CS221841B2 - Synergic means for selective destroying the weeds - Google Patents

Abstract

1. A synergistic composition for selectively controlling weeds, which composition comprises, on the one hand, a 4-(3',5'-dichloropyridyl-2'oxy)-alpha-phenoxypropionic acid propargyl ester of the formula I see diagramm : EP0043802,P15,F1 wherein Z is oxygen or sulfur, and, on the other, one of 3-(3'-chloro-4'-methylphenyl)1,1-dimethylurea (IIa), 3-(3'-chloro-4'-methoxyphenyl)-1,1-dimethylurea (IIb), 3-(4'-isopropylphenyl)-1,1-dimethylurea (IIc), 1-benzothiazol-2-yl-1,3-dimethylurea (IId), 4-hydroxy-3,5-diiodobenzonitrile (IIe) or 3,5-dibromo-4-hydroxybenzaldehyde-O-(2',4' -dinitrophenyl)-oxime (IIf), together whith carriers and/or other adjuvants.

Description

The present invention relates to a synergistic composition comprising a combination of herbicidal active ingredients which is excellently suited for the selective control of weeds in cereal crops. The invention also relates to the control of weeds, in particular in cereals, by the use of this novel composition.

At present, the most common and most important weeds in cereal cultures are the weeds of the genera Sinapiš (mustard), Chnrysanthemum (daisy) and certain species of Avena (deaf oats).

An excellent selective herbicides against weeds in jednoděložrým-postemeegent the appli-cation of the oil uWzaly ^ ^ Lester 4- ⁽³ * 5 * ^{- d d} ichlorpyri ^{yl-2-oxy) -a-Star} ftnoyypoopitnov acids of formula I

Cl

in which

Z is oxygen or sulfur.

^Both composites formula i.e. p ^ ^ ojDar ester of 4- (3 ^ 5 * - 'ctlorpyridyl ^{di-2-ol from: χ У)} · ^ASF -phenol ypropionov ^ ^é ^ ny tyse formula Ia and ^ ^ rojaar lester 4- ⁽³ * 5 ^a - ^d ic ^hl orpyridyl ^{2-yl-oxy) -a} · -fenoxythiopropionové acids of formula Ib, their preparation and their poožití as selective herbicides is disclosed in European patent No. pubMkaci. 3114.

As is well known, dicotyledonous weeds in cereals, but also some monocotyledonous weeds can often be successfully controlled with urea derivatives of the general formula II after post-emergence application.

(II) wherein ^b u3

R 1 is hydrogen,

R 1 represents a methyl group and

R 2 is J-chloro-4-methylphenyl, 3-C 3-8 -methoxyphenyl, or

A-isopropylphenyl, or

R 1 represents a methyl group,

R 1 is hydrogen and

R 2 is bennoohiazoo-4-yl.

The compounds represented by the general formula (II) are shown in the following formulas IIa to IId:

3- ^(3'-chloro-4 * -methylfeeyl) -l, ^{1, d h} ylmočcvina IMET ^{(СШогtoluen)} IIa

NH-CO-N (CH312

Cl (Ila)

3- (3'-Chloro-4'-methoxyphenyl) -1,1-dimethylurea (Metoxuron) of Formula IIb

NH-CO-N _{(CH3) 2} (IIb), (4 (i * tPoprρpytfynyl) -1,1-dimethylurea (Isčprčturty) IIc

NH-CO-N (CH3) ₂ (IIc) β 1 -benzothiazol-2-yl-1,1'-dimethylaminamide (Methabeeythlazuron) ·· formulas lid

CH ₃ N-CO-NH — CH ₃ (lid)

The compounds of formulas II and their herbicidal activity are described, for example, in the following literature:

Ch ^h ortoluron (comp ^ ni-on formula IIa), in C. r. 5 ^e Conf. Com. French: Maauaises Herbea (COLWA), 1969, II, 349,

Metoxuron (compound of formula IIb) in Z. HXkrankh., PLPath., * Kf.Schutz, 1968, £ 5, 233,

Isoproiuron (compound of Formula IIc) in German Patent No. 2,107,774 a

Liihabenzthiazuron · (compound of formula IId) in PflSehutz-Nachr. Baer, 1969, 22, 314.

Surprisingly, it has now been found that the coefficient of Uo variation in certain measures of the combination of the two active compounds of formulas I and II has a synergistic effect which makes it possible to control a greater number of important weeds in cereals without damaging cereal cultures. P4oom destroys the major weed species in cereals, such as the Chrysanthemum and Sinapis Specialized Species, as well as certain Avena oats (deaf oats), in a selective manner in already-grown horticultural cultures.

It is surprising that the combination of the active compound of the formula I with the active compound of the formula II does not produce only the principally expected summation effect in the spectrum of effects on conventional weeds occurring in cereal crops, but is this combination. it achieves a synergistic effect which extends the limits of the effects of both of these preparations in two respects.

Firstly, the applied number of individual compounds of formulas I and II is substantially reduced with an equally good effect. Second, a high degree of weed control is achieved with the combined mixture even where the two mono-active compounds in the range of too low application rates were completely ineffective. This results in a substantial widening of the weed spectrum which can be controlled and, moreover, an increase in the safety for the cultivation of cereals, which is necessary and desirable for an overdose of the active substance.

In addition to cereal cuttings such as barley, rye and in particular wheat, the composition according to the invention can also be used for thickened weed control in other monocotyledonous retinas with similar susceptibility to efficacy and weed growth, such as maize and rice.

The active compound combination according to the invention contains the active compound of the formula I and one of the active compounds of the formula II in a formulated form, usually with an excess of one or the other component. Particularly preferred are excesses of component II in a ratio of up to 1: 25, but particularly preferred is a ratio of components I: II = 1: 1 to 1: 10.

The nominations of the active compounds according to the invention show an excellent weed control without, in a remarkable manner, influencing the culture in a quantity of 0.2 to 4 kg, preferably 0.5 to 3 kg per hectare, which is common in cereal crops. plants.

The following combinations have proven to be particularly effective synergistic synergists:

a) ^ ^ haze Lester 4- (3 #, 5 ^a - ^{U t} ic LTR ^pp yiUУ- · ² · t * ^χ y) -t f ^{fh h} nto ^yp for ^PT sulfonic tyseliny ^(Ia) and 3 · ( 3 * -Chltr-4Z-methyl-1,1'-dimethyl-urea (Formula IIIa),

b) propargyl Löster-4- ^{(3 a,} 5 ^a - ic ^{U t U} r ^py lor dyl22 t0 * ^yj JTA ^fa fefntoyy ^t H ^t P ^{t P} tρp nnooé tyseli ^ Formula (Ib) and 3- (4 ^of -ctltУ -4 mhtt ^of lfeoyl ^yl) -1,1-UimettylmoČovina (formula IIa)

c) Proper T.l.c. © ster 4- (3 * 5 * 2 * -UictlorpyriUyl -txy) -tlaa fonyppooptonové-acid (formula Ia) and 3- (4 ^of -tstprtpplfernl) -1,1-dimhthylmoČovina (IIc) and

U) 4- (3 * -, 5'-Dimethylpyrrolidyl-2 * -tyl) -tlaafthiolpeptylpeptide (formula Ib) and 3- (4'-methylpropyl ester) prop-1-yl ester-1,1,1-dimethylmethylamine (formula IIc) ).

The present invention also relates to the use of the composition according to the invention, that is to say a method of selectively controlling weeds and grassy weeds in cereals for post-emergence application of the composition.

The novel active ingredient composition according to the invention contains, in addition to the active ingredients mentioned, suitable carriers and / or other additives. These additives may be solid or liquid and correspond to the substances customary in such compositions, such as natural or regenerated minerals, solvents, dispersants, wetting agents, adhesives, thickeners, binders or fertilizers. Thus, suitable application forms are, for example, emulsion concentrates, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granules, also encapsulated, for example, in polymeric substances. Application procedures such as spraying, fogging, dusting, sprinkling or potting are appropriately selected as well as the type of compositions according to the desired objectives and proportions.

Compositions comprising as active ingredient a mixture of the active compounds of the formula I and of the formula II and optionally a solid or liquid additive and concentrates or other preparations of this type are prepared in a known manner, for example by thoroughly mixing and / or grinding the active compounds with fillers such as solvents, solid carriers, and optionally surfactants (surfactants).

Suitable solvents are: aromatic hydrocarbons, preferably fractions containing 8 to 12 carbon atoms, such as mixtures of xylenes or substituted naphthalenes, phthalic acid esters such as dibutyl phthalate or dioctyl phthalate, aliphatic hydrocarbons such as cyclohexane or paraffin hydrocarbons, alcohols and glycols, and their ethers and esters, such as ethanol, ethylene glycol, ethylene glycol monomethyl ether or ethylene glycol monoethyl ether, ketones such as cyclohexanone, strongly polar solvents such as N-methyl-2-pyrrolidone, dimethylsulfoxide or dimethylformamide, and optionally epoxidized vegetable oils such as epoxidized coconut oil or soybean oil, or water.

As solid carriers, for example for dusts and dispersible powders, natural stone flours such as limestone, talc, kaolin, montmorillonite or attapulgite are generally used. Highly disperse silicic acid or highly dispersed absorbent polymers may also be added to improve physical properties. Suitable granular adsorptive carriers for the granulates are porous types, such as pumice, brick pulp, sepiolite, or bentonite, as non-sorptive carrier materials, for example limestone or sand. In addition, a large number of pre-granulated materials of inorganic or organic origin, such as in particular dolomite or comminuted plant residues, may be used.

Suitable surface-active compounds are non-ionic, cationic and / or anionic surfactants having good emulsifying, dispersing and wetting properties. Surfactants are also understood as meaning mixtures of surfactants.

Suitable anionic surfactants can be both water-soluble soaps and water-soluble synthetic surfactants.

Soaps include alkali metal, alkaline earth metal, or corresponding optionally substituted emmonium salts of higher fatty acids (C 10 -C 22), such as sodium or potassium salts of oleic acid or stearic acid, or mixtures of natural fatty acids which they are obtained, for example, from coconut oil or 2 tallow oil. The fatty acid salts of methyl taurine must also be mentioned.

however, so-called synthetic surfactants, in particular, fatty sulfonates, fatty sulfates, sulfonated benzimidazole derivatives or alkylarylsulfonates, are more commonly used.

Fatty sulfonates or fatty sulfates are generally present as salts with. alkali metals, alkaline earth metals or optionally substituted ammonium salts and contain an alkyl radical of 8 to 22 carbon atoms, the alkyl also comprising an alkyl portion of the acyl radicals, such as, for example, sodium or potassium salt of lignosulfonic acid, doddeyysulphonic acid ester or a mixture The fatty alcohol alcohols are made from natural fatty acids. This also includes salts of sulfuric acid esters and sulfonic acid esters of butyric alcohols with ethylene oxide. The sulfanated benzimidazole derivatives preferably contain 2 sulfo groups and a C 8 -C 22 fatty acid residue. Alkyl alkyls of peppermint are, for example, sodium, calcium or tretane ammonium salts. dodecylbenzenesulfonic acid, iiblthylphthalenesulfonic acid or the condensation product of nartalenesulfonic acid and formaldehyde.

Also suitable are phosphorous phosphates, such as, for example, the phosphoric acid ester salt of the p-norylphenol adduct with -ethylene oxide (4 to 14).

Suitable non-ionic surfactants are derivatives of polysiloxide of aliphatic or alcohols, saturated or unsaturated fatty acids and alkylphenols, which may contain 3 to 30 illyl ether groups and 8 to 20 carbon atoms. and 6 to 18 carbon atoms in the allyl residue of α1Уtlphenyls.

Other suitable nonionic surfactants are the water-soluble adducts of poly (propylene glycol), poly (ethylene diamine) propyl (propylene glycol) and (C 1 -C 10) alkyl poly (propylene propylene glycol) alcohols, from 20 to 100 ethylene glycol groups. These compounds are generally 1 to 5 units of ethylene-1-propylene glycol per unit.

Examples of non-ionic surfactants include, but are not limited to, polyethylene glycol, polyglyceryl oil, polypropylene adducts with polyethylene oxide, tris-butoxy-oxy-ethanoethane, poly-ethylene glycol, and ethyl-sillyl glycol.

Also suitable are esters of the fatty acids derived from the gas of the gas, such as polylythyl ether sulfate trilleate.

The cationic surfactants are predominantly quaternary ammonium salts which contain as a substituent on the nitrogen atom at least one alkyl radical having 8 to 22 carbon atoms and which is occupied by a substituent. as further tubing, lower or optionally halogenated alkyl radicals, benzyl radicals or lower hydrated alkyl radicals. These salts are preferably salified in the form of halides, methoxysulfates or ethersulfates, for example stearyl.

trimethyl ammonium fluoride or Seniyl-k- (2-chloroethyl) uthylamine [lSrc> mid.

Surfactants to be used in the manufacture of the compositions of the present invention are described, among others, in the following publications:

Mi Cutchzon's Detergents and Emlaifier · 'Arnual Му Co op., Ridgewood,

New Jersey, 1979.

Sislay and Wood, 'Encctcllpe of Surfacz Active Ageens', by Chernmcal PyslUsUini Co., Inc. New York, 1964.

The active compound content of the commercially available formulations is between 0.1 and 95% by weight, preferably between 1 and 80% by weight.

Preferred compositions are in particular in the following composition (percentages are percentages by weight):

Solutions:

active ingredient: 5 to 95 conveniently 10 to 80 % solvent: 95 to 5 conveniently 90 to 0 % surfactant: 1 to 30 conveniently 2 to 20 May %. Emulsifiable concentrates: active ingredient: 10 to 50 conveniently 10 to 40 % surfactant: 5 to 40 conveniently 10 to 20 May % liquid carrier 20 May to 95 conveniently 40 to 80 %. Dust: active ingredient: 0.5 to 10 conveniently 2 to 8 % solid carrier: 99.5 to 90 conveniently 98 to 92 %. Suspension concentrates: active ingredient: 5 to 75 conveniently 10 to 50 % water: 94 to 25 conveniently 90 to 30 % surfactant: 1 to 40 «> conveniently 2 to 30 %. Wettable powder: Active active substance: 5 to 90 conveniently 10 to 80 % a especially 20 May to 60 % surfactant: 0.5 to 20 May *. conveniently 1 to 15 Dec % solid carrier: 5 to 90 conveniently 30 to 70 %. Granulates: active active substance: 0.5 to 30 conveniently 3 to 15 Dec % solid carrier: 99.5 to 70 conveniently 97 to 85 %.

While commercially available formulations are preferably concentrated formulations, generally dilute formulations are used for the final use. The dosage forms can be diluted to a concentration of 0.001% of active ingredient.

Other biocidally active substances or compositions can be admixed with the compositions of the present invention. Thus, the novel compositions may contain, for example, insecticides, fungicides, bactericides, fungistatics, bacteriostatics or nematicides in addition to the compounds of the formulas I and II in order to broaden the spectrum of activity.

The synergistic effect of herbicides always occurs when the herbicidal effect of the active ingredient combination I + II is greater than the sum of the effects of the individually applied active substances.

The expected growth of E plants for a given combination of two herbicides can (cf. COLBY,

S. R., Calculating Synergistic and Antagonistic Response of Herbicide Combinations, Weeds 15, pp. 20-22 (1967), is calculated as follows:

X. Y

E = ------- 100

It means:

X percentage of growth (compared to untreated plants) in herbicide I treatment using p kg of application per 1 ha,

Ϊ percentage of growth with herbicide II treatment from q kg applied per ha,

The expected growth in the percentage growth of the ionic plants after treatment with herbicide mixtures

I and II under the application rate of p + q kg of active substance per ha.

If the actually observed value is lower than the expected value of E, then a thy- er occurs. gismu.

The synergistic effect of the combinations of active substances I and II is thus illustrated by the following examples:

Example a 1

The test plants are sown in a greenhouse in plastic cabinets, which contain liters of sterile horticultural soil. After flowering, the plants in the 2-3 leaf stage are coated with an aqueous dispersion of the active ingredient combination. The amount of dispersion applied is 50 ml per m ² . ^p 15 days at te ^ OTE 1 ^0-20 ° C rela ^ ve vlhtoosi air ⁶⁰ and ^70% and daily watering enclosure contents ^ ICI plants vyhodnnH experiment.

The degree of damage shall be assessed by the following scale:

: dead plants: strijni effect: normal condition

For different proportions of the components in the mixture and for the different amounts of active ingredient, the following results were obtained:

(a) Table 1:

Tolerance and the ARK ^ ^ L ^ ^ haze smear 4- (3 * 5 * - ⁱ ichlurp ^y ri ^l-iy * -OX 2 ^s.) -HI ^h LL-fonuxypropionuvé acid (formula Ia) and compounds of formulas IIa to people and mixtures thereof. in post-emergence application.

test plant compound of formula Ia kg / ha added component kg / ha 1, o 0 0.5 Coliiri wheat 0 0.5 1.0 0.5 0 0.25 1.0 0.5 a compound of formula IIIa 9 9 6 7 7 7 7 8 a compound of formula IIi 9 9 6 6 9 7 9 9 the compound of formula IIc 9 9 6 6 6 7 9 9 the compound of formula IIi 9 9 6 7 7 7 9 9 test plant Avena fatua compound of formula Ia kg / ha 0 0.5 0.25 added ingredient kg / ha 1.0 0.5 0 1.0 0.5 0 1.0 0.5 a compound of formula IIIa 9 9 2 2 2 2 2 2 a compound of formula Ui 9 9 2 2 2 2 2 2 a compound of formula Uc 7 9 2 2 2 2 2 2 the compound of formula IIi 9 9 2 2 2 2 2 2

test plant compound of formula Ia kg / ha added component kg / ha 0 Sinapis arvensis 0.25 1.0 0.5 0 0.5 1.0 0.5 0 1.0 0.5 a compound of formula IIIa 3 6 9 2 3 9 2 3 a compound of formula IIb 2 3 9 2 3 9 1 2 a compound of formula Hc 1 1 9 1 1 9 1 · 1 a compound of formula HHd 2 3 9 1 2 9 1 2 test plant Protect with segesim compound of formula Ia kg / ha 0 0.5 0.25 added ingredient kg / ha 1.0 0.5 0 1.0 0.5 0 1.0 0.5 a compound of formula IIa 6 6 9 3 4 9 4 6 a compound of formula HHb 2 6 9 2 2 9 2 3 a compound of formula Hc 4 5 9 2 3 9 2 3 a compound of formula HHd 9 9 9 4 4 9 3 4

When the values calculated for the cumulative effect according to Colby's method are compared to those of Table 1, the observed growth values for the mustard (Sinapis arvensis) and the daisy (Chiyrsanhhmrnum segetum) are found to be lower than the effects calculated. This demonstrates the synergistic effect of the mixture of proparboxylate 4- (3 *, 5 * di-pyridopyridine-2 * 1'-alpha-phenoxypropionic acid) with the compounds of formulas IIa to IId (cf. Table 2).

Table 2:

Values calculated according to the method described by Colby to demonstrate synergism between 4- (3 *, 5 * + dichloropyridyl-12-yl) -aliphenylenoxyponic acid (compound of formula Ia) and compounds of formulas IIa to Hd.

CoOibri wheat plant tested ”

compound of formula Ia kg / ha 0.5 0; , 25 added ingredient kg / ha 1 1.0 0.5 1 1.0 0.5 n o n O n 0 n O a compound of formula IIIa 75 62 75 62 75 75 87 75 a compound of formula HHb 62 62 100 62 100 ALIGN! 75 100 ALIGN! 75 a compound of formula HHc 62 62 62 62 100 ALIGN! 75 100 ALIGN! 75 a compound of formula HHd 75 62 75 62 100 ALIGN! 75 100 ALIGN! 75 test plant Avena fatua compound of formula Ia kg / ha 0.5 0, , 25 added ingredient kg / ha 1 l, o 0.5 1 1.0 0.5 n o n O n O n O a compound of formula IIa 12 12 12 12 12 12 12 12 a compound of formula HHb 12 12 12 12 12 12 12 12 a compound of formula HHc 12 9 12 12 12 9 12 12 a compound of formula HHd 12 12 12 12 12 12 12 12

221В41 continued table 2 test plant

Sinapis arvensis

compound of formula Ia kg / ha 0.5 0, 25 added ingredient kg / ha 1 I, 0 0.5 1 , 0 0.5 n 0 n 0 n O n 0 the compound of Formula IIIa 12 25 25 62 1 2 25 25 62 a compound of formula IIb 12 12 25 25 1 12 12 25 the compound of formula IIc 1 1 1 1 1 1 1 1 a compound of formula IId 1 12 12 25 1 12 12 25 testovaná rostinna Chry запретит segetue compound of formula Ia kg / ha 0.5 0, 25 added ingredient kg / ha 1 1.0 0.5 1 , 0 0.5 n O n O n O n O a compound of formula IIa 25 62 37 62 37 62 62 62 a compound of formula IIb 12 12 12 62 12 12 25 62 the compound of formula IIc 12 37 25 50 12 37 25 50 a compound of formula Ud 37 100 ALIGN! 37 100 ALIGN! 25 100 ALIGN! 37 100

Note: n = measured value o = calculated value

(b) Table 3:

Tolerance and activity ^{of p} ro ^p r ^g ester of 4- ⁽³ * 5 * ^p dichloro pyrid-2 ^{yl -} ^ (^> ^ ^y) - ^Ail ^ - ^e ^ n ox ^y thiopropionic acid (compound of formula Ib ) and compounds of formulas IIIa to IId and their simulations in post-emergence application:

test plant compound of formula Ia kg / ha added component kg / ha 0 1.0 0.5 0 wheat 0.5 1.0 Ccoibi 0.5 0 0.25 1.0 0.5 a compound of formula IIa 9 9 7 7 7 7 9 9 a compound of formula IIb 9 9 7 9 9 7 9 9 the compound of formula IIc 9 9 7 8 8 7 9 9 a compound of formula IId 9 9 7 9 9 7 8 8 testovaná rdstinna Avena f atua compound of formula Ia kg / ha 0 0.5 0.25 added ingredient kg / ha 1.0 0.5 0 i, o 0.5 0 ',O 0.5 a compound of formula IIIa 9 9 2 2 2 2 2 2 a compound of formula IIb 9 9 2 2 2 2 2 2 the compound of formula IIc 7 9 2 2 2 2 2 2 a compound of formula IId 9 9 2 2 2 2 2 2 test plant Sinapis arvensis compound of formula Ia kg / ha 0 0.5 0.25 added ingredient kg / ha 1.0 0.5 0 1.0 0.5 0 1.0 0.5 a compound of formula IIIa 3 6 9 2 4 9 2 3 a compound of formula IIb 2 3 9 2 3 9 3 3 the compound of formula IIc 1 1 9 1 1 9 1 1 a compound of formula IId 2 3 9 1 2 9 1 2

Table 3: Chτys8alheemvш segetim test plant compound of formula Ia kg / ha added component kg / ha 0 1> 0 0.5 0 0.5 1.0 0.5 0 0.25 1.0 0.5 a compound of formula IIIa 6 6 9 2 4 9 4 4 a compound of formula IIb 2 6 9 2 3 9 1 2 a compound of formula Ile 4 5 9 2 2 9 3 3 a compound of formula IId 9 9 9 6 6 9 6 9

If the values calculated for the cumulative effect according to Colby's method compare with the results of Table 3, then the observed growth values for the mustard (Sinapis arvensis) and the daisy (Chrysanheemtm segetum) are found to be lower than the effects calculated. . This synergism is demonstrated, g c ^k ± ý effect of the mixture of propan-ester of 4- ⁽³ * 5 * - * -v ^d iehlvrpylidyll2 ^χl "alphal -feavxythiopropVonové ester (compound Ib) with compounds of the formulas IIa to IId (cf. Table 4).

Table 4:

Values calculated by the method described by Colby, the proof synergism MEEI propadlesterem ⁴ - ⁽³ * 5 * - ^d ichlorp ^l r ^{l d} dy -2 ⁱⁿ ols) ⁿ -alffe evolyth ⁱⁿ opvo ^N octanoic ^acid; and ^L-torches (Ib) and compounds of formulas IIIa to IId.

test plant wheat compound of formula Ia kg / ha 0. , 5 0.25 added ingredient kg / ha 1 , 0 0.5 1.0 0.5 n O n O n 0 n 0 a compound of formula IIIa 75 75 75 75 100 ALIGN! 75 100 ALIGN! 75 a compound of formula IIb 100 ALIGN! 75 100 ALIGN! 75 100 ALIGN! 75 100 ALIGN! 75 a compound of formula IIc 87 75 87 75 100 ALIGN! 75 100 ALIGN! 75 a compound of formula Ild 100 ALIGN! 75 100 ALIGN! 75 87 75 87 75 test plant Avena fatua compound of formula Ia kg / ha 0. , 5 0.25 added ingredient kg / ha 1 1.0 0.5 1.0 0.5 n O n O n O n O a compound of formula IIIa 12 12 12 12 12 12 12 12 a compound of formula Ib 12 12 12 12 12 12 12 12 compound of formula Ш 12 9 12 12 12 9 12 12 a compound of formula Ild 12 12 12 12 12 12 12 12 test plant Sinapis arvensis compound of formula Ia kg / ha O, , 5 0.25 added ingredient kg / ha 1 , 0 0.5 1.0 0.25 n O n O n O n O a compound of formula IIIa 12 25 37 62 12 25 25 62 a compound of formula Ib 12 12 25 25 25 12 25 25 compound of formula IIc 1 1 1 1 1 1 1 1 a compound of formula Ild 1 12 12 25 1 12 12 75

Chrysanhhemum segetum

0,5 0,25

0,5 1,0 0,5 Table 4 continuation:

test plant compound of formula Ie kg / ha added component kg / ha

1,0 n

n O n

O n O

compound formulas Ila 12 62 37 62 37 62 37 62 compound formulas lib 12 12 25 62 1 12 12 62 compound formulas IIc 12 37 12 50 25 37 25 50 compound formulas Ild 62 100 ALIGN! 62 100 ALIGN! 62 100 ALIGN! 100 ALIGN! 100 ALIGN!

Note: n = measured value o = calculated value

Example 2

The following results were obtained in field trials on wheat sown plots. Growth data is in percent compared to untreated control plot.

(a) field trial in Cisse (France) application on 18 March 1980, evaluation 85 days after application (10 June 1980)

Compound No. Used Growth Avena fatua Wheat Growth mmnexpected as expected by g / ha Colby

Ia: 150 50 - 100 ALIGN! Ib; 200 55 - 100 ALIGN! Ila: 2 000 60 - 100 ALIGN! IIc: 1 250 90 - 100 ALIGN! Ia + Ha: (150 + 2 000) 12 30 100 ALIGN! Ia + IIc: (150 + 1 250) 6 45 ' 100 ALIGN! Ib + Ila: (200 + 2,000) 12 33 100 ALIGN! Ib + IIc: (200 + 1,250) 5 50 100 ALIGN!

b) field trial in Pouant (France)

application on March 19, 1980 evaluation 84 days after application (10 June 1980) Growth of wheat Compound No. Pouuité g / ha Growth of Avena fatua observed expected by Colby Ia: 150 15 Dec - 100 ALIGN! Ib: · 200 20 May - 100 ALIGN! Ila: 2 000 80 - 100 ALIGN! IIc: 1 250 70 - 100 ALIGN! Ia + Ila: (150 + 2 000) 2 12 100 ALIGN! Ia + IIc: (150 + 1 250) 0 10.5 100 ALIGN! Ib + Ila: (200 + 2,000) 3 16 100 ALIGN! Ib + IIc: (200 - 1 250) 2 12 100 ALIGN!

Examples illustrating the composition and preparation of formulations:

Example 3

Examples of compositions of allergic mixtures of the active substances of formulas I and II (% =% by weight)

(a) Wettable powder and) (b) C) (d) the active ingredient Ia or Ib 10% 20% 5% 30% one of the active substances II 10% 40% 15% 30% tatriюligtitsULFotát 5% 5% 5% 5% to triuolauurlstufá t 3% - 3% - · n ^ 1 ^: ri iso č i iso iso iso iso iso iso u u u u u u u t t t t t - 6% - 6% octylphenolpolyethylene glycol ether (7 to 8 moles of ethylene oxide) - 2% - 2% highly disperse silicic acid 5% 27% 5% 27% kaolin 67% - 67% _-

Active ingredient mixture well mixed te t te tmět additives and ground well in a suitable mill to give te · t ^ ^ Mali LNY powder - ¹ which gives te - diluted with water to the desired concentration tutpenze ·

(b) Enzyme conc.

and) (b) C) 5% 5% 12% 5% 20% 13 % 3% 3% 3% 3% 3% 2% 4% 4% 4% 30% 30% 31% 50% 35% 35%

'Emulsions of any desired concentration can be prepared from these endenates by dilution with water.

o) Dust and) (b) C) (d) the active ingredient Ia or Ib 2% 4% 2% 4% one of the active substances II 3 « 4% 4% 8% talc 95% - 94% - kaolin - 92% . - 88%

Directly dustable powder is obtained by mixing the three active ingredients with the carrier

and the mixture obtained is ground in a suitable mill. d) Extruded granules and) (b) C) the active ingredient Ia or Ib 5% 3% 5% one of the active substances II 5% 7% 15% natri uoligni 2% 2% 2% carboxymeehhlcelulóza 1% 1% 1% kaolin 87. % 87% 77%

The active ingredient mixture is then mixed with the ingredients and grinded and granulated with water.

e) .Packaged granulate and) (b) Active ingredient Ia or Ib 1.5 % 3% one of the active substances II 1.5 % 5% polyttylltyglycol (molecular weight 200) 3 % 3% kaolin 94 % 89%

The finely divided active compound mixture is uniformly applied to a kaolin moistened with polyethylene glycol in a suitable mixer. In this way a dust-free coated granulate is obtained.

f ^ Suspension ^ поспУ ^!

and)

(b) Active substance Ia or Ib 20% One of the active substances II 20% Ethyltyl chloride 10% Polyethylene glycol (15 moles of ethylene oxide) 6% Yatylmligyl sulphoyate 10% Carboxymethylcellulose I% 37% Aqueous solution of Fojraaldehyde 75% aqueous solution in oily form 0.2% -ze 0,8% water 32%%

%%

%%

%

0.2%

0.8%%

The finely divided active compound mixture is thoroughly concentrated concentrate, from which it can be mixed with additives by dilution with water. It is obtained. . a suspension suspension of each desired concentration.

Claims (6)

First synergistic agent for selectively controlling weeds ICI ^ significance in that in addition to carriers and / or other additives containing as active ingredients on the one hand ^{opargrlester-4- (3,} 5 ^{(- d} ic ^h ltrpyli ^d-2-yl, -OX ^yl) -a ^{ea t} e Yoo: ^l φrop ontvé ^t k ^{l l} ieliУ general formula I in which Z is oxygen or sulfur, and on the side a second urea derivative of the formula II (II) wherein hydrogen is Bj zynamyn methyl group and R 3 is a 3-carbon-4-methylethyl group, a 3-carbon-4-methylthiophenyl group A 4-POOPYPROLLY group, or R, is not a methyl group, R denotes hydrogen and, R 1 is a benzothiazol-2-yl group, in a weight ratio of 1: 1 to 1: 25. 2. A composition according to claim 1, characterized in TIA as active ingredient obsOiuje pro- pargyl- ter-4- (3 * 5 * 2 * -dichlorpyridyl ooχy) n _E n aeieno2ιp'pooiOinooé acid (In) N 3 (3'-chloro-4'-ethylphenyl) -1,1-diaethylacetic acid (Hr). . 3. A composition according to claim 1, wherein the active ingredient is 4- (3 *, 5 * -dichloropyridyl-2-oxo) -propyl-4-chloro-hydroxy-propionate (Ib) n 3- (4'-chloro-4 *) -propyl ester. (methylphenyl) -1,1-diaethylarea (1i). 4. A composition according to claim 1, wherein the active ingredients are 4- (3 *, 5 * -dichloropyridyl) -2'-olyl-a-a-ionolppoopoic acid propargyl ester (Ia) and 3- (4). 1 -isopropylphenil) -1, 1-diaethylarea (IIc). 5. A composition according to claim 1, characterized ICI ^ conforms to the TIA, as active ingredient contains propargyl ^ c ^ ter 4- (3 ^* 5 * -dCch0orpyri ^l-yl 2 ^o ols) ^-N- e ^{i 0} ynoic onolythiopoop of acid ⁽ I ^b) and 3- ^(4'- isopropylphenyl) -1,1-diaethyliuric acid (IIc). 6. A composition according to any one of Claims 1 to 5, wherein the composition is selected from the group consisting of: 6. The method according to claim 1, wherein the thoracic carrier is between 1: 1 and 1: ezi between component I and component II.