DD201967A5 - SYNERGISTIC MEANS AND METHODS OF SELECTIVE OROCHAPTERING, ESPECIALLY IN CEREALS - 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

gistisehes means and method for selective weed control

Field of application of the invention

The present invention relates to a synergistic agent which contains a herbicidal active ingredient combination which is outstandingly suitable for selective weed control I in cereal crops. The invention also relates to a method for controlling weeds, in particular in cereals, and the use of the novel agent,

Currently the most common and important weeds in cereals are species of the genus Sinapis (mustard), chrysanthemum (wildflower) and certain Avena species (wild oats).

Characteristic of the known technical solutions

As excellent postemergic selective herbicides against monocotyledonous we have 4- (3 ^T »5 ^f -Dichlorpyridyl-2'-oxy) -Of-phenoxypropionsäurepropargylester of the formula I.

-X-O-Y-O-CH-CO-Z-CHX-CSCH (I),

where Z is oxygen or sulfur.

The two compounds of the formula I, namely 4- (3 ', 5'-dichloropyridyl-2- ^f -oxy) -oc-phenoxy-propionic acid propargyl ester (Ia) and 4- (3', 5'-dichloropyridyl-2 ' -oxy) -OC-phenoxypropionthiolic acid propargyl ester (Ib), their preparation and use as selective herbicides are described in European Patent Publication No. 3114.

231584 8.

It is known that dicotyledonous weeds in cereals, but also some monocotyledonous weeds in postemergic application, often successfully with S-O'-chloro-A'-methylphenyD-l-dimethylurea (chlortoluron) of the formula Ila

H ₃ C 1-5 -NH-CO-N (CH ₂ J (Ha) Cl

or with 3- (3'-chloro-4'-methoxyphenyl) -1, l-dimethylurea (metoxuron) of the formula Hb

HC-O- / ^ -NH-CO-N (CH-) (lib)

• a · /

Cl

or with S-iA'-IsopropylphenyD-ljl-dimethylharnsttoff (isoproturon) of the formula Hc

1-H ₇ C - ^ y- NH-CO-N (CH) (lic)

or with l-benzothiazol-Z-yl-l ^ S-dimethylurea (methabenzthiazuron) of the formula Hd

I l -N-CO-NH-CH, (lld)

or with 4-hydroxy-3,5-diiodobenzonitrile (joxynil) of the formula He

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AP A 01 I / 231 584 59 368 11

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---] _χ OH

Il j (he)

NC ^ '\. ^ * ^Χ J

or with 3,5-dibromo-4-hydroxybenzaldehyde 0- (2 ', 4 ^f dinitrophenyl) oxime (bromophenoxime) of the formula Hf

br

(Hf)

Br H

be fought.

The compounds of the formulas II and their herbicidal activity have been described, for example, in the following references:

Chlortoluron (verb Ha) in Cr. 5 Conf.Com. franc,:

Mauvaises Herbes (COLUME.), 1969, H, 349, Metoxuron (verb. Lib) in Z. PfIkrankh., PflPath., PflSchutz, 1968, 7, 233, isoproturon (verb lic) in DE-PS 2 107 774, Methabenzthiazuron (verb Hd) in PflSchutz-Nachr.

Bayer, 1969, 22, 314,

Joxynil (verb) in Nature, London, 1963, 200 , 28 and

Bromofenoxime (Comp. Hf) in Proc. 3rd EWRC Symp. "New Herbicides", Paris, 1969, p. 177.

Aim of the invention;

The aim of the invention is the provision of new weed control agents with increased Y / effectiveness, which are particularly suitable, the most important and z. Z. frequently destroy weeds in cereal crops selectively.

_/ β 4 Ö

3a Presentation of the essence of the invention

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AP A 01 * / 231 584 59 368 11

The object of the invention is to use mixtures of certain known herbicides for weed control and to achieve a biological effect which is stronger than the additive effect of the individual components.

According to the invention, the novel synergistic selective weed control agent contains, in addition to carrier and / or other additives as an effective component, on the one hand, a 4- (3 '> 5 ^f -dichloropyridyl-2'-oxyJ-CC-phenoxy-propionsäurepropargylester of formula I.

XO-CH-CO-Z-CH ₀ -C = CH (I),

wherein Z is oxygen or sulfur, and on the other hand, 3- (3'-chloro-4'-methylphenyl) -1,1-dimethylurea (Ha) or 3- (3'-Chloro-4 ^{f-methoxyphenyl)} -1,1- dimethylurea (Hb) or 3- (4'-isopropylphenyl) -1,1-dimethylurea (lic) or 1-benzothiazol-2-yl-1,3-dimethylurea (Hd) or 4-hydroxy-3,5-diiodobenzonitrile ( He) or 3 '5-dibromo-4-hydroxybenzalde.hyd-0- (2', 4 -dinitrophenyl ^f) oxime (Hf).

It has now surprisingly been found that a quantitatively variable within certain limits combination of the two classes of active substances I and II unfolds a Synergistisehe effect that is able to combat the majority of all important crop weeds, without damaging the grain culture. It will be the main weeds of the

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Grain crops, such as species of Dikotyledonengattung Chrysanthemum and Sinapis and certain Avena species (wild oats) selectively destroyed in the accumulated crops.

It is surprising that the combination of an active compound of the formula I with an active ingredient of the formulas II not only causes a generally expected additive supplementation of the spectrum of action on the usual grain-associated weeds, but that it achieves a synergistic effect, the limits of action of both preparations expanded under two aspects.

Once the application rates of the individual compounds I and II are significantly reduced with consistently good effect. On the other hand, the combined mixture also achieves a high degree of weed control there, where both individual compounds have become completely ineffective in the area of too low application rates. This results in a significant broadening of the weed spectrum and an additional increase in the safety margin on cereals, as it is necessary and desirable for unintended drug overdose.

The composition of the invention may be used, except in cereal crops such as barley, rye and, in particular, wheat, for selective weed control in other monocotyledonous cultures of similar drug sensitivity with similar weed stock, e.g. Corn and rice.

The active ingredient combination according to the invention contains an active compound of the formula (I) and one of the formulas (II) in any desired mixing ratio, generally with an excess of one over the other component. Particularly preferred are excesses of component II to 1:25, but especially Mixing ratio (I) :( II) = 1: 1 to 1:10.

The active compound combinations according to the invention show an excellent action against weeds, but without cereal crops in

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Usual application rates of 0.2 to 4 kg, preferably 0.5 to 3 kg per hectare to influence appreciably.

! '..: '! As very, particularly effective synergistic mixtures of active ingredients, the following combinations have been found:

a) 4- (3 ', 5 * -Dichlorpyridy1-2'-oxy) -afphenoxy-propionsäurepropargy1 ester (Ia) and 3- (3'-chloro-4 ^{l-methylphenyl)} -l, l-dimethylurea (Ha) .

b) 4- (3 ', 5'-Dichlorpyridy1-2'-oxy) -ot-phenoxy-thiopropionsäurepropargylester (Ib) and 3- ^{(4-chloro-f f} 4-methylphenyl) -l, l-dimethylurea (Ha) .

c) 4- (3 ', 5'-dichloropyridy1-2'-oxy) -α-phenoxy-propionic acid propargyl ester (Ia) and 3- (4'-isopropylphenyl) -1,1-dimethylhydric (lic), and

d) 4- (3 ', 5-dichloropyridyl-2'-oxy) -α-phenoxy-thiopropionic acid propargyl ester (Ib) and 3- (4'-isopropylphenyl) -1,1-dimethylurea (lic).

The present invention also relates to the use of the agent according to the invention, ie a method for selective üngras- and weed control in cereals under post-emergent application of the agent.

The agent according to the invention with the new active ingredient combination contains, in addition to the active substances mentioned, suitable carriers and / or other additives. These may be solid or liquid and correspond to the usual in the formulation art materials such. natural or regenerated mineral substances, solvents, dispersants, wetting agents, adhesives, thickeners, binders or fertilizers. Suitable applications are therefore e.g. Emulsion concentrates, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granules, including encapsulation in.z.B. polymeric substances. The application methods such as spraying, misting, dusting, scattering or pouring are chosen as well as the type of means according to the desired goals and the given circumstances.

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The formulations, i. the compositions, preparations or compositions containing the active substance of the formula I and, where appropriate, a solid or liquid additive are prepared in a known manner, e.g. by intimately mixing and / or grinding the active ingredients with diluents, e.g. with solvents, solid carriers, and optionally surface-active compounds (surfactants).

Suitable solvents are: Aromatic hydrocarbons, preferably the fractions C to C, -, such. Xylolge-

o IZ

mixed or substituted naphthalenes, phthalic acid esters such as dibutyl or dioctyl phthalate, aliphatic hydrocarbons such as cyclohexane or paraffins, alcohols and glycols and their ethers and esters such as ethanol, ethylene glycol, Aethylenglykolmonomethyl- or -äthyläther, ketones such as cyclohexanone, strongly polar solvents such as N-methyl 2-pyrrolidone, dimethyl sulfoxide or dimethylformamide, and optionally epoxidized vegetable oils such as epoxidized coconut oil or soybean oil; or water.

As solid carriers, e.g. For dusts and dispersible powders, ground natural minerals are generally used, such as calcite, talc, kaolin, montmorillonite or attapulgite. To improve the physical properties, it is also possible to add highly dispersed silicic acid or highly dispersed absorbent polymers. As granular, adsorptive granule carriers are porous types such. Pumice, broken brick, sepiolite or bentonite, as non-sorptive carrier materials e.g. Calcite or sand in question. In addition, a variety of pre-granulated materials of inorganic or organic nature, in particular dolomite or crushed plant residues can be used.

Suitable surface-active compounds are nonionic, cationic and / or anionic surfactants having good emulsifying, dispersing and wetting properties. Surfactants are also surfactant mixtures.

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Suitable anionic surfactants may be both so-called water-soluble soaps and water-soluble synthetic surface-active compounds.

As soaps are the alkali, alkaline earth or optionally substituted ammonium salts of higher fatty acids (C _1n ~ C ₂ _), such as the Na or K salts of OeI- or stearic acid, or of natural Fettsäuregemisehen, for example, from coconut or tallow oil can be obtained, called. Furthermore, the fatty acid methyl taurine salts should be mentioned.

More often, however, so-called synthetic surfactants are used, especially fatty sulfonates, fatty sulfates, sulfonated benzimidazole derivatives or alkylarylsulfonates.

The fatty sulfonates or sulfates are generally present as alkali, alkaline earth or optionally substituted ammonium salts and have an alkyl radical of 8 to 22 carbon atoms, alkyl also including the alkyl moiety of acyl radicals, e.g. the Na or Ca salt of lignosulfonic acid, of dodecylsulphuric acid ester or of a fatty alcohol sulphate mixture prepared from natural fatty acids. This subheading also covers the salts of sulfuric acid esters and sulfonic acids of fatty alcohol / ethylene oxide adducts. The sulfonated benzimidazole derivatives preferably contain 2-sulfonic acid groups and a fatty acid residue having 8-22 C atoms. Alkylarylsulfonates are e.g. the sodium, calcium or triethanolamine salts of dodecylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid, or a naphthalenesulfonic acid-formaldehyde condensation product.

Furthermore, corresponding phosphates, e.g. Salts of the phosphoric acid ester of a p-nonylphenol (4-14) -ethylene oxide adduct in question.

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Suitable nonionic surfactants are primarily polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, saturated or unsaturated fatty acids and alkylphenols, which may contain from 3 to 30 glycol ether groups and from 8 to 20 carbon atoms in the (aliphatic) hydrocarbon radical and from 6 to 18 carbon atoms in the alkyl radical of the alkylphenols.

Further suitable nonionic surfactants are the water-soluble polyethylene oxide adducts containing from 20 to 250 ethylene glycol ether groups and from 10 to 100 propylene glycol ether groups with polypropylene glycol, ethylene diaminopolypropylene glycol and alkylpolypropylene glycol having from 1 to 10 carbon atoms in the alkyl chain. The compounds mentioned usually contain 1 to 5 ethylene glycol units per propylene glycol unit.

Examples of nonionic surfactants are nonylphenolpolyäthoxyäthanole, Ricinusölpolyglykolähter, polypropylene polyethylene oxide adducts, Tributylphenoxypolyäthoxyäthanol, polyethylene glycol and octyl

phenoxypolyäthoxyäthanol mentioned.

Further also come; Fatty acid esters of polyoxyethylene sorbitan such as the polyoxyethylene sorbitan tri-oleate.

The cationic surfactants are, above all, quaternary ammonium salts which contain as N-substituents at least one alkyl radical having 8 to 22 C atoms and contain, as further substituents, lower, optionally halogenated alkyl, benzyl or lower hydroxyalkyl radicals. The salts are preferably in the form of halides, methylsulfates or ethylsulfates, e.g. stearyltrimethylammonium chloride or benzyldi (2-chloroethyl) ethylammonium bromide.

The surfactants commonly used in formulation technology are i.a. described in the following publications:

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"McCutcheon's Detergents and Emuslifiers Annual" MC Publishing Corp., Ringwood, New Jersey, 1979.

Sisely and Wood, "Encyclopedia of Surface Active Agents", Chemical Publishing Co., Inc. New York, 1964.

The active ingredient content in marketable agents is between 0.1 to 95 weight percent, preferably 1 to 80 weight percent.

In particular, preferred formulations are composed as follows: (% by weight)

solutions

Active Ingredient: Solvent: Surfactant:

Emulsifiable concentrates

Active ingredient: Surfactant: Liquid carrier:

5 to 95%, preferably 10 to 80% 95 to 5%, preferably 90 to 0% 1 to 30%, preferably 2 to 20%.

10 to 50%, preferably 10 to 40% 5 to 40%, preferably 10 to 20% 20 to 95%, preferably 40 to 80%.

dusts

Active ingredient:

solid carrier:

0.5 to 10%, preferably 2 to 8% 99.5 to 90%, preferably 98 to 92%,

Suspensory Concentrates Active Ingredient: Water: Surfactant :

5 to 75%, preferably 10 to 50% 94 to 25%, preferably 90 to 30% 1 to 40%, preferably 2 to 30%.

Wettable powders Active ingredient:

Surfactant: solid carrier:

5 to 90%, preferably 10 to 80% and

in particular 20 to 60% 0.5 to 20%, preferably 1 to 15%

5 to 90%, preferably 30 to 70%.

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- ίο -

granules

Active ingredient: 0.5 to 30%, preferably 3 to 15% solid carrier: 99.5 to 70%, preferably 97 to 85%.

While merchandise tends to be concentrated, the end user typically uses diluted medications. The use forms can be diluted down to 0.001% of active ingredient.

The described inventive compositions can be mixed with other biocidal agents or agents. Thus, in addition to the compounds of general formula I and formula II, Insecticides, fungicides, bactericides, fungistatics, bacteriostats or nematocides to broaden the efficacy

Spectrum included.

A synergistic effect is always present in herbicides if the herbicidal action of the active ingredient combination I + II is greater than the sum of the effect of the individually applied active ingredients.

The expected plant growth E for a given combination of two herbicides can be calculated as follows (see COLBY, S.R., "Calculating synergistic and antagonistic response of herbicidal combinations", Weeds 15, pages 20-22, 1967):

100

Mean: X »percent growth (compared to untreated plants) when treated with a herbicide I with ρ kg application rate per hectare,

Y * percent growth in treatment with a herbicide II with q kg application rate per hectare

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E = Expected growth in percent of the control plants after treatment with herbicide mixture I + II at an application rate of ρ + q kg of active substance per hectare.

If the actually observed value is lower than the expected value E, then there is synergism.

embodiment

The invention is explained in more detail below with reference to some examples. The synergistic effect of the combinations of agents I and II is demonstrated in the following examples.

Example 1 ; The test plants are sown in plastic containers containing 30 1 sterilized garden soil in the greenhouse. After emergence, the plants are sprayed in the 2- to 3-leaf stage with an aqueous dispersion of the active ingredient combination. The application rate of dispersion is 50 ml per m, After 15 days at temperatures of 10 to 2O ⁰ C, a relative humidity of 60 to 70 % and daily irrigation of the container, the evaluation is carried out.

The degree of damage of the plants becomes linear according to the following

Scale rated:

1: plants dead

5: medium effect

9: normal condition,

Purely different mixing ratios and total active ingredient amounts are obtained the following results:.

^a ) Table 1; Tolerance and activity of propyl 4- (3 ^f »5'-dichloropyridyl-2'-oijcyclophenoxy-propionate (Compound Ia) and the compounds Ha to Hf and their mixtures in postemergic use.

Test plant Wheat "Colibri" 0 0.5 0.5 0 1.0 0.5 12:25 0 1.0 0.5 Avena fatua 1.0 0.5 0.5 0 1.0 0.5 12:25 0 1.0 0.5 Sinapis arvensis 0.5 0.5 0 1.0 0.5 12:25 0 1.0 0.5 Chrysanthemum segetuin 0.5 0.5 0 1.0 0.5 12:25 0 1.0 0.5 Verb.Ia kg AS / ha 1.0 9 6 7 7 7 7 8th 0 9 9 2 2 2 2 2 2 .0 6 9 2 3 9 2 3 0 6 9 3 4 9 4 6 Mix partner kg AS / ha 9 9 6 6 9 7 9 9 9 9 2 2 2 2 2 2 1.0 3 9 2 3 9 1 2 1.0 6 9 2 2 9 2 3 Verb. Ha 9 9 6 6 6 7 9 9 7 9 2 2 2 2 2 2 3 1 9 1 1 9 1 1 6 5 9 2 3 9 2 3 Verb Hb 9 9 βΠ 7 7 7 9 9 9 9 2 2 2 2 2 2 2 3 9 1 2 9 1 2 2 9 9 4 4 9 3 4 Verb Hc 9 9 6 8th 8th 7 9 9 9 9 2 2 2 2 2 2 1 2 9 1 2 9 1 2 4 4 9 2 3 9 1 3 Verb. Hd 9 9 6 9 9 7 9 9 9 9 2 2 2 2 2 2 2 3 9 1 1 9 1 2 9 3 9 I 3 9 1 3 Verb 9 1 , 2 Verb. Hf 2 1

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If the values calculated using the Colby method for additive effect are compared with the results from Table 1, it can be seen that the observed growth values for Sinapis arvensis and Chrysanthemum segetum are smaller than the calculated effects. This proves the synergistic effect of the mixture of 4- (3 ', 5'-bichloropyridyl-2'-oxy) -a-phenoxypropionic acid propargyl ester with the compounds Ha to Hf (see Table 2).

Table 2: Values calculated by Colby's method to demonstrate the synergism between 4- (3 ', 5'-dichloropyridyl-2'-oxy) -ophenoxypropionic acid propargyl ester (Compound Ia) and the compounds Ha to Hf.

l-l Ml

i-S

XT

IH

ro

ro η c

ro η a ·

ro ³ η

he

5C "Ö

t-f ce

l> ft ft

\ ro

oo ro

If

Ό Η

i-h ro

-53 "Ln

CD

ro

oo

ro

ln

O O

ln

on to

ON

ro

measured value

O\

to

to

ON

to

expected value

VJ

ln

ON

to

measured value

ON

ro

ON

ro

On to

expected value

ο Ln

measured value

VJ

ln

VJ

ln

VJ

ln

expected value

ο o

measured value

VJ

ln

vj Ln

vj Ln

expected value

O Ln

ul

ro

ul

ro

to

to

ro

to

ro

ro

to

ro

ro

measured value

to

to

expected value

to

to

to

measured value

ro

to

to

expected value

ln

ro

ro

ro

measured value

to

ro

expected value

ro

to

to

measured value

to

to

to

expected value

ro

ui

Mi (a η

ro

ro

to

ro

to

measured value

to

to

expected value

to

IO

ln

measured value

ro

ln

ro

ln

expected value

O Ln

measured value

to

to

expected value

to

to

measured value

ro

ln

to

ln

expected value

O Ln

O Ui

ro

ul

Ό Η · CO

ro

to

LO vj

U>

ro

ln

LO

LO vj

ro

ro

measured value

LO

VJ

to

expected value

LO

vj

to Ln

to

measured value

Ln O

On to

expected value

O Ui

ro

ul

to

to

measured value

LO

vj

expected value

vj

ro

ln

(O

ln

measured value

Ui

on

ro

expected value

O Ln

O Ui

ro

Ui

r \

C7

! 3158 4 8

b) Table 3 ; Tolerance and activity of propyl 4- (3 ', 5'-dichloropyridyl-2- ^T -oxy) -α-phenoxy-propionthiolate (Comp. Ib) and the compounds Ha to Hf and their mixtures in post-emergence application.

Test plant Wheat "Colibri" 0 0.5 0.5 0 1.0 0.5 12:25 0 1.0 0.5 Avena fatua 1.0 0.5 0.5 0 1.0 0.5 12:25 0 1.0 0.5 Sinapis arvensis 0.5 0.5 0 1.0 0.5 12:25 0 1.0 0.5 Chrysanthemum segetum 0.5 0.5 0 1.0 0.5 12:25 0 1.0 O.i Verb.Ib ky AS / ha l.O 9 7 7 7 7 9 9 0 9 9 2 2 2 2 2 2 0 6 9 2 4 9 2 3 0 6 9 2 4 9 4 4 Mix partner kg AS / ha 9 9 7 9 9 7 9 9 9 9 2 2 2 2 2 2 1.0 3 9 2 3 9 3 3 1.0 6 9 2 3 9 1 2 Verb. Ha 9 9 7 8th 8th 7 9 9 7 9 2 2 2 2 2 2 3 1 9 1 1 9 1 1 6 5 9 2 2 9 3 3 Verb Hb 9 9 7 9 9 7 8th 8th 9 9 2 2 2 2 2 2 2 3 9 1 2 9 1 2 2 9 9 6 6 9 6 9 Verb Hc 9 9 7 9 9 7 9 9 9 9 2 2 2 2 2 2 I 2 9 1 2 9 1 1 4 4 9 2 2 9 2 3 Verb. Hd 9 9 7 9 9 7 9 9 9 9 2 2 2 2 2 2 2 3 9 2 2 9 - - 9 3 9 1 3 9 1 3 Verb.lie 9 1 2 / Erb. Hf 2 1

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If the values calculated according to Colby for additive effect are compared with the results from Table 3, it can be seen that the growth values for Sinapis arvensis and Chrysanthemum segetum are smaller than the calculated effects. Thus, the synergistic effect of the mixture of 4- (3 ', 5'-dichloropyridyl-2'-oxy) -a-phenoxypropionthiolsäurepropargylester (verb Ib) with the compounds Ha to Hf proved (see Table 4).

Table 4: Values calculated by method Colby for the detection of

Synergism between 4- (3 ', 5'-dichloropyridyl-2- ^f -oxy) -aphenoxy-propionic acid propargyl ester (Comp. Ib) and the compounds Ha to Hf.

- 81 -

rc rc rc (6 rc ⁵ rc measured value η pi f OQ rc «, N? bi tr T σ σ tr expected value ► does D BS? x rc ι > he \ ι-ι C CB it rt l-h rc a. η ο * O measured value ta S3 rc 100 001 100 09 years ago 100 VJ expected value »- * 0.5 Ui ul ul Ui ul ul measured value ©, n> N 100 001 100 OO vj 100 vj ui expected value O O rc p Ui Ui Ui Ui ul Ui measured value Ui N) Ui O o 100 ΟΟΐ OO vj 100 I- * O 100 expected value 1-· ι- * vj vj Ul vj Ui vj ui Ui measured value O η 100 100 OO VJ 100 100 100 expected value O O U * VJ Ui VJ Ul vj Ui vj Ui VJ Ui vj Ui measured value Ui NS NS N) N) N) NS expected value rc NS NS N) VO NS NS measured value O is NS NS N) N) NS NS expected value O O IO fatua N) NS NS NS NS NS measured value Ui N) NS N) N) N) N) expected value • O NS N) IN) vo N) (- · N) measured value O NS N) N) N) N) NS expected value Ui O IA NS N) NS N) N) N) measured value 1-' Ui S it N) N) NS expected value O Ό ce NS NS N) N) Ul measured value O arvenfi N) N) I- ¹ N) t- ¹ N) Ui US vj expected value Ui O ι- ·· CB N) Ui t- ¹ N) N) Ul ! - N) Ui NS measured value _. N) Ui I ^ t " N) Ui N) expected value O t t " 1-> N) N) N) ui measured value O 0.5 η I - f · N) - N) Ui NS Ui expected value Ui 12:25 Irya I t- "NS vj Ui I- ¹ N) Ui IO measured value C * W 9 rt I- ¹ t- 'NS N) N) N) I- ¹ NS expected value O rc I- ¹ NS 8th us vj (- N) NS measured value O B cn NS Ui I- * NS N) I- ¹ N) NS Ul us vj expected value iegetun NJ Ui us 100 Ui O N) NS measured value   - NS N) NS Ul US vj expected value O I * I- ¹ NS 001 US vj N) NS O Ui Ui 100 ui N) VJ ul NS Ui US vj Ul O NS NS

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Example 2: In field trials on wheat fields, the following results were obtained. The percentage of growth is given in comparison to the untreated nuclear field:

a) Field trial in Cisse / France. Application on March 18, 1980

 Evaluation 85 days after application (10 June 1980).

Connection no. 2000) Growth AVENA FATUA expected to COLBY growth Application rate g / ha 1250) observed - wheat: ~ ^: Ia: 150 2000) 50 - 100 Ib: 200 1250) 55 - 100 Ha: 2000 60 - 100 lic: 1250 90 30 100 Ia + Ha: (150 + 12 45 100 Ia + Hc: (150 + 6 33 100 Ib + Ha: (200 + 12 50 100 Ib + Hc: (200 + 5 100

b) Field trial in Pouant / France. Application on March 19, 1980

 Evaluation 84 days after application (10 June 1980).

Connection no. 150 Growth AVENA FATUA erwartet.nach COLBY growth Application rate g / ha 200 observed - WHEAT Ia: 2000 15 100 ib: 1250 20 - 100 LIa: Ha: (150 + 2000) 80 - 100 lic: Hc: (150 + 1250) 70 12 100 Ea + Ha: (200 + 2000) , 2 10.5 100 Ea + lic: (200 + 1250) 0 16 100 Eb + 3 12 100 Ib + 2 100

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formulation Examples Example 3 : Formulation examples of synergistic mixtures of active ingredients

Formulas I and II (Z "Weight percent)

a) spray powder

Active ingredient Ia or Ib of one of the active ingredients II Na lignosulfonate Na lauryl sulfate Na diisobutylnaphthalenesulfonate

Octylphenolpolyethylene glycol ether 7-8 moles of AeO)

Highly dispersed silica kaolin

a) b) c) d) 10% 20% 5% 30% 10% 40% 15% 30% 5% 5% 5% 5% 3% - 3% - - 6% - 6% - 2% - 2% 5% 27% 5% 27% 67% 6-7% ' _-

The active substance mixture is mixed well with the additives and ground well in a suitable mill. This gives spray powder which can be diluted with water to give suspensions of any desired concentration.

b) Emulsions Kon2entrat active ingredient Ia or Ib one of the active ingredients II

Octylphenolpolyethylene glycol ether (4-5 moles of AeO)

Ca-Dodecylbenzenesulfonate Ricinusölpolyglykoläther (36 moles of AeO) cyclohexanone xylene mixture

a) b) c) 5% 5% 12% 5% 20% 13% 3% 3% 3% 3% 3% 2% 4% 4% 4% 30% 30% 31% 50% 35% 35%

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From these concentrates, emulsions of any desired concentration can be prepared by dilution with water.

c) dusts

Active ingredient Ia or Ib of one of the active ingredients II talcum kaolin

a) b) c) d) 2% 4% 2% 4% 3% 4% 4% 8th% 95% 94%

92%

88%

Ready-to-use dusts are obtained by mixing the active ingredient mixture with the carrier and grinding on a suitable mill.

d) extruder granules active ingredient Ia or Ib one of the active ingredients II iTa lignosulfonate carboxymethyl cellulose kaolin

a) b) c) 5% 3% 5% 5% 7% 15% 2% , 2% 2% 1% 1% 1% 87% 87% 77%

The active ingredient mixture is mixed with the additives, ground and moistened with water. This mixture is extruded and then dried in a stream of air.

e> coating granules active ingredient Ia or Ib of one of the active ingredients II polyethylene glycol (MW 200) kaolin

a) b) 1.5% 3% 1.5% 5% 3% 3% 94% 89%

31584 8

«Ι * - * η /, η -2ΐ-

The finely ground active substance mixture is applied uniformly in a mixer to the kaolin moistened with polyethylene glycol. In this way, dust-free coating granules are obtained.

f) suspension concentrate active ingredient Ia or Ib one of the active ingredients II ethylene glycol

Nonylphenolpolyethylene glycol ether (15 moles of AeO)

Na ligninsulfonate

carboxymethylcellulose

37% aqueous formaldehyde solution

Silicone oil in the form of a 75% aqueous emulsion

water

The finely ground active substance mixture is intimately mixed with the additives. This gives a suspension concentrate from which suspensions of any desired concentration can be prepared by dilution with water.

a) b) 20% 20% 20% 40% 10% 10% 6% 6% 10% 10% 1% 1% 0.2% 0.2% 0.8% 0.8% 32% 12%

Claims (11)

1. Synergistic agent for selective weed control, characterized in that it dai3 next carrier and / or other additives as an effective component, on the one hand, a 4- (3% 5'-Mchlorpyridyl-2'-oxy) -oi-phenoxypropionic acid propargyl ester of the formula I. Cl. ' VO -. ^ ^ .- 0-CH-CO-Z-CH ₀ -CSCH (I), wherein Z is oxygen or sulfur, and on the other hand 3- (3'-chloro-4 ^f -methylphenyl) -1,1-dimethylurea (Ha) or 3- (3 ^f -chloro-4 ^f -methoxyphenyl) -1, 1-dimethylurea (lib) or 3- (4'-isopropylphenyl) -1,1-dimethylurea (lic) or 1-benzothiazol-2-yl-1,3-dimethylurea (ldd) or 4-hydroxy-3 »5 di-iodobenzonitrile (He) or 3> 5-dibromo-4-hydroxybenzaldehyde-O- ( ^2f , 4'-dinitrophenyl) -oxime (Hf). Composition according to item 1, characterized in that it comprises effective components 4- (3 ^f , 5 ^f -dichloropyridyl-2'-OXy) -ophenoxy-propionic acid propargyl ester (Ia) and 3- (3'-chloro-4'-methylphenyl ) -1,1-dimethylurea (IIa). Composition according to item 1, characterized in that it contains effective components 4- (3 '> 5 ^f -dichloropyridyl-2'-oxy) -Qfphenoxy-thiopropionic acid propargyl ester (Ib) and 3- (4'-chloro-4'-methylphenyl ) -1,1-dimethylurea (Ha). 4 * Agent according to item 1, characterized in that it contains active components 4- (3 '»5 ^t -dichloropyridyl-2- ^t -oxy) -o (-phenoxypropionic acid propargyl ester (Ia) and 3- (4- ^f- isopropylphenyl) -1, 1-dimethy! Urea (lic) contains. ^ 31584 8 5. Composition according to item 1, characterized in that it contains effective components 4- (3 ^f »5 ^f -dichloropyridyl-2'-oxy) -oC-phenoxythiopropionic acid propargyl ester (Ib) and 3- (4» -isopropylphenyl) -1,1 contains dimethylurea (lic), 6. Composition according to one of the items 1 to 5, characterized in that in said agent the component (II) over the component (I) is present in approximately the same weight ratio or in excess, 7. Composition according to item 6, characterized in that the weight ratio between component (I) and component (II) 1: 1 to 1: 25, preferably 1: 1 to 1: 10. 8. A method for selective weed control in cereals, characterized in that post-emergently treated weeds cereal crops with an effective amount of an agent according to any one of items 1 to 7. 9. The method according to item 8, characterized in that cereal crops containing as weeds dicotyledons of the genus Chrysanthemum and Sinapis and Wildhaferarten treated with said agent. , - 9. 11. 1981 AP A 01 BT / 231 584 59 368 11 - 24 - 9. 11. 1981 AP A 01 U / 231 584 231584 8 _ ₂₃ _ ^5936811 invention claim 10. The method according to item 8 and 9, characterized in that the grain culture treated with said agent in application rates corresponding to 0.2 to 4 kg, preferably 0.5 to 3 kg total active substances per hectare. 11. Use of an effective amount of an agent according to any one of items 1 to 7, characterized in that it is used for post-nemesis selective weed control in cereal crops.