 0 25 10 0 0 0 (B-70) POST .25 80 10 10 0 10 80 70 60 80 0 65 80 60 40 10 PRE .25 80 15 10 0 70 100 100 90 90 25 90 10 0 70 0 (B-71) - POST .25 90 0 25 0 65 100 70 70 90 25 90 70 65' 0 0 PRE .25 100 80 60 80 100 90 100 90 80 90 (B-72) POST .25 100 10 15 90 100 100 70 70 100 90 80 100 60 PRE .25 100 70 40 50 90 100 100 70 75 85 (B-73) POST .25 100 60 50 15 90 100 100 80 70 100 90 90 100 90 PRE .25 100 90 65 70 100 100 100 100 100 100 100 100 100 90 70 (B-74) POST .25 100 85 55 15 100 100 100 90 100 90 100 100 100 100 60 PRE .25 100 80 30 20 85 100 100 70 100 100 100 100 90 100 60 (B-75) POST .25 100 65 10 100 100 100 90 100 85 100 95 100 100 65 PRE .25 100 90 70 70 90 100 100 70 100 100 100 100 100 100 90 (B-76) POST .25 100 65 50 30 100 100 100 100 100 90 100 90 100 100 60 PRE .25 100 90 30 60 100 100 100 100 100 90 100 100 100 100 70 (B-77) POST .25 100 70 30 30 100 100 100 90 90 80 100 100 100 100 70 PRE .25 90 70 20 30 80 100 100 40 100 100 100 100 100 95 70 (B-78) POST .25 100 50 20 100 100 100 85 95 75 100 100 100 100 60 PRE .25 100 80 60 90 100 100 100 80 100 90 100 100 80 100 65 (B-79) POST .25 100 70 65 30 100 100 100 ?0 100 90 100 90 100 100 70 o β β c co i- IΛ CM CD OS 0\ CD CD t CD to OO CM PLANT RESPONSE SCREENING (Herbicide) U P L A H D H E E D S P E C I E S PADDY HEED SPECIES XSC CHEH. TYPE kg/ha NO. REF. LYPES TRZAH GLXHX ZEAHX DACGL AHAVI DIGSA RUHJA POLHY AESIN CAGHE ORYSA ECHOR CYPDI ANEXE PRE .25 100 60 0 30 60 90 ' 100 50 90 0 80 90 70 90 50 (C-2) POST .25 70 10 0 0 60 90 65 10 70 10 30 60 55 50 15 PRE .25 90 20 0 0 55 90 90 10 80 0 60 100 70 80 50 (C-3) , POST .25 80 10 0 0 30 80 ' 65 10 60 0 35 70 60 40 10 _ PRE .25 100 70 0 20 70 90 100 60 90 0 100 90 90 80 70 (CM) POST .25 100 15 0 15 70 90 90 40 80 0 95 80 70 80 25 PRE .25 100 70 0 15 90 100 100 70 90 0 100 100 90 90 60 (C-5) POST .25 100 60 0 10 60 90 80 35 70 0 80 70 100 90 60 PRE .25 100 60 0 10 50 80 100 20 80 10 ?S 100 100 90 70 (C-67 POST .25 IOC 60 10 50 100 90 25 90 100 70 100 100 20 POST .25 70 10 0 0 40 100 70 15 70 0 65 80 70 60 0 (C-7) PRE .25 100 40 0 65 95 100 90 90 0 70 100 30 90 0 (C-8) POST .25 95 15 20 0 20 100 65 10 75 0 100 100 100 50 35 PRE .25 80 60 40 80 95 15 80 0 85 90 60 90 15 ( C-9 ) POST .25 90 35 10 20 90 100 0 70 0 100 70 80 20 0 PRE .25 100 40 15 65 90 100 80 80 100 80 90 20 ( C-10 ) POST .25 100 40 10 10 65 100 90 40 90 ' 0 100 100 100 100 30 PRE .25 100 70 25 70 90 100 35 70 100 100 90 50 (C-U ) POST .25 100 70 0 30 60 100 100 70 90 100 100 90 100 2D PLANT RESPONSE SCREENING (Herbicide) U P L A N D H E E D S P E C I E S PADDY HEED SPECIES XSC CHEH. TYPE kg/ha NO. REF. LYPES TRZAH GLXHX ZEAHX DACGL AHAVI DIGSA RUHJA POLHY AESIN CAGHE ORYSA ECHOR CYPDI ANEXE PRE .25 90 75 0 10 70 90 100 60 90 0 100 100 95 90 70 (C-l2) β POST .25 100 70 0 10 65 100 85 20 80 0 90 70 100 80 60 PRE .25 90 20 0 0 60 90 85 35 70 10 60 75 70 90 0 (C-13) POST .25 80 15 10 0 20 100 70 10 60 0 60 30 65 0 0 PRE .25 100 60 0 20 85 90 100 90 0 95 100 95 100 25 (C-14) POST .25 70 60 10 10 50 100 80 .50 80 0 100 90 70 65 30 PRIMARY SCREENING (Herbicide) UP AND H E E.D SPECIES PADDY HEED SPECIES XSC CHEH. TYPE kg/ha NO. REF. • LYPES TRZAH GLXHX ZEAHX DACGL AHAVI DIGSA RUHJA POLHY AESIN CAGHE ORYSA ECHOR CYPDI ANEXE PRE .25 100 40 10 20 90 100 100 80 0 80 100 60 90 60 (C-18) .125 80 20 0 0 90 80 100 70 0 70 100 20 70 50 .06 70 0 0 0 80 80 100 65 0 60 100 0 70 30 .03 70 0 0 0 80 70 70 60 0 50 100 0 70 0 POST .25 100 10 0 0 30 100 60 30 0 100 100 100 100 50 .125 80 0 0 0 20 100 50 20 0 75 90 65 80 20 .06 50 0 0 0 20 75 10 10 0 60 65 30 65 0 .03 30 0 0 0 0 ' 65 0 10 0 20 60 30 60 0 AB B CD CD CD CD SO so CD CD CD lO - —• . O CD tO CO O PRE .25 100 50 5 5 100 90 100 BO 0 90 100 65 100 70 (C-22) .125 80 30 0 0 100 90 (GO 70 0 70 100 40 100 40 .06 80 10 0 0 ?0 80 (00 60 0 40 100 20 90 0 .03 70 0 0 0 δo 80 65 60 0 (0 90 0 90 0 POST .25 100 30 10 10 50 100 LOO 40 0 95 100 95 95 50 .125 75 20 0 0 30 100 80 20 0 70 95 60 70 0 .06 65 10 0 0 20 ?5 50 10 0 50 65 30 70 0 .03 55 0 0 0 !0 90 0 10 0 45 50 0 50 0 PRE .25 90 40 0 10 70 90 ?s 70 0 90 (C-23) POST .25 100 20 10 10 50 90 9JJ 50 0 90 65 50 SO 70 CD CD OS CD CD CD ■ CD CD CD CD CD cr- —• O * -- CD o o CM CD CD § g' ε s g CD CD SO CD CD cn CD CD -^ . CD CD CD CD CD CD O tn 1 CD 2 to cs CD CD CD CD CD CD IN. CD CD o CD O i CD 1 CD CD CD 1 CD CD 1 CD PLANT RESPONSE SCREENING (Herbicide) U P L A N D U E E D S P E C I E S PADDY HEED SPECIES KS C CHEH. TYPE kg/ha - - N0 . REF. LYPES TRZAU GLXHX ZEAHX OACGL AHAVI DIGSA RUHJA POLHY AESIH CAGHE ORYSA ECHOR CYPDI ANEKE PRE .25 90 90 0 70 80 9 !00 90 90 20 90 *0 90 ' 100 90 ( D-D POST .25 40 60 0 70 60 70 30 55 30 25 40 70 60 70 15 PRE .25 90 90 0 70 70 90 90 80 90 15 70 100 60 100 70 (D-2) POST .25 40 60 0 70 75 70 60 70 80 10 65 70 65 70 10 PRE .25 90 90 0 SO 70 90 90 90 90 0 90 90 70 90 70 (D-3) .... OST .25 55 30 0 65 70 70 SO 60 70 10 65 90 85 70 55 PRE .25 90 90 65 60 70 90 70 50 SO 50 65 60 30 50 50 (D-4) POST .25 100 90 90 100 • 80 • -0 90 00 30 80 100 100 100 50 90 PRE .25 90 90 0 70 60 90 90 80 90 0 90 JQ 70 90 70 (D-5) POST .25 60 35 0 65 60 70 70 55 70 15 45 70 • ?c 65 30 EXAMPLE 6: Wettable Powder 3- (N-methyl-N-3-fluorophenylaminooxoacetyl)-2- (4-isopropyl- 4-methyl-5-oxo-2-imidazolin-2-yl)-5-methylpyridine : 50% sodium al ylnaphthalenesulfonate: 2% low viscosity methyl ceollulose : 2% diatomaceous earth : 46% The ingredients are blended, coarsely hammer-milled a then, air milled to produce particles of active essentially all below 10 microns in diameter. EXAMPLE 7: Emulsifiable concentrate 3- (N-methyl-N-3-chloro-4-methoxyphenylaminooxo-acetyl)-2- (4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl) -5- methylpyridine: 10% chlorobenzene : 84% sorbitan monostearate and polyoxyethylene condensates thereof : 6% The ingredient are combined and stirred to produce a solution which can be emulsified in water for application EXAMPLE 8: Dust 3-(N-methyl-N-3-fluorophenylaminooxoacetyl) -2-(4-isopropyl- 4-methyl-5-oxo-2-imidazolin-2-yl)-5-methylpyridine : 10% attapulgite : 10% pyrophylite : 80% The active ingredient is blended with attapulgite and then passed through a hammer-mill to produce particles substantially all below 200 microns. The ground concentrate is then blended withpowdered pyrophylite until homogeneous. EXAMPLE 9: Granule wettable powder of Example : 6% attapulgite granules : 95% (U.S.S. 20-40 mesh ; 0.84 ~ 0.4 mm) A slurry of wettable powder containing 25% solids is sprayed on the surface of attapulgite granules in a double- cone blender. The granules are dried and packaged.

Claims: WHAT IS CLAIMED IS 1. 3- (aminooxoacetyl) -2- (2-imidazolin-2-yl) -pyridine derivatives and its salts having the structure of general formula (I) . wherein, R 1 is C 2 - C 4 alkyl; R 2 is C λ - C 4 alkyl, C 3 - C 5 cycloalkyl or C, - C 4 alkyl optionally substituted with 1 - 4 fluorine; R 3 is hydrogen, C x - C 3 alkyl, C t - C 3 alkyl optionally substituted with substituents contained in the following group I, C 2 - C 4 alkenyl or C 2 - C 4 alkynyl ; R 4 is the same as R 3 ; or phenyl, benzyl, pyridyl, furanyl, thiophenyl, benzofuranyl, dihydrobenzofuranyl, benzothiophenyl, dihydrobenzothiophenyl, indolyl, indolinyl, optionally substituted with 0-3 same or different substituents selected from the substituents contained in group II ; and when taken together, connecting R 3 and R 4 , a 3-7 membered ring may be formed, in which may contain 0-3 double bonds or 0-3 0, N, SOn(n=0-2) ; W is 0 or S; X is hydrogen, C α - C 4 alkyl, C, - C 4 alkoxy, C- x - C 4 alkoxyalkyl, or halogen; Y, Z are each hydrogen, halogen, C, - C 6 alkyl, C x - C 6 alkoxy, C x - C 6 alkoxyalkyl, C x - C 6 alkylthio, phenoxy, C, - C 6 haloalkyl, C x - C 6 alkylamino, C x - C 6 alkylsulfonyl or phenyl optionally substituted with one C,- C 4 alkyl, C 2 - C 4 alkoxy or halogen; and when taken together, a 5-6 membered ring may be formed in which may contain 0,N,S,double bonds or -(CH 2 )n-(n=0-4); A is hydrogen or -COR 5 (where R 5 is hydrogen, methyl or CH 2 C1) ; when A is hydrogen, tautomeric ii . er may exist; Group I contains hydroxy, alkoxy, haloalkoxy, cyano, -CO R 6 (where R 6 is hydrogen, alkyl, alkenyl, or alkynyl) , alkylthio, alkylsulfonyl, phenylthio, phenylsulfonyl, haloalkylthio, alkenoxy, alkoxy, -NR 6 R 7 (where R 6 , R 7 are each hydrogen, alkyl, alkenyl or alkynyl or R 6 , R 7 may form a ring) , phenyl, or phenoxy ; Group II contains group I substituents, halogen, nitro, haloalkyl, alkoxyalkyl, alkyl, alkenyl, alkynyl, alkylthioalkyl, -COR 8 (where R 8 is hydrogen, alkyl or phenyl) -CO2 R 9 (where R 9 is hydrogen or alkyl) ,-S0 3 R 10 (where R 10 is hydrogen or alkyl) ,-S0 2 NR 6 R 7 , -CONR 6 R 7 (R 6 ,R 7 are the same as above) , or (CH 2 )ru^ -N (CH,)π^ (where n, m are an integer of 1-3, D is a single bond or double bond, 0 2 , S, S0 2 , NCH 3 ) . 2. Compounds of Claim 1 where R 1 is methyl; R 2 is ethyl or isopropyl; R 3 is hydrogen, methyl, ethyl, methoxymethyl, methylthiomethyl, or allyl ; R 4 is C x - C 2 alkyl optionally substituted 0-2 substituents selected from halogen, hydroxy, alkoxy, alkylthio, R 6 NR 7 (where R 6 , R 7 are hydrogen, alkyl, alkenyl, or alkynyl) , phenyl, phenoxy, or phenyl optionally substituted with 0-3 same or different substituents selected from substituents contained in the above group II ; NR 3 R 4 is (where n, m are an integer of 1-3, D is single bond, or double bond, 0, NCH 3 , S, SO, S0 2 ) ; A is hydrogen ; I is 0 ; X is hydrogen, Y is hydrogen, methyl or ethyl ; Z is hydrogen, methyl or ethyl ; 3. Compounds of Claim 2 where R 2 is ispropyl; R 3 is methyl or CH 2 CH 3 ; R 4 is phenyl substituted with substituents contained in the above group II; NR 3 R 4 Y is hydrogen, methyl or ethyl. Compounds of Claim 3 where R 3 is phenyl optionally substituted 0-2 substitutes with 3,4,5 phenyl selected from methyl, ethyl, propyl, isopropyl, butyl, tert- butyl, cyclohexyl, methoxy, ethothy, isopropoxy, phenoxy, SCH 3 , S0 2 CH 3 , Cl, Br, F, (CH 3 ) 2 N and CF 3 ; Y is methyl. 5. Compounds of Claim 1 having said general formula(I) of 3-(N-methyl-N-3-fluorophenyl-aminooxoacetyl) -2-(4- isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl) -5-methyl- pyridine. 6. Compounds of Claim 1 having said general formula(I) of 3-(N-methyl-N-3-chloro-4-methoxy-aminooxoacetyl) -2-(4- isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl) -5-methy1- pyridine. 7. Compounds of Claim 1 having said general formula(I) of 3- (N-methyl-N-3,5-dimethylphenyl-aminooxoacetyl) -2- (4- isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)-5-methyl- pyridine. 8. Compounds of Claim 1 having said general formula (I) of 3- (N-methyl-4-n-butylphenyl-aminooxoacetyl) -2- (4- isoproρyl-4-methyl-5-oxo-2-imidazolin-2-yl) -5-methyl- pyridine. 9. Compounds of Claim 1 having said general formula(I) of 3- (N-methyl-N-4-t-butylphenyl-aminooxoacetyl)-2- (4- isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)-5-methyl- pyridine. 10.Compounds of Claim 1 having said general formula (I) of 3-(N-methyl-N-4-phenoxy-aminooxoacetyl)-2-(4- isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl) -5-methyl- pyr-dine. 11.Compounds of Claim 1 having said general formula (I) of 3-(N-methyl-N-3-chlorophenyl-aminooxoacetyl) -2- (4- isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl) -5-methyl- pyridine. 12.Compounds of Claim 1 having said general formula(I) of 3-(N-methyl-N-4-cyclohexaphenyl-aminooxoacetyl)-2-(4- isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl) -5-methyl- pyridine. 13.Compounds of Claim 1 having said general formula(I) of 3- (N-methyl-N-4-dimethylamionophenyl-aminooxoacetyl)-2- (4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)-5- methyl-pyridine. 14.Compounds of Claim 1 having said general formula(I) of 3-(N-methyl-N-3-trifluoromethylphenyl-aminooxoacetyl) - 2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)-5- methyl-pyridine. 15.Compounds of Claim 1 having said general formula(I) of 3-(N-methyl-N-3, -dichlorophenyl-aminooxoacetyl)- 2- (4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)-5- methyl-pyridine. 16.Compounds of Claim 1 having said general formula(I) of 3- (N-methyl-N-4-trifluoromethylphenyl-aminooxoacetyl) - 2- (4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)-5- methyl-pyridine. 17.Compounds of Claim 1 having said general formula (I) of 3- (N-methyl-N-3-methylphenyl-aminooxoacetyl)-2- (4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl) -5- methyl-pyridine. 18.The method of manufacturing pyridine derivatives described in general formula(I) of Claim 1 by acylating the compounds of following formula(II) . Wherein, R 1 , R 2 , A, X, Y, Z and W are the same as afore¬ mentioned. 19.The method of manufacturing pyridine derivatives of Claim 18 described in the following general formula (III) in said acylation reaction. Wherein, R 1 , R 3 , R 4 are the same as aforementioned ; neither of R 3 and R 4 is hydrogen. 20.The method of manufacturing pyridine derivatives described in general formula (I) by reacting following general formula (II) with following genral formula (IV) . ) Wherein, R 1 , R 2 , R 4 , A, X, Y, Z and W are the same as aforementioned. 21.The method of manufacturing pyridine derivatives described in general formula(I) - y reacting following general formula(II) with following genral formula (VI) . Wherein, R 1 , R 2 , A, X, Y, Z and W are the same as aforementioned, in which n is 1 ~ 6 and R 3 in general formula(I) is hydrogen or hydroxy. 22.Herbicides or plant-growth modulator containing the compounds of Claim 1 as an active ingredient, described in general formula(I) . 23.Herbicides in a form of wettable powder, wherein said compounds of general formula(I) are characterized by following formula: active ingredient of 45 ~ 80 wt %, micro-powder carrier of 20 ~ 40 wt %, dispersing agent of 2 ~ 5 wt %, and non-ionic surfactant of 2 ~ 5 wt %. 24.Herbicides in a form of flowable liquid, wherein said compounds of general formula(I) are characterized by following formula: active ingredient of 30 ~ 50 wt %, gelator of 1 ~ 3 wt %, dispersing agent of 1 ~ 5 wt %, alcohol of 0.1 - 3 wt %, and water of 40 ~ 60 wt %. 0 25.Herbicides in a form of emulsifiable concentrates, wherein said compounds of general formula(I) are characterized by following formula: active ingredient of 5 ~ 25 wt %, carrier of 65 ~ 90 wt %, and non-ionic surfactant of 5 ~ 10 wt %. N 26.Herbicides in a particle form, wherein said compounds of general formula(I) are characterized by following formula: active ingredient of 3 ~ 20 wt % and granular carrier of 97 ~ 80 wt %. 27.The method of using herbicides, wherein said compounds of general formula(I) are applied in a ratio of about 0.03 ~ 10 kg/ha.

Inventors: CHANG HAE SUNG, HWANG IN TAEK, JEON DONG JU, KIM DAE WHANG, RYU JAE WOOK, CHANG, HAE, SUNG, HWANG, IN, TAEK, JEON, DONG, JU, KIM, DAE, WHANG, RYU, JAE, WOOK
Applicants: KOREA RES INST CHEM TECH, KOREA RESEARCH INSTITUTE OF CHEMICAL TECHNOLOGY
Application year: 1991
Main classification: C07D417
IPC codes: A01N43, C07D401, C07D405, C07D409, C07D413, C07D417