CS220778B2 - Herbicide means - Google Patents

Abstract

The invention relates to a new synergistic herbicidal composition comprising one or more active compounds of the formula <IMAGE> in which Z is chlorine or bromine, R is straight-chain or branched alkyl group with 1 to 18 carbon atoms or phenyl, X is oxygen or sulphur and Y is sulphur and if X is sulphur, Y also may be oxygen, and of one or more compounds of the formula <IMAGE> in which Z' is bromine or iodine and R' is alkyl with 4 to 10 carbon atoms, the combination having a high selective and synergistic action when used for combating weeds, especially in grain cultures and maize cultures, and to a process for combating weeds by treatment with the said composition.

Description

Hal is chlorine or bromine,

R 1 represents a straight or branched (C 1 -C 18) alkyl group or a phenyl group,

X is oxygen or sulfur; and

Y is a sulfur atom, and when X is a sulfur atom, Y may also be oxygen, have herbicidal properties and are well tolerated by numerous crop plants, including cereal crops.

In particular, O- [3-phenyl-6-chloropyridazin-4-yl] -S- (n-octyl) thlokarbonate ("Pyridate") is used as an agent for weed control in cereal and maize cultures (Diskus et al., Proc. 9th Bnitish Weed Control Conf., 1976, vol. 2, 717) and has a broad spectrum of weed control.

However, in practical application on field plots, it has been shown that some weed species, such as Stellaria media and Polygonum conviolvulus, can only be combated with relatively high doses of the active ingredient, such as poppies (Papaver rhoeas), cannot be combated at all. This is particularly the case if weeds are at an advanced stage of development.

It is further known that compounds from the 3,5-dihalogen-4-hydroxybenzonitrile series have good properties as contact herbicides (Nature, London, 1963, Vol. 200, p. 28). In particular, octyl ester of α-hydroxy-N-diiodobenzonitrile (2077) 8u ("thioxynil-octanioate") and 4-hydroxy-3,5-dibromobenaonitrile ("Bromoxyml-octanoate") are used against annual, broadleaf weeds in post-emergence application (H. Martin) , Ch. R. Worthing, "Pesticide Manual" 5th edition 1977, pp. 293 and 54). On the other hand, a number of weeds have become more resistant with increasing time, so that relatively high application rates are required to control them. These weeds include Galium aparine and Galeopsis tetrahit (Kurth H: 'Chemiische Unkťautbekampfung', Fischer Verlag Jena, 1975, p. 170).

It has now been found that mixtures of active substances from the group of phenylpyridazines of the general formula I, in particular O- [3-phenyl-6-chloropyridazin-4-yl] -S- (n-octyl) thiocarbonate ("Pyridate") with active substances of the series 3,5-dihalo-s-hydroxybenzonitrile, particularly 4-hydroxy {^. ^^ _i x3, IJJ ^^ ^ C ^] ^ (^ i ^^ nzoniii] ^ o ^ kťanoátem ( "Ioxyniloctanloate" ) and 4-hydroxy-3,5-dibromobenzonitrile calcanoate ('Brornoxyiiiloctanoate') provide a degree of herbicidal activity which is significantly higher than that which would be expected by the mere sum of the effects of the two components, thus a true synergistic effect , which on this scale must be regarded as unpredictable and explicitly surprising.

Accordingly, the present invention relates to a herbicidal composition comprising, as active ingredient, 14 to 50% by weight of at least one compound of the formula I

Hal is chlorine or bromine,

R 1 represents a straight or branched (C 1 -C 18) alkyl or phenyl group;

X is oxygen or sulfur; and

Y represents a sulfur atom, and when X represents a sulfur atom, Y may also be oxygen, together with 3 to 20% by weight of the compounds of formula II

O-C-R?

• II

O (li) in which

Hal represents a bromine or iodine atom and

R 2 is a C 4 -C 10 alkyl group, the amount of compounds of formula II being given in phenol equivalents.

This increased herbicidal degree of action of the active compound mixture, which greatly exceeds the summation effect alone, achieves considerable technical advantages, since it makes it possible to significantly reduce the application rate of the individual components on the treatment area.

Among the compounds of the formula I, in combination with the compounds of the formula II, the following compounds offer a marked increase in action:

O- [3-phenyl-6-chloropyridazin-4-yl] -S- (n-propyl) thiocarbonate,

O- [3-phenyl-6-chloropyridazin-4-yl] -5- (n-butyl) thiocarbonate,

O- [3-phenyl-6-bromopyridazin-4-yl] -5- (n-butyl) thiocarbonate; and

O- [3-phenyl-6-chloropyridazin-4-yl] -5- (n-dodecyl) thiocarbonate.

A particularly active compound of the compounds of formula I is O- [3-phenyl-6-chloropyridazin-4-yl] -5- (n-octyl) thiocarbonate ("Pyridate").

Of the compounds of formula II, good results are obtained, in particular with 4-hydroxy-3,5-diiodobenzomethyltrioctanoate ("Ioxynil-octanoate") and / or with 4-hydroxy-3,5-dibromobenzonium octanoate ("Bromoxinyl-octanoate") .

The combinations according to the invention can be converted into conventional compositions such as solutions, emulsions, dispersions, powders, pastes and granules. These compositions are prepared in a manner known per se, for example by mixing the active compounds with fillers, i.e. liquid solvents and / or solid carriers, optionally using surfactants, i.e. emulsifiers and / or dispersants.

Jakl solid carriers' substances are essentially: natural minerals, such as kaolins, clays, talc and chalk, and synthetic rock flours, such as highly-dispersed silicic acid and silicates: · as emulsifiers ^and Tory; nonionic and anionic emulsifiers such as polyoxyethylene fatty acid esters, fatty alcohol polyoxyethylene ethers, alkylsulfonates, arylsulfonates and alkyls, arylsulfonates; as wetting and dispersing agents there are suitable: for ^dp and sulphite liquors ^{d y y} meth lcelulóza latitude and sodium oleyl methyl tauride.

The ratio of the compound of formula I to the compounds of formula II in the mixture (phenol equivalent) may vary within a certain range, for example from 1: 1.6 to 1: 0.1, mixtures where the proportion of the compounds of formula I predominates are particularly preferred.

Quantity. compounds of formula ¹¹ with ^{UV, and} di in the phenol equivalents, given that the compounds will hydrolyze more readily to ioxynil or bromoxynil having one phenolic hydroxyl group and is often considered as a private účrnné l ^{y and} TK.

Eno ioxynn i.e. ⁴⁰⁰ g / eq LTIR phenol from ^p ov ^{IDA 536} g / liter Iox niloktanoátu or ^y, whereas the specitická thereby weight ^1.14 kg / L to ^47.02% by weight.

Bromoxynil i.e. 400 g / liter phenol-ek vwatentu by ^p s ^d and ^{582.16 g /} / liter of bromoxynil. No · ^d ^ vzMe em whereas specific. the weight is 1,139 kg / ζ ^51,08 % taotoostrnbo.

The active compound combination according to the invention can be formulated, for example, according to the following formulation as a wettable powder or as an emulsion concentrate:

účrnná ^substances of formula ¹ and ^{14 and 50% by} weight ^for čm.n ^{and fabrics} and patterns ^{11 3} and ^20% by weight (based on phenol elkvivalent) · wetting or dispersing · ^ Tor 5 and ^15% by weight of inert filler or carrier ^{e la} t ^ky: l to ^00%

These compositions are suspended or, if desired, dissolved in water for application. The compositions may also contain other known active ingredients, such as herbicides, fungicides or plant growth regulators. Particularly favorable ^and the combination of active ^t where ⁱ la from Group fenioxykarboxylových acids such as MCPA, CMPP, 2,4-DP and 2,4-D, or salts or esters thereof, relative to the knapsack that can be combated by using the ^t and ^Ke is the chaff vtaetaté ^d nom pracovmm step.

The compositions of the invention are used postemergence.

^T and ^to the color combination of ^the aplltované mniožsM active tek ^la may vary within the range of urate. · The amount depends on the composition of the active kombmace ^la te ^to a kind of whisper. Usually the active substance of the formula · ¹ is used in an amount of from ^0.25 to ^{1.0 kg /} / hectare and ^teaches nn ^and dad of 'Formula ¹¹ in only the ^{I and} V mnloížství ^{.1 to 0.4 kg /} ha.

Particularly preferred is the application of the compositions according to the invention in crops of cereals and maize, whereby the active compound of formula ¹ in .množství ^{0.5 and 1.0 kg / h} and · ^s and ^{of the} active ^ingredient of ^the formula ¹¹ in Fifejdy City Hospital ^0.2 and ^{f 0.4 kg / h} a.

In order to determine whether a mixture · has cumulative or syneegic effects, it is usually based on the following formula:

[Limpel, L.E., P.H. Schuldt, D. Lamont, 1962, Weed control by dimethyltetrachlorloterephtalate alone and in certain combinations, Why. NEWCC 16: 48-53, based on Gotving, D., P. 1960, Comments on tests of herbicide mixtures, Weeds, 8: 379-391).

E = (when additive action) expected degree herbicidmho ^the implication (% destruction of weeds) after using A + B using p + q ^{kg /} · ^

X - degree ^of účmku in% using lat ^of active ^{s to} Y and the quantity ^pk g / ^ha,

Y - degree ^{of CIN to} UV ^{at PPLICATION% of the} active compound B ^s in an amount ^{of q kg /} ha.

If the experimentally found value for E is higher than the value calculated by the above formula, then synergism occurs when ^at this hotoota MŽ ^ ^p and ^k to ^{cMzí-antagonism.}

From the results obtained by ^{line examples} Uve ^d enýc ^h taboo ^weeps CH ^{1-5 clearly} shows that all téměiř. ^{p at} pH and ^d all the herbictarn stu ^p e ^{n u} act ^to u (% exterminate weeds) · kombmace účrnných ^{l ATE 1} + ^{I1 or} I + III considerably higher than očbkávan ^E (in ^YP what ^t ENE) Ho-of unit in ^at net cumulative effect.

The practical use of synergism to the extent outlined here is extremely high. As is known, based on the evaluation grades herbmtaního ^EFFECTIVE n ^k u by ^{E. W.} RC sctómatu of approximately exponential function between STUP UC-Inca (% v ^YH ubem weeds) and the respective číselnbu value (or rating), so that in a practical range ^and between ⁸⁵ and ^100% exterminate murmur is · evaluation performed substantially differentiated than economically uninteresting ^{é í} m ranges between ⁰ and 85% ^y killing (see scheme EWRC evaluation).

The degree of action is in the upper range ^T in a substantially ^{trough width} významěj not ^from him at al · range. Improvement efficacies on ^p nklad from ⁹⁵ to ^100% (+ 5%) odpovtaá improvement of two numbers in ^evaluation, whereas, growth ^{of p} Osuna them účteL napříktad · ^ from 70% to 80% (+ 10%) corresponds to only one number · In the evaluation and, moreover, is of little significance (both 70% and 80% of eradication should be considered insufficient).

However, as can be seen from the example, especially in the range between 85% and 100% by weed control, a synergistic increase in effect can be found in all cases on an economically significant scale.

The example further shows that already with 0.25 kg of compound of formula I (Pyridate) per ha and 0.1 kg of compound of formula II (Ioxynil-octanoate) per ha, the degree of herbicidal activity is significantly higher than the sum of the effects individual components. The synergistic effect in this case is particularly pronounced, and for example, it is + 26, + 27 and + 29 percent for weeds of Galeopsis tetrahit, Lamium purpureum and Veronica hederifolia.

In combination with 0.25 kg of compound of formula I per ha with 0.2 - kg of compound of formula II per 1 ha, a shift of the degree of action against 98% extinction of Galium aparine is very practical, which corresponds to a very good effect EWRC 'evaluation For a combination of 0.5 kg of a compound of formula I per ha with 0.2 kg of a compound of formula II per ha, all weed species, in particular also Galium aparine, are killed at 100%, with the exception of cotton. .

Compound III (Bromoxyniiloctanoate) is very similar in its chemical, physical and biocidal properties to Compound II (Ioxynil-octanoate). Correspondingly, synergistic effects occur to a similar extent, as can be seen in Tables 4 and 5.

Example

Rectangular plastic containers (35 X 38 X 7 centimeters J) in which the weeds were planted were used as test units. The following, mostly economically important weed species were used in the experiments:

white goosefoot (Chenopodium album) == A cannabis (Galeopsis tetrahit) = B bedstraw (Galium aparine) = C deadnet (Lamium purpureum) = D common cabbage (Lapsana communis) == E common squirrel (Lithospermum arvense) == F chamomile '(Matricaria chamomilla) = G Poppy (Papaver rhoeas) = H cotton (Polygonum convolvulus) - I Chickweed (Stellaria media) = K Speedwell (Veronica hederifoliaj = L

When the weeds reach that stage of development in which postemergence herbicide treatment (Galium aparine) is usually carried out in cereal crops, for example, branched with 3 to 6 whorls (side shoots), Lapsana communis at 6 to 8 leaves, Matricaria chamomilla at stages 8 to 6 10 leaves, Stellaria media already branched, with 4 to 6 pairs of leaves on 1 side shoots, Galeopsis tetrahit with 2 to 3 pairs of leaves already developed, etc., spraying the active compounds or combinations of active compounds at the weed doses indicated. The amount of spray suspension is uniformly 500 liters per ha.

weeks after spraying, the herbicidal effect was determined. The remainder of the weeds are harvested, separately by species, and their fresh weight is determined. The same procedure applies to weeds which remain on the untreated areas of the comparative test vessels.

The weed remainder is compared to weeds on untreated areas, and in this way the appropriate degree of herbicidal effect (% weed control) is determined. These values are then examined in the case of the combination formulation using the Limpel formula and a possible synergistic effect is determined.

The compound "Pyridate" was used in the following composition:

70.0% active substance,

7.5% emulsifier based on a mixture of alkylarylsulphonate and polyoxyethylene,

22.5% solvent.

The compounds Ioxyniloctanoate or Bromoxynil-oecanoate were used in the form of the following. products:

active substance emulsifier mixture of aromatic hydrocarbons

Ioxyniloctaooate 47.02% 4.38% (equivalent to 400 grams per liter phenol equivalent)

Bromoxynil-octanoate 51.08% 4.38% (equivalent to 400 grams per liter phenol equivalent) up to 100% to 100%

The data on kg of active substance per ha in the tables in the case of loxynil or Bnomoxyniil ioctanioate, respectively, refer to the corresponding free phenol equivalents.

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Claims (2)

OBJECT OF THE INVENTION Herbicidal composition, characterized in that, as active ingredient, 14 to 50% by weight of at least one compound of the formula I also contains oxygen, in admixture with 3 to 20% by weight of compounds of the formula II, in which: Hal is chlorine or bromine, R 1 represents a straight or branched (C 1 -C 18) alkyl group or a phenyl group, X is oxygen or sulfur; and Y is a sulfur atom, wherein when X is a sulfur atom, Y may be in which Hal is bromine or iodine and R 2 is a C 4 -C 10 alkyl group, the amount of compounds of formula II being given in phenol equivalents. 2. A composition according to claim 1 comprising O- [3-phenyl-6-chloropyridazin-4-yl] -S- (n-octylthuccinate) in combination with 4-hydroxy-3,5-diiodobenzoniiril octanoate. or / and with 4-hydroxy-3,5-dibenzobenzonitrile octane.