MXPA98004988A - New compositions herbici - Google Patents

Abstract

The invention relates to compositions comprising (a) a 2-cyano-1,3-dione derivative or a salt, metal complex or enol tautomeric form, agriculturally acceptable thereof, and (b) at least one member thereof. group consisting of a triazine herbicide, a chloroacetamide herbicide, a 2,6-dinitroaniline herbicide, aclonifen, which consists of 2-chloro-nitro-3-phenoxyaniline, diuron, which consists of 3- (3, 4-dichlorophenyl) -1,1-dimethylurea, and a hydroxybenzonitrile herbicide and with its use as a herbicide

Description

NEW HERBICIDAL COMPOSITIONS Description of the invention This invention relates to new herbicidally active compositions comprising a 2-cyano-l, 3-dione derivative and another herbicide. The European patent publications Nos. 0496630, 0496631, 0625505 and 0625508 describe certain l-phenyl-2-cyano-l, 3-dione derivatives which possess herbicidal properties. European Patent Publication No. 0213892 describes herbicidally active enols. While they possess a good level of herbicidal activity, many of these compounds lack a sufficiently broad spectrum of activity to control certain weed-infested areas used or to be used to grow crops (for example, corn or sugarcane). A variety of known herbicides provide control of many weeds that infect crop growing areas. These include: 1, 3, 5-triazine and 1,2,4-triazinone herbicides (hereinafter referred to as triazine herbicides) such as amethrin (N2-ethyl-N4-isopropyl) 6-methylthio-l, 3, 5-triazin-2,4-diamine), atrazine (6-chloro-N 2 -ethyl-N 4 -isopropyl-1,3,5-triazin-2,5-diamine), terbutrin ( N2-tert-butyl-N4-ethyl-6-methylthio-l, 3,5-triazine-2,4-diamine) and metribuzin (4-amino-6-tert-butyl-3-methylthio- REF: 27734 1, 2,4-triazine-5 (4H) -one Chloroacetamides such as alachlor (2-chloro-2 ', 6'-diethyl-N-methoxymethylacetanilide), acetochlor (2-chloro-N-ethoxymethyl-6'-ethylacet-o) -toluidide), metolachlor [2-chloro-β '-ethyl-N- (2-methoxy-1-methylethyl) acet-o-toluidiu-ro], propachlor (2-chloro-N-isopropylacetanilide) and dimethanamide [2- chloro-N- (2,4-dimethyl-3-thienyl) -N- (2-methoxy-1-methylethyl) acetamide]; 2,6-dinitroaniline herbicides such as pendimethalin [N- (1-ethylpropyl) -3) , 4-dimethyl-2, 6-dinitrobencena ina] and trifluralin [2,6-dinitro-N, N-dipropyl-4- (tri fluoromethyl) benzenamine]; aclonifen (2-chloro-6-nitro-3-phenoxyaniline), diuron [3- (3,4-dichlo-phenyl) -1,1-dimethylurea]; and hydrobenzonitrile herbicides, such as bromoxynil [3, 5-dibromo-4-hydroxybenzonitrile] and ioxynil [4-hydroxy-3,5-diiodobenzonitrile], each of which is described in "The Pesticide Manual" , 10th edition (British Crop protection Council, 1994. As a result of research and experimentation, it has been found that the use of one or more of these herbicides, in combination with certain 2-cyano-l, 3-dione derivatives, extends Accordingly, such combinations represent an important technological advance The term "combination" as used in the specification refers to the "combination" of the 2-cyano-l, 3-dione derivative and the Associated herbicide Surprisingly, in addition to this, it has been found that under certain conditions, the combined herbicidal activity of certain 2-cyano-l, 3-diones with certain other herbicides for the control of important weed species such as Setaria viridis, Setaria viridis or Ec hinochloa crus-galli is higher than expected, without an unacceptable increase in the phototoxicity of the crop, this is the mixture shows synergism as defined by Limpel, L.E., P.H. Schuldt and D. Lamont, 1962, 1 Proc NEWCC 16, 48-53, using the formula: E = X + Y - XY 100 also known as the Colby formula (Colby, S.R., 1967, Weeds 15, 20-22), where: E = is the expected percent inhibition of growth by a mixture of two herbicides A and B, at defined doses. X = percent inhibition of growth by herbicide A at a defined dose. Y = percent inhibition of growth by herbicide B at a defined dose.

When the observed percentage of inhibition by the sample is greater than the expected E value, using the above formula, the combination is synergistic. This unexpected synergistic effect gives an improved reliability for the control of these competitive weeds of many crop species and contributes to a considerable reduction in the amount of active ingredient required for weed control. This remarkable synergistic effect, provides improved reliability of control of a diversity of weed species and allows the reduction in the amount of active ingredients used. A high level of control of these weeds is desirable to prevent: 1) loss of yield, through competition and / or difficulties with harvest, 2) contamination of the crop leading to storage and cleaning difficulties, and 3) a return of the weed seed, not acceptable, to the soil. According to the present invention, a method is provided for controlling the growth of the weeds in a site, which comprises the application to the site of a herbicidally effective amount of: (a) a herbicide of 2-cyano-l, 3- dione or a salt, metal complex or agriculturally acceptable enol tautomeric form thereof, and (b) at least one member of the group consisting of a triazine herbicide, a chloroacetamide herbicide, a 2,6-dinitroaniline herbicide , aclonifen, diuron and a hydroxybenzonitrile herbicide. For this purpose, the associated 2-cyano-l, 3-dione herbicide is normally used in the form of herbicidal compositions (ie, in association with a herbicidally acceptable diluent or carrier and / or surfactant), for example, as is described hereinabove. In this description, it will be understood that the term "associated herbicide" means at least one element of the group consisting of a triazine herbicide, a chloroacetamide herbicide, a 2,6-dinitroaniline herbicide, aclonifen, diuron and a herbicide of hydroxybenzonitrile. Preferably, the 2-cyano-l, 3-dione derivative has the formula (I): wherein R1 is alkyl of 1 to 6 carbon atoms or a cycloalkyl of 3 to 6 carbon atoms, optionally bearing an alkyl of 1 to 6 carbon atoms; R2 is selected from halogen, -S (0) pMe and alkyl or haloalkyl of 1 to 6 carbon atoms, n is two or three; and p is zero, one or two. The compounds of formula I above can exist in enol tautomeric forms which can give rise to geometric isomers around the enolic double bond. In addition, in certain cases, the groups R ^ and R2 give rise to stereoisomers and geometric isomers. All of such forms are encompassed by the present invention. The term "agriculturally acceptable salts" means salts, cations or anions of which are known and accepted in the art for the formation of salts for agricultural or horticultural use. Preferably, the salts are soluble in water. Suitable salts with bases include alkali metal (eg, sodium and potassium), alkaline earth metal (eg, calcium and magnesium), ammonium and amine (diethanolamine, triethanolamine, octylamine, morpholine and dioctylmethylamine) salts. Suitable acid addition salts, formed by the compounds of the formula (I) containing an amino group, include salts with inorganic acids, for example, hydrochlorides, sulfates, phosphates and nitrates and salts with organic acids, for example, acid acetic. The term "metal complexes" means compounds in which one or both of the oxygen atoms of 1,3-dione act as chelating agents for a metal cation. Examples of such cations include zinc, manganese, cupric, cuprous, ferric, ferrous, titanium and aluminum cations. It will be understood that in the description that follows, reference to 2-cyano-1,3-diones includes agriculturally acceptable salts, metal complexes or enol tautomeric forms thereof. In the above formula (I), the compounds of preference R1 is 1-methylcyclopropyl or more preferably cyclopropyl. In formula (I) above, the compounds in which n is three and groups (R2) n occupy the positions 2,3- and 4 of the benzoyl ring; or in which n is two and groups (R2) n occupy positions 2 and 4 of the benzoyl ring are preferred. In formula (I) above, R 2 is preferably selected from halogen (preferably chlorine or bromine), -S (0) pMe and trifluoromethyl. In formula (I) above, preferably one of the groups R2 is -S (0) pMe.

The most preferred compound of the formula (I) above is 2-cyano-3-cyclopropyl-1- (2-methylsulfonyl-4-trifluoromethylphenyl) propan-1,3-dione, which is hereinafter referred to as the compound A. Preferably, the triazine herbicide is a compound of formula II wherein R 11 represents chloro or an alkylthio or straight or branched chain alkoxy having from one to six carbon atoms; R 12 represents azido, monoalkylamino, dialkylamino or cycloalkylamino, in which the alkyl or cycloalkyl portions may be optionally substituted by one or more substituents selected from cyano and alkoxy; and R 3 represents straight or branched chain N-alkylamino having from one to six carbon atoms; or of formula (Ua) wherein R- ^ 4 represents a straight or branched chain alkyl having from one to six carbon atoms.

Preferred compounds of formula II above are those in which RÜ represents chloro, R ^-3 represents N-ethylamino and R 12 represents N-ethylamino, N- (2-methylpropanitrile) amino or N-isopropylamino, respectively known as simazine , cyanazine and atrazine, atrazine is the most preferred compound. Another preferred compound of formula (II) above is the compound wherein R ^ is methylthio, R12 is N-isopropylamino and R13 is N-ethylamino, which consists of ametrin. The use of ametryn is particularly preferred when the method is used on site or will be used to grow sugarcane. A preferred compound of formula Ia above is the compound in which R ^ -1 represents methylthio, R14 represents tert-butyl, which is known as metribuzin. Preferably, the chloroacetamide herbicide is of formula (III). Ar-N (R31) C0CH2C1 (III) wherein R31 represents hydrogen, alkyl of 1 to 6 carbon atoms, haloalkyl, alkoxy or alkoxyalkyl, alkenyl, haloalkenyl, alkynyl, haloalkynyl or acylamidoalkyl having up to six carbon atoms; Ar represents thienyl or phenyl optionally substituted by one or more groups selected from the group consisting of halogen, amino, alkyl of 1 to 6 carbon atoms, haloalkyl, alkoxy and alkoxyalkyl. The group R31 can give rise to optical stereoisomers, and it will be understood that the racemic and enantiomeric forms of this compound are included in this definition. Compounds of formula (III) above in which Ar represents phenyl or thienyl, optionally substituted by one or preferably two groups which may be the same or different, selected from ethyl and methyl are also preferred. A preferred compound of formula (III) is the compound wherein R31 represents methoxymethyl and Ar represents 2,6-diethylphenyl, which is known as alachlor. Another preferred compound of formula (III) is the compound wherein R31 represents ethoxymethyl and Ar represents 2-ethyl-β-methylphenyl, which is known as acetochlor. Another preferred compound of formula (III) is the compound wherein R31 represents 2-methoxy-1-methylethyl and Ar represents 2-ethyl-6-methylphenyl, which is known as metolachlor. The racemic form of the metolachlor and the partially resolved form, known as alpha-metolachlor, and mixtures thereof, are preferred.

Another preferred compound of formula (III) is the compound wherein R31 represents 1-methylethyl and Ar represents phenyl, which is known as propachlor. Another preferred compound of formula (III) is the compound wherein R31 represents 2-methoxy-1-methylethyl and Ar represents 3- (2, 4-dimethyl) thienyl, which is known as dimethenamide. The racemic form of dimethenamid and the partially resolved form (S) known as S-dimethenamid, and mixtures thereof are preferred. Preferably, the 2,6-dinitroaniline herbicide is a compound of formula IV (IV) wherein R41 represents: straight or branched chain alkyl or alkenyl having up to 12 carbon atoms, which may be substituted by one or more halogen atoms or cycloalkyl groups; R42 represents hydrogen or a group R4 ^ as defined above, R41 and R42 are the same or different; R43 represents: hydrogen or halogen; a straight or branched chain alkyl having from 1 to 12 carbon atoms, which may be substituted by one or more halogen atoms; or an unsubstituted amino group; R44 represents: halogen; a straight or branched chain alkyl having from 1 to 12 carbon atoms, which may be substituted by one or more halogen atoms; a straight or branched chain alkylsulfonyl having from 1 to 12 carbon atoms which may be substituted by one or more halogen atoms; or sulfamoyl. Preferred compounds of formula (IV) include those wherein R ^ are selected from the group consisting of ethyl, propyl, butyl, 1-ethylpropyl, 2-methyl-1-propenyl, cyclopropylmethyl and 2-chloroethyl. Preferred compounds of formula (IV) include those wherein R42 is selected from hydrogen, ethyl and propyl. Preferred compounds of formula (IV) include those in which R42 is selected from hydrogen, methyl and unsubstituted amino.

Preferred compounds of formula (IV) include those wherein R44 is selected from methyl, tert-butyl, isopropyl and trifluoromethyl. Especially preferred compounds of formula (IV) are: 2,6-dinitro-N, N-dipropyl-4- (trifluoromethyl) benzene-amine and N- (1-ethylpropyl) -3,4-dimethyl-2,6- dinitrobenamine, which are respectively known as trifluralin and pendimethalin, pendimethalin is the most preferred compound. The hydroxybenzonitrile herbicide is preferably bromoxynil or ioxynil in the form of the original phenol (equivalent acid, ae), an agriculturally acceptable salt or ester thereof, preferably an agriculturally acceptable metal or amine salt, or an agriculturally acceptable ester thereof. an alkanoic acid containing from 2 to 10 carbon atoms, or a mixture thereof. In particular, the esters of butyrate, octanoate and heptanoate or mixtures thereof are preferred, the octatonate ester is most preferred. The amounts of 2-cyano-l, 3-dione and another herbicide, applied, vary depending on the weeds present and their population, the compositions used, the application program, the climatic and edaphic conditions and (when they are used to control the growth of weeds in crop growing areas) the harvest to be treated. In general, when taking these factors into account, the dose proportions given below are used. However, it will be understood that higher or lower application rates may be used, depending on the problem of weed control encountered. When applied to a crop growing area, the application rate should be sufficient to control weed growth without causing substantial permanent damage to the crop. The method described above can be used to control a very broad spectrum of annual broadleaf weeds and grass weeds in crops, for example, of corn or sugar cane, without significant permanent damage to the crop. The combined use described above offers a foliar and residual activity and consequently can be used over a very long period of time of development of the harvest, that is, from the pre-harvest sprout to a post-weed post-harvest sprout. In the method according to this feature of the present invention, the combined use of (a) and (b) to control grass weeds in corn or sugar cane is preferred. Where (b) is a member of the group consisting of a chloroacetamide herbicide, a 2,6-dinitroaniline herbicide, aclonifen and a hydroxybenzonitrile herbicide, the method is preferably used to control grass weeds in corn. Where (b) is diuron, the method is preferably used to control grass weeds in sugarcane. Where the associated herbicide is an element of the group consisting of a triazine herbicide, a chloroacetamide herbicide, a 2,6-dinitroaniline herbicide, aclonifen and diuron, the herbicides are generally applied in the pre-emergence period of weeds (for example, by surface application and in particular incorporated in the pre-plantation) and can be applied after planting a crop (where they are present); or prematurely in the post-outbreak of weeds and crops. More preferably, these herbicides are applied in combination with (a) after planting a crop and pre-sprouting weeds or pre-planting incorporated. Where the associated herbicide is a hydroxybenzonitrile herbicide, the combination with (a) is generally applied in the post-emergence period of the weeds, more preferably a premature post-emergence. In accordance with usual practice (and a preferred method according to the present invention) a tank mixture can be prepared before use by combining separate formulations of the individual herbicide components.

Where the associated herbicide is a triazine herbicide, the application rates of 5 grams to 500 g of 2-cyano-l, 3-dione and from 250 g to 5000 g of the triazine herbicide per hectare generally provide good results. For the selective control of weeds in a weed infestation site, which is an area used or used for the cultivation of crops, the application rates of 5 g to 500 g of 2-cyano-l, 3-dione and from 250 g to 5000 g of triazine herbicide per hectare are particularly suitable, preferably from 25 to 200 g of 2-cyano-l, 3-dione and from 500 g to 1500 g of the triazine herbicide per hectare. Where the triazine herbicide is ametryn, it is preferably used in combination with a 2-cyano-l, 3-dione at a dose rate of 250 to 4000 grams per hectare of ametryn, more preferably from 500 to 2000 g per hectare. Where the associated herbicide is a chloroacetamide herbicide, the application rates of 0.5 g to 512 g of 2-cyano-l, 3-dione and from 8 to 4000 g of the chloroacetamide herbicide per hectare generally give good results. For the selective control of weeds in a weed infestation site which is an area used, or to be used, for the cultivation of crops, the application rates of 0.5 g to 512 g, of 2-cyano-1,3-dione and from 20 to 4000 g of the chloroacetamide herbicide per hectare are particularly suitable, preferably from 20 to 200 g of 2-cyano-l, 3-dione and from 200 to 3000 g of chloroacetamide herbicide per hectare, even more than preference of 25 to 150 g of 2-cyano-l, 3-dione and 350 to 2000 g (especially 450 g to 2000 g) of the chloroacetamide herbicide per hectare. Where the associated herbicide is a 2,6-dinitroaniline herbicide, the application rates of 0.5 g to 512 g of 2-cyano-l, 3-diones and of 8 g to 3000 g of the 2,6-dinitroaniline herbicide per hectare They give good results in general. For the selective control of weeds in a weed infestation site, which is an area used or to be used for growing crops, the application rates of 5 g to 512 g of 2-cyano-1,3-dione and from 150 g to 3000 g of the 2,6-dinitroaniline herbicide per hectare are particularly suitable, preferably from 20 g to 200 g of 2-cyano-l, 3-dione and from 150 g to 2000 g of the herbicide from 2 to 6 g. dinitroaniline per hectare, more preferably from 25 g to 150 g of 2-cyano-1,3-diones and from 250 g to 1000 g of the herbicide of 2,6-dinitroaniline per hectare. Where the associated herbicide is aclonifen, the application rates of 1 g to 500 g of 2-cyano-1,3-dione and from 30 g to 2500 g of aclonifen per hectare give good results, more preferably from 10 g to 200 g from 2-cyano-l, 3-dione and from 500 g to 1000 g of aclonifen per hectare. Where the associated herbicide is diuron, the application rates of 0.5 g to 500 g of 2-cyano-1,3-dione and 100 g to 3000 g of diuron per hectare give good results, more preferably from 25 g to 150 g of 2-cyano-l, 3-dione and from 500 g to 2000 g of diuron per hectare. Where the associated herbicide is a hydroxybenzonitrile (HBN) herbicide, the application rates of 5 g to 500 g of 2-cyano-l, 3-dione and of 30 g to 600 g of equivalents of acid (ae) of herbicide of HBN per hectare give good results, more preferably from 20 to 300 g of 2-cyano-l, 3-dione and from 60 g to 200 g ae of HBN herbicide per hectare. The method of the invention is most preferably used for the control of weeds at a site used or to be used for the cultivation of a crop. When applied to a crop growing area, the application rate should be sufficient to control the growth of the weeds without causing substantial permanent damage to the crop. The dose ratio of the combination used should generally provide a sufficiently persistent level of activity to control the crops for some time after application to the site. Preferably, the treatment must be persistent for 45 to 60 days after application. The mixtures of the present invention can also be used to control the growth of weeds in places which are not crop growing areas, but which control of weeds is nevertheless desirable. Examples of such areas that are not for crop cultivation include airfields, industrial sites, railroads, roadsides, river banks, irrigation routes and other roads, roughing lands and virgin or uncultivated land, particular where weed control is desired in order to reduce fire risks. When used for such purposes, in which a total effect of the herbicide is frequently desired, the active compounds are normally applied at higher dosage ratios than those used in the crop growing areas as described hereinabove. The precise dose will depend on the nature of the treated vegetation and the desired effect. The following non-limiting examples illustrate the invention. In the description that follows, the following trademarks appear: Lasso, Frontiere, Duelor, Harness Plus, Prowl, Propixine, Buctril. The abbreviation 'a. i. means active ingredient. Also, certain weeds and crops are indicated by their Bayer codes.

Example 1 Setaria faberi, Setaria viridis or Echinochloa crus-galli seeds are seeded in a black clay soil, not sterilized in plastic pots of seven centimeters by seven centimeters. The pots are irrigated and allowed to drain. Then, the soil surface is sprayed with a range of concentrations of either compound A, pendimethalin, metolachlor, acetochlor, aclonifen, atrazine or diuron individually or mixtures of compound A with each of these herbicides, dissolved in a ratio of 50 / 50 weight / weight of acetone / water. In all cases technical material is used. The solutions are sprayed using a device for chemical weeding, which provides the equivalent of 290 liters / ha to 43 centimeters above the surface of the soil. Four replicas are carried out and the treated pots are placed randomly and kept in a greenhouse, they remain in a humid capillary mantle under lights, with irrigation from the top three times a day. Two weeks after the treatment, the percent reduction in the growth of the plant is determined, compared to a reference or control without treating and the average result is determined for each application rate. The Colby formula is applied to the results to determine the nature of the interaction between the herbicide mixtures. In the tables given below, the figures shown in parentheses represent the expected reduction in growth by mixtures of herbicides according to the Colby formula.

Results: Table 1 Compound A and pendimethalin Setaria faberi Pendimethalin C n A Table 2 Compound A and pendimethalin against Echinochloa crus-galli Pendimetalin Com A Table 3 Compound A and metolachlor against Setaria viridis Metolachlor CpdA TABLE 4 Compound A and acetochlor against Setaria viridis Atrazine CpdA Table 5 Compound A and aclonifen against Echinochloa crus-galli Aclonifen Cpd Table 6 Compound A and atrazine against Echinochloa crus-galli Atrazine CpdA Table 7 Compound A and diuron against Echinochloa crus-galli Diuron CpdA Example 2 The following field studies were carried out using compound A (formulated as a wettable powder containing 50% by weight of a. I.) With several associated pre-sprout crop weed and weed herbicides. The studies were conducted in Raymondville, United States (a clayey black clay soil, referred to herein as "Site USl") and in Pretoria, South Africa (a black clay soil, which is made hereinafter referred to herein as "Site ZA1") using compound A alone and in combination with alachlor (as the commercial formulation "Lasso", an emulsifiable concentrate containing 480 g / 1 ai), dimethenamid (as the commercial formulation " Frontiere ", an emulsifiable concentrate containing 900 g / 1 of ai), metolachlor (as the commercial formulation" Duelor ", an emulsifiable concentrate containing 960 g / 1 of ai) pendimethalin (as the commercial formulation" Prowl ", a concentrate in suspension containing 400 g / 1 of ai), atrazine (as the commercial formulation "Propixine", a suspension concentrate containing 500 g / 1 of ai), and acetochlor (as the commercial formulation "Harness Plus", a concentrate emuls ionable containing 840 g / 1 of a.i.). Each of the associated herbicides was also sprayed individually. Two replicas were carried out. 34 days after treatment (in USl) or 52 days after treatment (in ZA1) the phytotoxicity percentage is determined in comparison with an untreated control or reference. The following results were obtained.

Table 8: Results of the USl Site (pre-outbreak, 34DAT) Table 9: Results of the ZAl Site (pre-emergence, 52DAT) Ej «ampio 3 The following field studies were carried out on the USl Site and in Waverley, USA (black clay soil, which is referenced later in the present as "Site US2") using Compound A (as used in Example 2 above), either alone or in combination of tank mix with bromoxynil (octanoate ester, using the commercial combination "Buctril 2EC" an emulsifiable concentrate containing 240 g / 1 a.i.) which was also sprayed alone. The compounds were applied in a premature post-emergence period to spring sown weeds found in spring harvests. The percentage of phytotoxicity is determined by comparison with an untreated control 34 days after treatment (DAT) at the US2 and 37 DAT sites in USl. Two replicas were carried out. The results shown in Tables 10 and 11 were obtained. In these tables, the figures in parentheses indicate the expected level of weed control according to the Colby formula. "Brom" means bromixinil.

Results TABLE 10: Site results US2 (premature post-outbreak, 34 days after treatment) TABLE 11: Results of the US2 Sites (premature post-emergence, 37 days after treatment) According to a further feature of the present invention, herbicidal compositions are provided which comprise: (a) a 2-cyano-1,3-dione derivative defined above or a salt, metal complex or enol tautomeric form, agriculturally acceptable same; and (b) at least one member of the group consisting of a triazine herbicide, a chloroacetamide herbicide, a 2,6-dinitroaniline herbicide, aclonifen, diuron, and a hydroxybenzonitrile herbicide; in association with, and preferably dispersed homogeneously in, one or more diluents or carriers, herbicidally acceptable, compatible and / or surfactants (ie, diluents or carriers or surfactants of the type generally acceptable in the art as suitable for use in compositions herbicides and which are compatible with the 2-cyano-l, 3-dione derivative and the other herbicide The term "homogeneously dispersed" is used to include compositions in which the combination of herbicides are dissolved in the other components. The term "herbicidal composition" is used in a broad sense to include not only compositions which are prepared for use as herbicides, but also concentrates which must be diluted before use.Preferably, the compositions contain from 0.05 to 90% by weight of derivative of 2-cyano-l, 3-dione and the associated herbicide.

The herbicidal compositions may contain a diluent or carrier and a surfactant (eg, humectant, dispersant or emulsifier). The surfactants, which may be present in the herbicidal compositions of the present invention, may be of ionic or non-ionic types, for example, sulforricinoleates, condensate-based products of ethylene oxide with nonyl- or octyl-phenols or esters of carboxylic acid of anhydrosorbitols which have been rendered soluble by etherification of the free hydroxy groups by condensation with ethylene oxide, alkali metal and alkaline earth metal salts or sulfuric acid esters and sulfonic acids such as dinonyl- and dioctyl-sodium sulfono-succinates and alkali metal and alkaline earth metal salts of high molecular weight sulfonic acid derivatives such as sodium and calcium lignosulfonates. Examples of suitable solid diluents or carriers are aluminum silicate, talc, calcined magnesia, kieselguhr (diatomaceous earth), tricalcium phosphate, powdered cork, absorbent carbon black, and clays such as kaolin and bentonite. The solid compositions (which may take the form of powders, granules or wettable powders) are preferably prepared by grinding 2-cyano-1,3-dione and herbicide associated with solid diluents or by impregnation of solid diluents or carriers with solutions derived from 2-cyano-l, 3-dione and the associated herbicide in volatile solvents, evaporation of the solvents and, if necessary, grinding of the products to obtain powders. Granular formulations can be prepared by absorption of the 2-cyano-1,3-dione derivative and associated herbicide (dissolved in volatile solvents) onto solid diluents or carriers in granular form and evaporation of the solvents, or by granulation of the compositions in powder form obtained as described above. The solid herbicidal compositions, particularly wettable powders, may contain wetting agents or dispersants (for example of the types described above), which may also be, when they are solids, serve as diluents or carriers. The liquid compositions according to the invention can take the form of aqueous-organic solutions, suspensions and emulsions, which can incorporate a surfactant. Suitable liquid diluents for incorporation into liquid compositions include water, acetophenone, cyclohexanone, isophorone, toluene, xylene and mineral, animal and vegetable oils (and mixtures of these diluents). The surfactants, which may be present in the liquid compositions, can be ionic or non-ionic (for example the types described above) and can, when they are liquids, also serve as diluents or carriers. Wettable powders and liquid compositions in the form of a concentrate can be diluted with water or other suitable diluents, for example mineral or vegetable oils, partially in the case of liquid concentrates in which the diluent or carrier is an oil, to give ready compositions for its use. When desired, the liquid compositions of the 2-cyano-l, 3-dione derivative and associated herbicide can be used in the form of self-emulsifiable concentrates containing the dissolved active substances in the emulsifying agents compatible with the active substances, the simple addition of Water to such concentrates produces ready-to-use compositions. The liquid concentrates in which the diluent or carrier is an oil can be used without further dilution using the electrostatic spray technique. The herbicidal compositions according to the present invention may also contain, if desired, conventional adjuvants such as adhesives, protective colloids, thickeners, penetrating agents, stabilizers, sequestering agents, retort antiforming agents, coloring agents and corrosion inhibitors. These adjuvants can also serve as diluents or carriers. The preferred herbicidal compositions according to the present invention are in the form of concentrates in aqueous suspension; wettable powders; granules dispersible in water; water soluble concentrates, liquids; emulsifiable liquid suspension concentrates; emulsifiable granules or concentrates. In addition, the compositions can be provided in the form of a gel. This is particularly useful where the composition is intended to be packaged in a water soluble pouch, for example as described in European Patent Publication Nos. 0577702 and 0608340, and U.S. Patent Nos. 5,222,595, 5,224,601, 5,351, 831, and 5,323, 906. The processes described in European patent publications Nos. 0496630, 0496631, 0625505, and 0625508 can be used to prepare the 2-cyano-1,3-dione herbicide derivatives. The herbicidal compositions according to the present invention may also comprise the 2-cyano-1,3-dione derivative and associated herbicide in association with, and preferably dispersed homogeneously in, one or more pesticidally active compounds and, if desired, one or more compatible, pesticidally acceptable diluents or carriers, surfactants or conventional adjuvants as described hereinabove. Preferred associates with the combination of the present invention include one or more other members of the group consisting of triazine herbicides (eg, atrazine, metribuzin or cyanazine), chloroacetamide herbicides (eg, alachlor, metolachlor, acetochlor or dimethenamide) ), 2, 6-dinitroaniline herbicides (eg, pendimethalin or trifluralin), aclonifen and diuron. Also, combinations that include other classes of herbicides such as sulfonylureas, imidazolinones, thiazoles, ureas and aromatic and heterocyclic di- and tri-ketones, etc. can be used. According to a further feature of the present invention, a product is provided comprising: (a) a 2-cyano-l, 3-dioa derivative as defined above or a salt, metal complex or agriculturally acceptable enol tautomeric form of the same; and (b) at least one member of the group consisting of a triazine herbicide, a chloroacetamide herbicide, a 2,6-dinitroaniline herbicide, aclonifen, diuron and a hydroxybenzonitrile herbicide, as a combined preparation for simultaneous use , separate or sequential, for example, in controlling the growth or cultivation of weeds in a site (for example, a harvest site). It is noted that, in relation to this date, the best method known to the applicant to carry out the aforementioned invention is that which is clear from the present description of the invention. Having described the invention as above, property is claimed as contained in the following

Claims (22)

1. CLAIMS 1. A method for controlling the growth of weeds in a site, characterized in that it comprises the application to the site of a herbicidally effective, synergistic amount of: (a) a herbicide of 2-cyano-l, 3-dione or a salt, metal complex or enolic tautomeric form thereof, agriculturally acceptable; and (b) at least one element of the group consisting of a triazine herbicide, a chloroacetamide herbicide, a 2,6-dinitroaniline herbicide, aclonifen, which consists of 2,6-chloro-nitro-3-phenoxyaniline. , diuron, which consists of 3- (3,4-dichlorophenyl) -1,1-dimethylurea; and a hydroxybenzonitrile herbicide.
2. 2. A method for controlling the growth of weeds in a site, characterized in that it comprises the application to the site of a herbicidally effective, synergistic amount of: (a) a 2-cyano-l, 3-dione derivative of the formula : D wherein R1 is alkyl of 1 to 6 carbon atoms, or cycloalkyl of 3 to 6 carbon atoms, optionally bearing an alkyl of 1 to 6 carbon atoms; R2 is selected from halogen, -S (0) pMe and alkyl or haloalkyl of 1 to 6 carbon atoms, n is two or three; and p is zero, one or two; and (b) a member of the group consisting of a triazine herbicide, a chloroacetamide herbicide, a 2,6-dinitroaniline herbicide, aclonifen, which is 2-chloro-6-nitro-3-phenoxyaniline; and diuron, which is 3- (3,4-dichlorophenyl) -1,1-dimethylurea.
3. 3. The method according to claim 2, characterized in that R! is 1-methylcyclopropyl or cyclopropyl.
4. 4. The method of compliance with the claim 2 or 3, characterized in that n is three and groups (R2) n occupy positions 2,3 and 4 of the benzoyl ring; or in which n is two and the groups (R ^) n occupy positions 2 and 4 of the benzoyl ring.
5. 5. The method of compliance with the claim 2, 3 or 4, characterized in that R2 is selected from halogen, -S (0) pMe and trifluoromethyl.
6. The method according to any of the preceding claims, characterized in that (a) is 2-cyano-3-cyclopropyl-1- (2-methylsulfonyl-4-trifluoromethyl-phenyl) propan-1,3-dione or a salt , metal complex or enolic tautomeric form, agriculturally acceptable thereof.
7. The method according to any of claims 1 to 6, characterized in that the triazine herbicide is a compound of formula II): wherein R ^ represents chloro or alkylthio or straight or branched chain alkoxy having from one to six carbon atoms; R ^ represents azido, monoalkylamino, dialkylamino or cycloalkylamino, in which the alkyl or cycloalkyl portions may be optionally substituted by one or more substituents selected from cyano and alkoxy; and R -'- 3 represents straight or branched chain N-alkylamino having from one to six carbon atoms; or of formula lia: (Ua) wherein R ^ -4 represents straight or branched chain alkyl having from one to six carbon atoms.
8. 8. The method according to claim 7, characterized in that the triazine herbicide is atrazine, which is (ß-chloro-N-ethyl-N-isopropyl-1,3,5-triazine-2,4-diamine) or metribuzin, which is (4-amino-6-tert-butyl-3-methylthio-l, 2,4-triazin-5 (4H) -one).
9. 9. The method according to any of claims 1 to 6, characterized in that the chloroacetamide herbicide is of formula (III) Ar-N (R31) C0CH2C1 (III) wherein R31 represents hydrogen, alkyl of 1 to 6 carbon atoms. carbon, haloalkyl, alkoxy or alkoxyalkyl; alkenyl, haloalkenyl, alkynyl, haloalkynyl or acylamidoalkyl having up to six carbon atoms; Ar represents thienyl or phenyl optionally substituted by one or more groups selected from the group consisting of halogen, amino, alkyl of 1 to 6 carbon atoms, haloalkyl, alkoxy and alkoxyalkyl.
10. The method according to claim 8, characterized in that the chloroacetamide herbicide is selected from acetochlor, which is 2-chloro-N-ethoxymethyl-6'-ethylacet-o-toluidide; and metolachlor, which is 2-chloro-6'-ethyl-N- (2-methoxy-1-methylethyl) acet-o-toluidide or an isomeric mixture thereof. eleven .
11. The method according to any of claims 1 to 6, characterized in that the 2,6-dinitroaniline herbicide is a compound of formula IV: Ov wherein R ^ l represents: a straight or branched chain alkyl or alkenyl having up to 12 carbon atoms, which may be substituted by one or more halogen atoms or cycloalkyl groups; R 2 represents hydrogen or a group R 1 l as defined above, R 1 and R 42 are the same or different; R43 represents: hydrogen or halogen; a straight or branched chain alkyl having from 1 to 12 carbon atoms, which may be substituted by one or more halogen atoms; or an unsubstituted amino group; R44 represents: halogen; a straight or branched chain alkyl having from 1 to 12 carbon atoms, which may be substituted by one or more halogen atoms; a straight or branched chain alkylsulfonyl having from 1 to 12 carbon atoms which may be substituted by one or more halogen atoms; or sulfamoyl.
12. The method according to claim 11, characterized in that the 2,6-dinitroaniline herbicide is pendimethalin, which is N- (1-ethylpropyl) -3,4-dimethyl-2,6-dinitrobenzenamine.
13. The method according to claim 1, characterized in that the hydrobenzonitrile herbicide is bromoxynil or ioxynil in the form of the original phenol or an agriculturally acceptable salt or ester thereof, or a mixture thereof.
14. 14. The method according to any of claims 1 to 13, characterized in that the site is an area used, or to be used for the cultivation of a crop.
15. 15. The method according to claim 14, characterized in that the harvest is corn or sugar cane.
16. 16. A composition, characterized in that it comprises a herbicidally effective, synergistic amount of: (a) a 2-cyano-l, 3-dione derivative as defined in claims 1 to 6 or a salt, metal complex or enol tautomeric form of the same, agriculturally acceptable; and (b) at least one member of the group consisting of a triazine herbicide, a chloroacetamide herbicide, a 2,6-dinitroaniline herbicide, aclonifen, which is 2,6-chloro-nitro-3-phenoxyaniline, diuron, which is 3- (3,4-dichlorophenyl) -1,1-dimethylurea; and a hydroxybenzonitrile herbicide.
17. 17. A composition, characterized in that it comprises a herbicidally effective, synergistic amount of: (a) a 2-cyano-l, 3-dione herbicide or a salt, metal complex or enol tautomeric form thereof, agriculturally acceptable; and (b) an element of the group consisting of a triazine herbicide, a chloroacetamide herbicide, a 2,6-dinitroaniline herbicide, aclonifen, which is 2,6-chloro-nitro-3-phenoxyaniline, diuron, which is 3- (3,4-dichlorophenyl) -1,1-dimethylurea.
18. 18. The composition according to claim 16 or 17, characterized in that the triazine herbicide is as defined in claim 7 or 8.
19. 19. The composition according to claim 16 or 17, characterized in that the chloroacetamide herbicide is as defined in claim 9 or 10.
20. The composition according to claim 16 or 17, characterized in that the 2,6-dinitroaniline herbicide is as defined in claim 11 or 12.
21. 21. The composition in accordance with claim 16, characterized in that the hydroxybenzonitrile herbicide is bromoxynil or ioxynil in the form of the original phenol or an agriculturally acceptable salt or ester thereof or a mixture thereof.
22. 22. A product characterized in that it comprises a herbicidally effective, synergistic amount of: (a) a 2-cyano-l, 3-dione derivative as defined in any of claims 1 to 6, or a salt, metal complex or agriculturally acceptable enol tautomeric form thereof; and (b) at least one member of the group consisting of a triazine herbicide, a chloroacetamide herbicide, a 2,6-dinitroaniline herbicide, aclonifen, which is 2,6-chloro-nitro-3-phenoxyaniline, diuron, which is 3- (3,4-dichlorophenyl) -1,1-dimethylurea; and a hydroxybenzonitrile herbicide; as a combined preparation for the simultaneous, separate or sequential use in controlling weed growth at a harvest site.