DK156982B - HERBICIDE AGENT CONTAINING A MIXTURE OF A PHENYLPYRIDAZINE DERIVATE AND A DIHALOGEN-BENZONITRIL DERIVATE - Google Patents

Description

DK 156982 B

The invention relates to a novel herbicidal active combination of active substances consisting of an already known phenylpyridazine derivative and of also known 3,5-dihalo-4-hydroxynitrile derivatives and which has a particularly strong selective and synergistic effect in - fighting weeds. The invention also relates to a method of controlling weeds, especially of difficult-to-access weeds in cereal and maize crops, using the composition of the invention.

It is known (AT Patent No. 326,409) that phenylpyridazines of the general formula 0 - / 1 nY-R.

Wherein H is a chlorine or bromine atom, a straight-chain or branched alkyl group having 1-18 C atoms or phenyl, X is an oxygen or sulfur atom and Y is a sulfur atom, Y may also be oxygen , when X is sulfur, possesses herbicidal properties and is also distinguished by good tolerance in many crops, including cereal crops.

In particular, the compound 0- [3-phenyl-6-chloro-pyridazinyl- (4) 3 -20-5- (n-octyl) -thiocarbonate has proved suitable as an agent for controlling weeds in cereal and maize cultures (Discus et al., Proc. 9th British Weed Control Conf.

1976, Vol. 2, 717) and encompasses a broad spectrum of weed plants.

25 When practiced outdoors, it has been shown that some weed species, such as the Stellaria 2

DK 156982 B

media (bird grass) and Polygonum convolvulus (windblown) only respond to relatively high doses of active substance, while other species, such as Papaver rhoeas (cereal-mue) has proven to be completely impervious to treatment. This is especially true when the weeds are at an advanced stage of development.

Furthermore, it is known that compounds from the group of 3,5-dihalogen-4-hydroxybenzonitriles have good properties as contact herbicides (Nature, London, 1963, vol. 200, p. 28). In particular, the octanoates of the compound 4-hydroxy-3,5-dibromobenzonitrile ("bromoxynil-octanoates") are used to control annual, broadleaf weeds for an advanced period of growth (H. Martin, Ch. R. Worth-ing, "Pesticide Manual "3rd edition 1977, page 293 and page 15 54). The fact is that a number of weeds with increasing aids become more resilient, so that for their control, relatively high doses must be used. These weed plants include: Galium apa-rine (climbing nose) and Galeopsis tetrahite (common male crow).

20 (Kurt H: "Chemical Weeding Camp", Fischer Verlag,

Jena, 1975, page 170).

It has now been found that mixtures of active substances from the group of phenylpyridazines of the general formula I, in particular the compound 0- [3-phenyl-6-chloro-pyridaziny1- (4)] - S- (n-octyl) -thiocarbonate , with the active substances of the group of 3,5-dihalo-4-hydroxy-benzonitriles, especially with compounds selected from 4-hydroxy-3,5-diiodo-benzonitrile octanoates ("oxyniloctanoates") and 4-hydroxy-3,5 -dibromobenzonitrile octanoates ("bromooxyniloctanoates") possess a herbicidal efficiency which is substantially higher than the efficiency expected from the sum of the effects of each of the components involved. There is thus much evidence of a genuine synergistic effect which, to a certain extent, was in no way

DK 156982 B

3 to foresee, and which, to a high degree, must be regarded as surprising.

The invention thus relates to a herbicidal agent, characterized in that it contains as an active ingredient a mixture of one or more compounds of the general formula //

j cx R

\ / - (V Hal (I) '

X-U N -N

wherein Hal represents chlorine or bromine, R 1 is a straight or branched alkyl group having 1-18 C atoms or phenyl, X is oxygen or sulfur and Y is sulfur, Y may also be oxygen when X is sulfur , with compounds of the general formula

CN

(H),

Hal 'Hal'

0-C-R

IN! Wherein Hal 'represents bromine or iodine and R5 is an alkyl group of 4-10 C atoms.

The elevated 15 herbicidal efficacy of the active substance mixture in addition to a mere additive effect brings significant technical advantages, since it is possible to significantly reduce consumption.

'I

DK 156982B

4 of the individual active substances per treated area unit.

Among the compounds of general formula I, the following compounds show significant increases in power in combination with compounds of general formula II: 5 O- [3-phenyl-6-chloro-pyridazinyl- (4)] - S- (n-propyl) - thiocarbonate, 0- [3-phenyl-6-chloro-pyridazinyl- (4)] - S- (n-butyl) thiocarbonate, Û- [3-phenyl-6-bromopyridazinyl- (4)] - S- (n -butyl) -thiocarbonate and 0- [3-phenyl-6-chloro-pyridazinyl- (4)] - S- (n-dodecyl) -thiocarbonate.

A particularly good effect is obtained by using the compound 0- [3-phenyl-6-chloro-pyridazinyl- (4)] - S- (n-octyl) -thiocarbonate.

Among the compounds of the general formula II, particularly good results were obtained using 4-hydroxy-3,5-diiodobenzonitrile octanoate ("oxynil octanoate") and / or 4-hydroxy-3,5-dibromobenzonitrile octanoate (" bromoxynil-octanoate ").

The compositions of the invention can be transmitted in the usual formulations, such as solutions, emulsions, dispersions, powders, pastes and granules. They are manufactured in a manner known per se, e.g. by mixing the active substances with excipients, i. liquid solvents 25 and / or solid carriers, optionally using surfactants, i. emulsifiers and / or dispersants. As solid carriers, especially natural stone flour, such as kaolin, lime, talc and chalk, and synthetic stone flour, such as high-dispersion silicas and silicates, are used. As emulsifying agent 5 is used

DK 156982 B

nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, alkyl sulfonates, aryl sulfonates, alkylaryl sulfonates. As wetting and dispersing agents, lignin sulfite bases, methyl cellulose and naoleyl methyl tauride are used.

The amount ratio of the compound of formula I contained in the mixture to the compounds of formula II may vary within certain limits, e.g. in the ratio of 10 from 1: 1.6 to 1: 0.1 by weight, with mixtures having a predominant proportion of compounds of formula I being particularly preferred.

The combination of active substances according to the invention can e.g. formulated according to the following prescription as spray powder or as emulsion concentrate: active substance according to formula I 14-50 wt.% active substance according to formula II 3-20 wt.% (calculated on phenolic equivalents) net or dispersant 5-15 wt.% 20 inert fillers or carriers up to 100% by weight.

This formulation is suspended or emulsified for use in water. It may also contain other known active substances, such as herbicides, fungicides or growth regulators. Particularly favorable is a combination of active substances from the group of phenoxycarboxylic acids, such as e.g. MCPA, CMPP, 2,4-DP and 2,4-D, respectively, salts or esters thereof, by the addition of these can also control several perennial weeds in the same workflow.

The agents of the invention can also be used to treat the plants after the end of the growing season.

6

DK 156982 B

Also, the size of the amounts of active ingredient used in combination may be varied within certain limits, depending on the composition of the combination and the species of the weed plants to be treated. As a rule 5, the active substance of formula I will be used in an amount of between 0.25 and 1.0 kg / ha and the active substance of formula II in an amount of between 0.1 and 0.4 kg / ha ha.

The compositions of the invention preferably find use in controlling weeds in cereals and maize crops, and for this purpose the active ingredient of formula I is dosed in an amount of between 0.5 and 1.0 kg / ha. and the active substance of formula II is dosed in an amount of between 0.2 and 0.4 kg / ha.

In order to determine whether a mixture has additive or synergistic effects, one usually uses the following formula r - X + Y _ L ·! L _ x Y 100 (according to L.E. Limpel, P.H. Schuldt, and D. Lamont, 1962,

Weed control by dimethyItetrachloroterephthalate alone and in certain combinations, Proc. NEWCC 16: 48-53, based on D.P. Govuing, 1960, Comments on tests of herbicide mixtures, Weeds 8: 379-391).

E = the expected herbicidal efficiency (% of weed killing) after using 25 A + B at p + q kg dosage / ha (by additive effect).

X = efficiency (%) using active substance A at p kg / ha.

Y = efficiency (%) using the active substance B at q kg / ha.

. DK 156982 B

7 When the experimentally found value is higher than the value calculated according to the formula, there is a synergism. On the other hand, when the value found is lower than the value calculated according to the formula, there is a lot of antagonism.

From Tables 1-5, it is clear that the herbicidal efficiency (% killing) when combined with the active substances I + II and I + III, respectively, in almost all cases is substantially above the expected values. (calculated) by pure additive action.

The practical benefits of synergism to the extent shown in the tables are extremely high. As is well known, the EWRC assessment schedule for the herbicidal efficiency is based on an approximately exponential function between the efficiency (% killing) and the present number size (or graduation), so that between 85 and 100% killing is subjected to a substantial -like finer modulation in the schedule than is the case with the economically uninteresting range between 0 and 85% 20 killing (see EWRC chart).

Therefore, an increase in the efficiency of the lower area has a substantially stronger significance than a corresponding ratio in the lower area. An improvement in the efficiency of e.g. 95% to 100% (+5%) corresponds to an improvement of 2 boniting degrees, whereas an increase in the efficiency e.g. from 70 ô to 80? (+ 10? □ ') corresponds to only one bonus step and, in practice, is of little importance, as both 70% and 80% killing only apply as "not sufficient". As will be seen from the example, it is especially in the range of 85% to 100% killing that synergistic effect increases can be demonstrated to an economically significant extent.

DK 156982B

8

Furthermore, from the example it will be seen that already at a dosage of 0.25 kg / ha of compound I and 0.1 kg / ha of compound II (in this case ioxynil-octanoate), the herbicidal efficiency of all tested 5 weeds is substantially over the effect of the sum of the individual components. The synergistic effect is particularly evident in this case. Thus, it is e.g. for the weed plants Galeopsis tetrahite (common male),

Lamium purpureum (row incisor) and Veronica hederifolia 10 (ivy-honors award) + 26, + 27 and + 29% respectively.

It is of great practical importance that by combining 0.25 kg / ha of Compound I with 0.2 kg / ha of Compound II (in this case, ioxynil-octanoate), it has been possible to increase the efficiency against the highly resistant weed plant Galium aparine (burdock-snare) for 98% killing, which corresponds to a very good effect according to the EWRC scheme. By combining 0.5 kg / ha of Compound I with 0.2 kg / ha of dioxin octanoate, it is possible to exterminate all weed plants, including Galium aparine (burrowing), up to 100 µg. , except for polygonum convolvulus (whisker arrow).

Compound III (bromoxynil-octanoate) bears a great resemblance to ioxynil-octanoate as far as its chemical, physical and biocidal properties are concerned. Accordingly, the compounds also exhibit the same synergistic effects as can be seen from Tables 4 and 5.

Example:

Rectangular plastic boxes (35 x 38 x 7 cm) which were planted with the various 30 weed plants were used as experimental units.

..... DK 156982B

9

The following economically significant field weeds were used for the seedlings:

Chenopodium album White flour goose foot = A

Galeopsis tetrahit Alm. male = B

5 Galium aparine Burre cords = C

Lamium purpureum Red tusk = D

Lapsana communis Haremad = E

Lithospermum arvense Ager stonefly = F

Matricaria chamomilla Odorless chamomile = G

10 Poppy rhoeas Corn - \ / almue = H

Polygonum convolvulus Snerle pilgrim = I

Stellaria media Alm. bird grass = K

Veronica hederifolia ivy honors award = L

After the weeds have reached the stage of development, 15 in which they are usually sprayed with herbicides in cereal crops (Galium aparine, for example, branched, with 3-6 spin dividing / lateral shoots, Lapsana communis in 6-8 leaf stage, Matricaria chamomilla in 8-10 leaf stage, Stellaria media already branched, with 4-6 leaf pairs per side shoot, 20 Galeopsis tetrahite with 2-3 leaf pairs, etc.), the active substances or combinations of active substances, respectively, were sprayed on the weeds in the indicated dosages. The dosage was in uniform distribution 500 l / ha.

Four weeks after spraying, the herbicidal efficacy was found. The remaining stock of weeds was harvested - each weed species and fresh weight were noted. Similarly we proceeded with the weeds in the boxes that had been exempted from spraying.

30 The residue of treated weeds was then subjected to assessment, the condition being assessed and compared to the weed population in the untreated 10

DK 156982 B

boxes to determine the herbicidal efficiency (% killing). The found values were then investigated for possible synergistic effects by means of Limpel's formula, using existing product mixtures.

The compound 0- [3-phenyl-6-chloro-pyridazinyl (4)] - 5- (n-octyl) thiocarbonate was used in the following composition: 70% active substance 7.3% alkylarylsulfonate-polyoxyethylene emulsifier mixture 22.5% solvent

The compound ioxynil-octanoate or bromoxynil-octanoate, respectively, was added in the following composition:

Mix of

Active Aromatic Substance Emulsifier Hydrocarbons

Ioxynil octanoate (equivalent to 400 g / l phenol equivalent) 47.02% 4.38% to 100%

Bromoxynil-octanoate 20 (corresponding to 400 g / l phenol equivalent) 51.08% 4.38% to 100%

The tables of kg / AS / ha of the tables refer to the relevant equivalents of free phenol for ioxynil and bromoxynil-octanoate, respectively.

11

DK 156982 B

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16 E.W.R.C. Value Chart:

Killing of the Effect of a Valuable_Crude_Preparation_ 1 100 excellent 2 97.5% very good 3 95% good 4 90% satisfactory 5 85% still sufficient 6 75 ° à not sufficient 7 65% poor 8 52.5% very poor 9 0 none

Claims (3)

1. Herbicidal agent, characterized in that it contains as active ingredients one or more compounds of the general formula K.Ri O-O-Hai (i> N 'N - N where Hal means chlorine or bromine, R 1 is a straight chain 5 or branched alkyl group having 1-18 C atoms or phenyl, X is oxygen or sulfur and Y is sulfur, Y may also be oxygen when X is sulfur in admixture with compounds of the general formula CN / VA Hal 'Hal' ° Τ1 where Hal 'means bromine or iodine and R 1 is an alkyl group 10 having 4-10 C atoms Herbicidal agent according to claim 1, characterized in that it consists of the compound 0- [3-phenyl -6-chloropyridazinyl- (4)] - S- (n-octyl) thiocarbonate in combination with the compound 4-hydroxy-3,5-diiodobenzonitrile octanoate and / or the compound 4-hydroxy-3,5-dibromobenzonitrile -octanoate DK 156982 B 3. Herbicidal agent according to claim 1 or 2, characterized in that the weight ratio of the compound 0- [3-phenyl-6-chloro-pyridazinyl- (4)] - S- (n-octyl) -thiocarbonate and the compound 4-hydroxy-3,5-diiodo-benzonitrile-5-octanoate or 4-hydroxy-3,5-dibromobenzonitrile-octanoate, respectively, is between 1: 1.6 and 1: 0.1, the amounts of hydroxybenzonitriles being given in phenolækvivalenter. A method for controlling weeds, characterized in that, after the plants are shot, the cultures are subjected to treatment with a mixture according to any one of claims 1-3, the active substance of the general formula Apply in an amount of 0.25-1 kg / ha while the active substances 4-hydroxy-3,5-diiodobenzonitrile octanoate or 4-hydroxy-3,5-dibromobonazonitrile octanoate in an amount of 0.1-0.4 kg / ha.