MX2008008312A - Herbicidal composition - Google Patents

Abstract

A herbicidal composition in the form of an emulsifiable concentrate which comprises, in addition to emulsifiers and water-insoluble solvents, 2,2-dimethyl-propionic acid 8-(2,6- diethyl-4-methyi-phenyl)-9-oxo-1 ,2,4,5-tetrahydro-9H-pyrazolo[1 ,2-d][1 ,4,5]oxadiazepin-7-yl ester and an alcohol.

Description

HERBICIDE COMPOSITION DESCRIPTION OF THE INVENTION The present invention relates to a herbicidal composition in the form of an emulsifiable concentrate comprising 8- (2,6-diethyl-4-methyl-phenyl) -9-oxo-l, 2, 4, 5 -tetrahydro-9H-pyrazolo [1,2-d] [1, 4, 5] oxadiazepin-7-yl ester of 2,2-dimethyl-propionic acid as herbicidally active compound, and to the use of the composition to control weeds in crops of useful plants. 8- (2,6-Diethyl-4-methyl-phenyl) -9-oxo-l, 2,4,5-tetrahydro-9H-pyrazolo [1,2-d] [1,4,5] oxadiazepin- 7-2-dimethyl-propionic acid 7-ester exhibits a herbicidal action against weeds in cereals, especially against grasses in wheat, barley and rye crops. The compound is also known as pinoxadene and is described, for example, in European Patent EP-A-1 062 217. The emulsifiable concentrates (EC) of 8- (2,6-diethyl-4-methyl-phenyl) ) -9-oxo-l, 2,4,5-tetrahydro-9H-pyrazolo [1,2-d] [1, 4, 5] oxadiazepin-7-yl ester of 2,2-dimethyl-propionic acid are known from Example Fl of the European Patent EP-A-1 062 217. It was found, however, that those EC do not have adequate stability and with the passage of time, the herbicide is decomposed or modified, for example, by hydrolysis reactions or transesterification. The problem of the present invention consists Ref: 193791 now in providing new emulsifiable concentrates of 8- (2,6-diethyl-4-methyl-phenyl) -9-oxo-l, 2, 4, 5-tetrahydro-9H- pyrazolo [1,2-d] [1, 4, 5] oxadiazepin-7-yl ester of 2,2-dimethyl-propionic acid distinguished by better storage stability. Surprisingly it was found that the problem can be solved by adding an alcohol as a solvent to the known EC of Example Fl of European Patent EP-A-1 062217 or by replacing the ketone that may be present by the alcohol. The present invention relates, accordingly, to a herbicidal composition in the form of an emulsifiable concentrate comprising, in addition to emulsifiers and water-insoluble solvents, a) 8- (2,6-diethyl-4-methyl-phenyl) - 9-oxo-l, 2, 4,5-tetrahydro-9H-pyrazolo [1,2-d] [1,4,5] oxadiazepin-7-yl ester of 2,2-dimethyl-propionic acid and b) an alcohol. The presence of the alcohol in the composition according to the invention surprisingly results in a marked stabilization of the EC. Contrary to expectations, no transesterification reactions of the herbicide are observed. The alcohols which are taken into account are preferably C1-C12 alkanols such as methanol, ethanol, propanol, hexanol, octanol and dodecanol. The alcohols may be straight or branched chain, for example, 2-ethylhexanol and isotridecanol, may be present in the form of diols or triols, for example, ethylene glycol, propylene glycol, dipropylene glycol and 2-methyl-2,4-pentanediol, may be present in the form of glycol monoethers such as butyl glycol and butyl diglycol, and also, for example, furfuryl and tetrahydrofurfuryl alcohol, benzyl alcohol, 4-hydroxy-4-methyl-2-pentanone, and may be present in the form of esters may be substituted. such as alkyl esters of lactic acid, for example, ethyl lactate and butyl lactate. The cyclic alcohols, preferably cyclopentanol and cyclohexanol, can also be used according to the invention. Preferred alcohols that may be mentioned are 2-ethylhexanol, n-octanol, benzyl alcohol, tetrahydrofurfuryl alcohol, 2-methyl-2,4-pentanediol, 4-hydroxy-4-methyl-2-pentanone and cyclohexanol, as well as lactate ethyl and butyl lactate. Particular preference is given to tetrahydrofurfuryl alcohol, benzyl alcohol and 2-methyl-2,4-pentanediol. Preferably, from 1 to 97% by weight of alcohol are present in the emulsifiable concentrates according to the invention. A content of 5 to 50% by weight, in particular 10 to 30% by weight, is particularly preferred. These alcohols can also be mixed with others or can be used in admixture with conventional water-insoluble solvents. Examples of such water insoluble solvents are aromatic hydrocarbons, such as toluene, xylene, eumeno, mixtures of aromatic hydrocarbons with a boiling point of 160 to 180 ° C (Solvesso 100) or of 180 to 210 ° C (Solvesso 150) or of 230 to 290 ° C (Solvesso 200) , aliphatic or cycloaliphatic hydrocarbons (Exxsol D80, Exxsol D100, Exxsol D120, Isopar H and Isopar V), acetates of fatty alcohols (Exxate 700, Exxate 1000), isobornyl acetate, benzyl acetate, lower alkyl esters of dicarboxylic acids such as maleic, fumaric, succinic, glutaric and adipic acid (DBE Solvent), benzoic acid esters such as benzyl benzoate, methyl benzoate and dipropylene glycol dibenzoate, as well as lower alkyl esters of higher fatty acids such as methyl acid esters fatty acid Cs-Cio and methyl esters of fatty acid Ci6-C? ß and ketones such as cyclohexanone, acetophenone, methyl-n-pentyl ketone. Preferably, from 0 to 95% by weight of water-insoluble solvent is present in the emulsifiable concentrates according to the invention. A content of 10 to 70% by weight, in particular 30 to 60% by weight, is particularly preferred. For the compositions according to the invention it is possible to use the emulsifiers commonly used in connection with the ECs. Examples which may be mentioned are castor oil ethoxylates, alcohol ethoxylates, tristyrylphenol ethoxylates, their mixtures and also mixtures with surfactant compounds such as the calcium salt of dodecylbenzenesulfonic acid or the sodium salt of dioctylsulfosuccinic acid. 0.5 to 50% by weight of emulsifier is present in the emulsifiable concentrates according to the invention. A content of 2 to 30% by weight, in particular 2 to 10% by weight, is particularly preferred. The compositions according to the invention may comprise, in addition to 8- (2,6-diethyl-4-methyl-phenyl) -9-oxo-1, 2,4,5-tetrahydro-9H-pyrazolo [1, 2- d] - [1, 4,5] oxadiazepin-7-yl ester of 2,2-dimethyl-propionic acid, one or more herbicides which are compatible therewith. "Compatible" means in this context that the herbicidal combination is chemically stable and does not exhibit antagonism or high phototoxicity with respect to useful plants. Such herbicides are preferably selected from the groups of the sulfonylureas, for example, triasulfuron, tribenuron, metsulfuron, thifensulfuron, flupyrsulfuron, chlorsulfuron, prosulfuron, amidosulfuron, mesosulfuron, sulfosulfuron and tritosulfuron, aryloxyphenoxypropionates and heteroaryloxyphenoxypropionates such as clodinafop-propargyl, fenoxaprop. -P-ethyl, diclofop-methyl and cyhalofop-butyl, triazolopyrimidines such as florasulam, metosulam and flu etsulam, arylcarboxylic acids, preferably dicamba and clopyralid, also aryloxycarboxylic acids, preferably esters of 2,4-D, 2,4-DP mecoprop, mecoprop-P, MCPA, MCPB, dichlorprop-P and fluroxypyr, cyclohexanedione oximes such as tralcoxydim, thiocarbamates such as trialate and prosulfocarb, hydroxybenzonitriles such as bromoxynil, bromoxynil octanoate, ioxynil and ioxyin octanoate, dinitroanilines such as pendimethalin and trifluralin, and also pyridinecarboxamides such as diflufenica do not. It is present from 1 to 50% by weight of herbicide 8- (2,6-diethyl-4-methyl-phenyl) -9-oxo-l, 2,4,5-tetrahydro-9H-pyrazolo [1,2-d] [1, 4, 5] oxadiazepin-7-yl ester of 2,2-dimethyl-propionic acid (alone or in mixture with one or several other herbicides) in the emulsifiable concentrates according to the invention. A content of 3 to 30% by weight, in particular 5 to 15% by weight, is particularly preferred. The compositions according to the invention allow the simultaneous use of antidotes, giving preference to cloquintocet-mexyl, mefenpyr-diethyl or isoxadifen-ethyl and its derivatives, as the corresponding acids and salts.

These antidotes are described, for example, in The Pesticide Manual, 12th Edition, BCPC, and in Danish Patent DE-A-43 31 448. Adjuvants may also be added to the compositions according to the invention, with the result that its activity can be increased. These adjuvants can be, for example: nonionic surfactants, mixtures of nonionic surfactants, mixtures of anionic surfactants with nonionic surfactants, organosilicon surfactants, mineral oil derivatives with and without surfactants, vegetable oil derivatives with and without the addition of surfactant, fish oils and other oils of animal nature and their alkyl derivatives with and without surfactants, natural higher mono- or polyunsaturated fatty acids, preferably with 8 to 28 carbon atoms, and their alkyl ester derivatives, organic acids which contain a system of aromatic rings and one or more carboxylic acid radicals, as well as their alkyl derivatives. Blends of individual adjuvants with others and in combination with organic solvents can result in further improvement of the action. Suitable adjuvants for the present invention are described in European Patent EP-A-1 062 217. The preparation of the ECs according to the invention is carried out substantially in accordance with the usual known method of dissolving the herbicide in alcohol and optionally in the water insoluble solvent and then the addition of a conventional emulsifier. The mixture obtained in this way is stirred until a clear solution is formed. While commercial products will preferably be formulated in the form of concentrates, the final consumer will normally employ formulations diluted with water. EXAMPLES Example 1: EC 1: An emulsifiable concentrate of 8- (2,6-diethyl-4-methyl-phenyl) -9-oxo-l, 2,4,5-tetrahydro-9H-pyrazolo [1, 2] is prepared. -d] [1, 4, 5] oxadiazepin-7-yl ester of 2,2-dimet i 1 -propionic acid by dissolving 10.5g of that herbicide and 2.7g of the cloquintocet-mexi lo antidote in a mixture of 1g of Soprophor TS / 10 (tries tirilfenol ethoxylated with 10 moles of ethylene oxide), 1 g of Atlas G-5000 (copolymer of butanol block OE / OP), 1 g of Rhodacal 60 / BE (calcium salt of dodecylbenzenesulfonic acid) and 86.7 g of Solvesso 200 ND (aromatic hydrocarbons). This corresponds substantially to the EC according to examples Fl. A) and b) of European Patent EP-A-1 062 217. EC2: An emulsifiable concentrate is prepared in the same manner as EC 1 but instead of 86.7 g of Solvesso 200 ND, only 56.7 g and additionally 30.0 g of cyclohexanone are used. This corresponds substantially to the EC according to examples Fl. c) and d) of European Patent EP-A-1 062 217. EC3: An emulsifiable concentrate is prepared in the same manner as EC 1 but instead of 86.7 g of Solvesso 200 ND, only 56.7 g and additionally 30.0 g are used. of tetrahydrofurfuryl alcohol. This corresponds to an EC according to the present invention. The concentrates are stored for 2 weeks at a temperature of 70 ° C. The results obtained are then indicated in Table 1 below. Table 1 Comparison between EC 1, EC 2 and EC 3 with respect to the stability of 8- (2,6-diethyl-4-methyl-phenyl) -9-oxo-l, 2,4,5-tetrahydro-9H-pyrazolo [1,2-d] [1, 4, 5] oxadiazepin-7-yl ester of 2,2-dimethyl-propionic acid contained therein.

The table shows that, when tetrahydrofurfuryl alcohol (EC 3) is used, it is possible to obtain a significantly more stable formulation than in the case of cyclohexanone (EC 2) and Solvesso 200D alone (EC 1). Example 2: An emulsifiable concentrate is prepared which contains 107g of 8- (2,6-diethyl-4-methyl-phenyl) -9-oxo-l, 2,4,5-tetrahydro-9H-pyrazolo [1,2- d] [1, 4, 5] oxadiazepin-7-yl ester of 2,2-dimethyl-propionic acid and 26 g of cloquintocet-mexyl upon dissolving those compounds in a mixture of 10 g of Soprophor TS / 10 (tristyrylphenol ethoxylated with 10%). mol of ethylene oxide), 10 g of Atlas G-5000 (copolymer block of butanol OE / OP), 10 g of Rhodacal 60 / BE (calcium salt of dodecylbenzenesulfonic acid), 524 g of Solvesso 200 ND (aromatic hydrocarbons) and 300 g of 2-methyl-2,4-pentanediol and stir until a clear solution is obtained. The concentrate prepared in this way is stored for 4 weeks at a temperature of 50 ° C, after which only a 2% loss of 8- (2,6-diethyl-4-methyl-phenyl) -9-oxo is observed. -l, 2,4, 5-tetrahydro-9H-pyrazolo [1,2-d] [1, 4, 5] oxadiazepin-7-yl ester of 2,2-dimethyl-propionic acid. Example 3: An emulsifiable concentrate is prepared as in Example 2, except that 300 g of diacetone alcohol is used in place of 2-methyl-2,4-pentanediol. The concentrate obtained in this way is stored for 4 weeks at a temperature of 50 ° C, after which only a 2% loss of 8- (2,6-diethyl-4-methyl-phenyl) -9-oxo is observed. -l, 2,4,5-tetrahydro-9H-pyrazolo [1,2-d] [1, 4, 5] oxadiazepin-7-yl ester of 2,2-dimethyl-propionic acid. Example 4: An emulsifiable concentrate containing 129 g of 8- (2,6-diethyl-4-methyl-phenyl) -9-oxo-1,2,4,5-tetrahydro-9H-pyrazolo [1, 2] is prepared. -d] [1, 4, 5] oxadiazepin-7-yl ester of 2, 2-dimethyl-propionic acid and 31 g of cloquintocet-mexyl by dissolving those compounds in a mixture of 10 g of Soprophor TS / 10 (tristyrylphenol ethoxylated with 10 mol of ethylene oxide), 50 g of Atlas MBA 1307 (mono-branched fatty alcohol alkoxylate), 1320 g of Solvesso 200 ND (aromatic hydrocarbons) and 500 g of tetrahydrofurfuryl alcohol and stir until a clear solution is obtained. The concentrate prepared in this way is stored for 4 weeks at a temperature of 50 ° C, after which only a 2% loss of 8- (2,6-diethyl-4-methyl-phenyl) -9-oxo is observed. -l, 2,4,5-tetrahydro-9H-pyrazolo [1,2-d] [1,4,5] oxadiazepin-7-yl ester of 2,2-dimethyl-propionic acid. Example 5: An emulsifiable concentrate containing 54 g of 8- (2,6-diethyl-4-methyl-phenyl) -9-oxo-l, 2,4,5-tetrahydro-9H-pyrazolo [1, 2] is prepared. -d] [1, 4, 5] oxadiazepin-7-yl ester of 2,2-dimethyl-propionic acid and 13 g of cloquintocet-mexyl by dissolving those compounds in a mixture of 10 g of Soprophor TS / 10 (tristyrylphenol ethoxylated with 10 mole of ethylene oxide), 10 g of Atlas G-5000 (butanol block copolymer OE / OP), 10 g of Rhodacal 60 / BE (calcium salt of dodecylbenzenesulfonic acid), 158 g of Solvesso 200 ND (aromatic hydrocarbons ), 450 g of rapeseed oil methyl ester and 250 g of tetrahydrofurfuryl alcohol and stir until a clear solution is obtained. The concentrate prepared in this way is stored for 4 weeks at a temperature of 50 ° C, after which only a 3% loss of 8- (2,6-diethyl-4-methyl-phenyl) -9-oxo is observed. -1,2,4,5-tetrahydro-9H-pyrazolo [1,2-d] [1, 4, 5] oxadiazepin-7-yl ester of 2,2-dimethyl-propionic acid. Example 6: An emulsifiable concentrate containing 60 g of 8- (2,6-diethyl-4-methyl-phenyl) -9-oxo-l, 2,4,5-tetrahydro-9H-pyrazolo [1, 2] is prepared. -d] [1,, 5] oxadiazepin-7-yl ester of 2,2-dimethyl-propionic acid and 15 g of cloquintocet-mexyl by dissolving those compounds in a mixture of 20 g of NANSA EVM63 / B (calcium dodecylbenzenesulfonate) , 50 g of SERVIROX OEG 59 E (ethoxylated castor oil), 675 g of Solvesso 200 ND (aromatic hydrocarbon) and 200 g of benzyl alcohol and stir until a clear solution is obtained. The concentrate prepared in this way is stored for 4 weeks at a temperature of 50 ° C, after which only a 3% loss of 8- (2,6-diethyl-4-methyl-phenyl) -9-oxo is observed. -l, 2, 4, 5-tetrahydro-9H-pyrazolo [1,2-d] [1,4,5] oxadiazepin-7-yl ester of 2,2-dimethyl-propionic acid. Biological examples: 8- (2,6-diethyl-4-methyl-phenyl) -9-oxo-l, 2,4,5-tetrahydro-9H-pyrazolo [1,2-d] [1, 4, 5] oxadiazepin-7-yl ester of 2,2-dimethyl-propionic acid to the plant or its locus at application rates of 5 to 200 g / ha, especially from 10 to 80 g / ha, more preferably from 30 to 60 g / ha. The application rates of the antidote are generally from 2 to 100 g / ha, preferably from 2 to 50 g / ha, especially from 7.5 to 15 g / ha. The concentration required to achieve the desired effect can be determined by experimentation. It depends on the nature of the action, the state of development of the cultivated plant and the weed and the application (place, moment, method) and can vary within wide limits depending on these parameters. The rate of application of the antidote to the herbicide is largely dependent on the mode of application. When a field treatment is carried out with a tank mix with a combination of antidote and herbicide or by separate application of antidote and herbicide, the rate of herbicide to antidote will usually be from 1: 1 to 10: 1, preferably from 4: 1 The herbicidal activity of the emulsifiable concentrates according to the invention is demonstrated in the following example: Example Bl: Herbicidal action after emergence of the plants (post-emergence action): monocotyledonous and dicotyledonous weeds are grown under nursery conditions in plastic pots with standard earth. The application of the emulsifiable concentrate is carried out in the leaf stage 3 to 6 of the test plants. For this purpose, the aforementioned EC 3 is dissolved in 400 liters of water / ha. The tests are evaluated after 20 days (% action, 100% = plant has died, 0% = no phytotoxic action); Test plants: Alopecurus mirosuroides, Lolium rigidum, Avena fatua, Setaria viridis. The results are shown in table 2 below: Table 2: Weed Control Plants (%) in a test application (g of ai / ha) of 8 16 64 Alopecurus 70 80 100 miosuroides Avena fatua 95 98 100 Lolium rigidum 100 100 100 Setaria viridis 80 100 100 It is noted that in relation to this date, the best method known by the applicant to carry out the aforementioned invention is that which is clear from the present description of the invention.

Claims (11)

1. CLAIMS Having described the invention as above, the content of the following claims is claimed as property: 1. A herbicidal composition in the form of an emulsifiable concentrate characterized in that, in addition to emulsifiers and water insoluble solvents, it contains a) 8- (2, 6-diethyl-4-methyl-phenyl) -9-oxo-l, 2, 4,5-tetrahydro-9H-pyrazolo [1,2-d] [1,4,5] oxadiazepin-7-yl ester of 2-acid , 2-dimethyl-propionic and b) an alcohol.
2. 2. A composition according to claim 1, characterized in that it comprises, as alcohol, 2-ethylhexanol, n-octanol, benzyl alcohol, tetrahydrofurfuryl alcohol, 2-methyl-2,4-pentanediol, 4-hydroxy-4-methyl- 2-pentanone, cyclohexanol, methyl lactate or butyl lactate.
3. 3. A composition according to claim 2, characterized in that it comprises, as alcohol, benzyl alcohol, tetrahydrofurfuryl alcohol or 2-methyl-2,4-pentanediol.
4. 4. A composition according to claim 1, characterized in that it comprises from 1 to 50% by weight of 8- (2,6-diethyl-4-methyl-phenyl) -9-oxo-l, 2, 4, 5- tetrahydro-9H-pyrazolo [1,2-d] [1, 4, 5] oxadiazepin-7-yl ester of 2,2-dimethyl-propionic acid.
5. 5. A composition according to claim 1, characterized in that it comprises from 1 to 97% by weight of alcohol.
6. 6. A composition according to claim 1, characterized in that it comprises another herbicide that is compatible with 8- (2,6-diethyl-4-methyl-phenyl) -9-oxo-l, 2, 4, 5-tetrahydro- 9H-pyrazolo [1,2-d] [1,4,5] oxadiazepin-7-yl ester of 2,2-dimethyl-propionic acid.
7. 7. A composition according to claim 6, characterized in that it comprises, as another herbicide, a member of the group of sulfonylureas, aryloxyphenoxypropionates, triazolopyrimidines, arylcarboxylic acids, aryloxycarboxylic acids, heteroaryloxycarboxylic acids, cyclohexanedione oximes, thiocarbamates, hydroxybenzonitriles, dinitroanilines and pyridinecarboxamides.
8. 8. A composition according to claim 1, characterized in that it comprises an antidote.
9. 9. A composition according to claim 8, characterized in that it comprises cloquintocet-mexyl, mefenpyr-diethyl or isoxadifen-ethyl.
10. 10. A composition according to claim 1, characterized in that it comprises an adjuvant.
11. 11. An unwanted growth control method of plants, characterized in that it comprises the application of a quantity of herbicidal efficacy of a composition according to claim 1 to the plants or their locus.