DD210196A5 - HERBICIDE MEDIUM - Google Patents

Abstract

The invention relates to herbicidal compositions characterized by a content of a compound of the formula I in which R =H, NH-low4, NA, K or one-half Ca, and X =OH or -NH-CH (CH'low3) -CONH-CH (CHtief3) -COOH, in combination with a compound of formula II, wherein X = CI or CHtief3 and Y = H, alkali, optionally substituted NH, denote deep4 or alkyl, and the compound of formula III or compound d.FormelIV. These show synergistic activity d.Use for anti-croaking, especially in tree or shrubby crops.

Description

The invention relates to a new combination of active substances that can be used as a herbicide in agriculture »

Well-known technical solutions

From DS-OS 2 717 440 are compounds of the general formula IO

HC Ü ^ c- °

""? - CH ₀ -CH ₀ -CH-C ^ "(I)

known in which

H = hydrogen, Mi ^, Ha, K or / 2 Ca and X = OH or -NH-CH (CH ₃ ) -COUH-CH (CE -) - COOH mean «

Also known are compounds of general formula II C1 - <OVO-CHo-C ^ (II)

Compounds of the formula II in which X is either chlorine (= compound Ha, common name: 2,4-D) or methyl (= compound lib, common name: MC? A) are already known as growth regulators. Silks are described, for example, in "Pesticide Manual", edited by C. H * Worthing (1979), page 145 (Ha) and page 326 (Hb), respectively. They are preferred as alkali (sodium, potassium) or STagne

iaFER1983 * O7O2O

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sodium or amine salts, ζ. T. also used as esters (Y = (C.-C,) - alkyl), Zo Β «as isopropyl or isobutyl ester.

Compounds of the formula III (common name Diuron)

and the formula IY (common name: Simazine)

Cl

-L

^υ 2 ^Λ 5

are already known as herbicides · »

Both are e.g. described in "Pesticide Manual", edited by C.R. Worthing (1979), page 224 (HI) and page 474 (IY), respectively.

Compounds of the formula I control mon- and perennial weeds of various botanical families in dosages of preferably 0.5 to 1.5 kg / ha of active ingredient, whereby the after-effect may be considerable in the case of perennial species Effect not always satisfactory. Although one obtains a relatively fast, short-term "burning-off effect ¹¹ on the green parts of plants (stems and leaves), however, often · no long-lasting lasting effect«

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Compounds of formula II can be used to control numerous broadleaf weed species, both annual and perennial. They are often used in cereal crops at doses below 1 kg / ha of active ingredient. Another focus of application is the use in perennial crops, especially tree or shrubby crops such as vines, fruit or citrus trees, various tropical plantation crops such as rubber, coffee, cocoa and the like, or in perennial crops such as sugar cane or banana. The dosages are here when used alone usually about 1 kg / ha, z. T. over 2 kg / ha active ingredient = In these cultures, because of the lower volatility -and the consequent lower risk of possible damage to crops preferably the salts of the compounds of formula II are used, the corresponding esters, however, only to a small extent. The above-mentioned active compounds of the formula II are taken up via the leaf and transported in the plant both in the direction of the root and in the direction of the shoot tip.

The compounds of formulas III and IV are also used in the above-mentioned permanent crops, depending on the culture, in a wide Dcsierungsbereich, which may be between 0.5 and 5 kg / ha of active substance. Although they have a certain effect on the existing ünkrautflora, but above all by their lasting effect in the soil prevent the feeder of weeds from seeds, while they have on the re-expulsion of surviving subterranean parts of plants ('roots, tubers, rhizomes) only a small effect'

It has also been disclosed that combinations of compounds of the formula I with compounds of the formulas III or IV, and on the other hand combinations of compounds

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of the formula I with compounds of the formula II have synergistic herbicidal effects (compare z "B-DS-OS 28 39 087 and DS-OS 28 56 260).

Object of the invention

It is an object of the invention to bring about a further increase in activity in herbicidal compositions.

Essence of the invention

The invention has for its object to provide new herbicidal compositions based on the combination of already known means and to increase the spectrum of action »

It has been found that both combinations of the known mixtures of compounds of the formulas I and II with compounds of the formulas III or IV, as well as combinations of compounds of the formula II with the known mixtures of compounds of the formulas I and III or I and IV surprising show additional synergistic herbicidal effects.

The present invention relates to herbicidal compositions which are characterized by a content of

(A) a compound of the formula I,

'- OH, - CH, - CH - C (1)

<- C. ι »ν.

RO '' ^ X

ϊΓΕί

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R = hydrogen, ^ H ₇ , Ha, K or 1/2 Ca, and A = GH or -JTH-CH (CH ₃ ) -COlTH-CH (CH ₃ ) -COGH, in combination with

(3) a compound of formula II,

_ 0

Oi

X = Cl or CH ₃ , and

'£ = hydrogen, alkali, ITH ^, UH ₃ -CH ₃ , ΈΈ. ^ (C _p E-) ₂ , HH ₂ (CH ₃ ) ₂ , UH ₃ -C ₂ H ₄ . OH, '! TH ₂ (C ₂ H ₄ .OH) ₂ , IiH (C ₂ I ₄ OH) ₃ or (C 1 -C ₄ ) -alkyl,

(C) the compound of formula III

⁰ / \ U ^ -

Cl ((Y) ITH-C- IT .. (III)

Cl or the compound of formula IV

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(IV)

NH-C ₂ Hg

The compound of the formula I where R = hydrogen and Z = -OH has also become known under the name phosphinotricin ·

Particularly preferred is the compound of formula I with R = Wd _± and Σ = -OH (= compound Ia, the ammonium salt of phosphinothricin). It is 2 »B. described in DE-OS 27 17 and can be used both as a racemate, and as an optically active L-form» Further preferred are compounds of formula I with X = -UH-CH (CHo) - - COIIH-CH (CH ₃ ) -COOH, as described, for. As described in DS-OS 28 48 224 are »

The surprising additional synergism of triple combinations according to the invention can be u. also by using the usual S * Colby formulas in connection with the discovery of synergism, by comparing the experimentally found effect (in % damage) of a triple combination with the calculable effect addition of the individual components. If the latter is less than the former, then synergism is indicated «

The weight ratios of the components (I): (II): (III) or (IV) in the combinations according to the invention can vary within wide limits, but they are preferably in the range of 1: (1 to 4): (0.5 to 6), especially in the range of

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1.: (1.5 to 2.5): (1 to 4).

The thirst combinations according to the invention can be used particularly advantageously in order to sustainably combat an existing broad spectrum of weeds of annual and perennial species-and at the same time to keep the treated surfaces free of later-accumulating weeds (long-term lasting effect). Depending on the dosage and depending on the proportion of the individual components, they can be used in tree or shrub-like cultures of the temperate and tropical zones, eg. 3. in raisins, citrus, apple, pear, plum, cherry, berry bushes, rubber, palm oil, coffee or cocoa; In addition, a use is also possible in perennial crops such as banana or Zuckerrohra

The combinations according to the invention can be used either as tank mixes in which the individually formulated active ingredient components are mixed together only immediately prior to application, or as ready mixes. As ready mixes they can be in the form of emulsifiable concentrates or. Preferred z. 3. be formulated in the form of wettable powders and then optionally contain "the usual formulation auxiliaries, such as. 3. ITetz-, adhesives, emulsifiers or dispersants, solid inert substances, grinding aids and solvents.

In the active ingredient combinations according to the invention, their concentrations in the formulations to be used may vary. They are generally from 2 to 95% by weight, preferably from 5 to 30% by weight.

The invention therefore also provides herbicidal compositions having a content of from 2 to 95% by weight, preferably from 5 to 80% by weight, of an active substance combination of compounds

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of formulas I + II + III or "IT as well as customary formulators"

In the wettable powders, the total active ingredient concentration (1 + II + III or "IT") varies in the range from about 10 to 80 Ge / / -%, the remainder to 100% by weight consists of customary formulation additives.

For use, the active compound concentrates according to the invention are optionally diluted in a customary manner, for. B. wettable powders and Smulsionskonzentrate. by means of water. With the external conditions, such as temperature, humidity and. a. It may also vary within wide limits and is generally between 0.5 and 20 kg / ha drug-three combination, preferably 1 to 10 kg / ha.

A. Formulation Examples

Wettable powders (wettable powders) with contents of active ingredient triple combinations according to the invention are preferably prepared in such a way that the sparingly soluble in water active ingredients, such as. B. the Terbindung III (= diuron) in finely ground and formulated as a wettable form form with the water-soluble active ingredients, such as the compound Ia (= ammonium phosphinothricin) and the sodium or Dime thy laminsalz the Terbindung Hb (= MCPA) or Ha (= 2,4-D) and the required final and dispersants under exclusion of moisture intensively mixed, expediently in a hammer mill · This highly intensive homogenization of the water-soluble active ingredients with the sparingly soluble in water compounds and the surface-active compounds, so that optimum wettability and suspensibility in the resulting wettable powders can be achieved.

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Ώ.βΏ.0

In order to increase the flowability of the wettable powders, these can advantageously contain, as carriers, fine synthetic silica, kieselguhr, clay or bentonite powder. Suitable dispersants are sodium dinaphthylmethanedisulfonate, lignin sulfonates, condensation products of alkylnaphthalenesulfonic acids with cresols, 2Ta trium- sulfite and formaldehyde, oleoyl-N-methyltauride, polyvinyl alcohols or polyvinylpyrrolidones, as wetting agents dibutylnaphthalenesulfurate sodium, alkylnaphthalenesulfonate sodium, alkyl sulfates, preferably z. B. Alkali and ammonium salts of sulfuric acid monoesters of aliphatic (C ₁ PC ^) - Alkoholpolyglykoläthern with 2-6 Athylenoxidein-. are called (^ wetting agent FES) «

Liquid or low-melting surface-active substances are expediently first absorbed on adsorptive silica to form pulverulent dry concentrates and admixed with the wettable powder in powder form. Suitable defoamers, if necessary, sodium or potassium salts of. Fatty acids and silicones »

example 1

Preparation of a wettable powder with 53.2% by weight of active substance triad combination, containing 10 % by weight of compound Ia + 16.6% C-ewo-% compound IIb sodium -f 26.6% by weight of compound III »

1.1 Formulation of a Spri tppulvers with 80 G ew .-% compound III;

A mixture of 80.0 wt .-% compound III

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12.0% by weight of synthetic silicic acid

6.0% by weight of sodium dinaphthylmethanedisulfonate

1.8% by weight of alkylnaphthalenesulfonic acids! sodium

0.2 C ewo-% oleoyl-N-methyltauride sodium

is ground to a fine powder with particle sizes less than 44 microns on a high speed pin mill.

1.2 Formulation of a Wetting Agent Adsorption Concentrate of Paste-Softening, Water-Containing (C ₀ -C,) Fatty Acid

ic. IO

Alcohol polyglycol ether sulfate sodium (= PES) and adsorbent synthetic silica: ·

In an intensive mixer, which contains a stirring shaft with revolving blades, intensive mixing is carried out at a stirrer speed of about 150 rpm · 60 parts by weight of a 70% strength by weight PES paste and 40 parts by weight colloidal synthetic silicic acid. to obtain a powdery adsorbate containing 42% by weight of T PES active substance.

1.3 ' Preparation of the wettable powder with 53 ^ 2% by weight of the active substance:

Be in an intensive mixer

33.25 parts by weight of Compound Ill-Spritspulver (80%),

prepared according to 1 »1, with 26.6 parts by weight of compound III fraction

-O

10.00 parts by weight of compound Ia

16.60 parts by weight of compound IIb-Efatriuinsalz

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23.30 parts by weight of wetting agent? S5 adsorbate, prepared

to 1.2, with 10 parts by weight FES share

5.15 parts by weight of sodium dinaphthylmethanedisulfonate. 2.00 parts by weight of dibutylnaphthalenesulfonic acid sodium 1.00 parts by weight of soap flakes 8.20 parts by weight of synthetic silicic acid

mixed under vacuum and then ground on a cross-hatch mill to give a pulverulent product.

Example 2

Preparation of a wettable powder with 40% active ingredient Gewo- triple combination containing 10 wt -.% Of compound Ia + 20% of compound Gewo- 'Ila sodium 4- 10 wt ° -% Compound II I.

Analogously to Example 1 are in an intensive mixer

12.5 parts by weight of compound ITI-Spritzpulver (SO%), prepared according to Ex. 1.1 ", with 10 parts by weight Verbdgo III content 10.0 parts by weight of compound la 20.0 parts by weight of compound Ila sodium salt 2358 parts by weight Wetting agent PES adsorbate, mfd.

according to example 1.2, with 10 parts by weight PES content

5.7 parts by weight of sodium dinaphthylmethanedisulfonate 3.0 parts by weight of sodium dibutylnaphthalenesulfonate 2.0 parts by weight of soap flakes 13) 0 parts by weight of synthetic silicic acid

mixed with exclusion of moisture and then on a beater mill to a finely powdered product se-

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grind.

B. Biological Examples

In the following biological examples I to IY, a distinction is made in the tested active substance combinations between the calculated and the found efficiency on the named weeds. "The calculation of the efficiency takes place according to the formulas of S * R Colby: Calculating synergistic and antagonistic responses of 'herbicidal combinations (Weeds Ύ3, p.20-22 , 1967) from the effects of the combination components in their single use applications The formula (1) for the combination of 2 active substances is:

100

X = % damage by herbicide A at χ kg / ha

Application rate, Y = % damage by herbicide 3 at y kg / ha

Application rate, ) E = the expected damage from the herbicides

A + Bbeix + y kg / ha application rate

means "

For the combination of 3 active ingredients, the formula (2) is given for the calculation of the efficiency in the same document:

(ΣΥ + XZ + YZ) _TV7 E = X ₊ Y ₊ Z- 100 + -, TOJ ⁽²⁾

Z = .% Damage by herbicide C at ζ kg / ha

Application rate means and

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X and Y have the same meanings as in formula (1) »

Is the actual, d. H. the experimentally determined damage is greater than calculated, the effect of the combination is more than additive, do ho there is a synergistic effect. »This proof is provided in the following biological examples of the combinations according to the invention, wherein in the combination treatments according to the invention in brackets also the effects calculated from the above formulas are given, while behind the actual effect against the respective weeds is listed.

In the biological examples I to IV not only the effect of the combination I + II + IH or IY is compared with that of the 3 individual active ingredients, but also with the effect of the already known combinations 1 -r ΙΓ and 1 -f III or IY , These application examples are field trials carried out under different climatic conditions. The results are summarized in the 'I to IY labels. All experiments were carried out in parcels of 10 to 20 m in area.

Example I

In a trial under tropical conditions on the weed MIkania cordata in a rubber culture, the monocompounds Ia, Ha and III were tested side by side and the known combination Ia + III. Combinations of these three compounds according to the invention resulted in a considerable increase in performance compared to the individual products, as compared to the known combination, which clearly exceeds the extent to be expected. The effect of the triple combinations is therefore considered to be synergistic

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to call. The result is summarized in Table I below. «

Table I

Combating Mikania cordata in a Kautschukkultu2

Treatment with active ingredient

Drug dose kg / ha

Effect (% damage) on Mikania cordata (field trial) 5 weeks after treatment

calculated

found

a) Si nz e Iwi k - la 0.4 matter Ha 0.8 connection Ha 0.4 connection III 0.4 connection b) known combination connection nation

Compounds Ta + III

c) combinations according to the invention

Verb.Ia + IIa + III Verb.Ia + IIa + III

0.4 + 0.4

0.4 + 0.4 + 0.4 0.4 + 0.8 + 0.4

50 60 40 10

70

90 1: 1: 1 96 1: 2: 1

calculated from the effect of the individual products calculated from the effect of the known combination and Ha

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Example ± I

From a series of experiments in grapevine and apple crops, which was created according to a uniform design plan, Table II shows the results of three hard-to-control weeds; Above all, the compound Hb with the known combinations Ia + III and Ia +) IV have been tested side by side, and the combinations Ia + IIo-III and Ia + Hb + IV according to the invention. The said triple combinations were significantly better in their herbicidal action would have been expected according to the calculations of the Colby formula au, the known combinations were each considered as uniform treatments, which means a synergistic increase in efficiency. The result is summarized in the following Table II give ge again β

O CVI

Table II

Control of difficult-to-control weeds in grapevine or apple crops

Treatment with active ingredient

Drug dose effect (% damage) on the following kg / ha weeds (field test)

Plantago Girsium arvense Convolvulus lanceolata in vines in grapevine cultivar in apple culture (6 weeks grape vine (4 weeks after treatment (6 weeks of treatment) after Be

plot

Compound Hb Compounds Ia + III Compounds Ia + IV

Kombinatjionan invention

Compounds Ia + IIb + III Compounds Ia + IIb + IV

0.5 + 2.0 0.5 + 2.0

0.5 + 1.0 + 2.0 0.5 + 1.0 + 2.0

50 98 60 5) 55 (80) (77,

75 30 30

(77.5) 92 (77.5) 90

80 50 50

(90) (90)

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Example III

In a further experiment on the weed Rumex acetosa in a cherry culture, the known combination Ia + Hb was tested in a mixture with compound III. It showed in the triple combination according to the invention an increase in activity, which significantly exceeds the expected extent, do h ", it is a synergistic effect before. The result is summarized in Table III below.

Table III

Control of Rumex acetosa in a cherry culture

Treatment with active ingredient

Active ingredient: dose

kg / ha

Effect {% damage) on Rumex acetosa (field trial) 6 weeks after treatment. calculated

Compounds Ia + Hb

Compound III

Compounds Ta + Hb + III

0.5 + 1.25

2.0 0.5 + 1.25 + 2.0

(84)

found

80 20

95

1: 2.5

Beisniel IV

In a manure plantation of oil palms, in which the rows of trees very strongly with Mikania cordata, Pueraria sp. and various grasses, especially Paspalum con.jugatum were infested, the preparations Ia, Ha and III alone, also tested in the known combinations Ia + Ha and Ia + III and in tri-combinations according to the invention. After 5 and 10 weeks, the weed effect as well as the crop damage were scored. In the effect on Paspalum showed

!8th

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itself that the compound Ia with 0.4 kg / ha of active ingredient already completely sufficient to achieve a i00% effect on the existing weed plants. However, every 10 weeks, numerous paspalum plants have re-accumulated from seeds present in the soil, since Compound Ia has no effect above the soil. On the other hand, in Plants treated with Compound III, the plants emerging from seeds were destroyed while On the other hand, the plots treated with combinations according to the invention were also free of old, ie present at the time of administration, as well as freshly germinated plants. All treatments with the compounds Ia or Ha had Pueraria and Mikania However, the known combinations were no longer sufficiently effective at this point in time * The triple combinations according to the invention, however, showed that especially the aftereffect was particularly good , an e ffekt, which was not to be expected so clearly and therefore can be described as synergistic. Although good aftereffect was also possible in the known combination Ia + Ha with 0.4 + 1.2 kg / ha; however, this was apparent. Young trees that had come into contact with the spray mixture on the bark or on parts of the palm fronds had marked growth damage (leaf distortions). By contrast, in the combination according to the invention in which the proportion of substance Ha was markedly reduced, these leaf damage could no longer be observed. The dosage of the combination could even be reduced by a quarter in order to further reduce the risk of leaf damage without significantly reducing the weed effect, in particular the after-effects 10 weeks after treatment (see Table IV, last line). It is possible by threefold invention

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Combinations thus achieve that the use of herbicides is safer and that at the same time achieves a significantly increased and thus sufficiently long aftereffect; under practical conditions this means that the time for the next herbicide treatment can be postponed; thereby u «a. also labor and preparation costs saved. The result is summarized in the following Table IY.

C \ I

O (X)

C-- "-s C ^

Table IV

Weed control in an oil palm seedling culture

Treatment with active ingredient

V / irkstoff- effect (% damage) to the following dose weeds kg / ha (field test) after 5 weeks Pueraria ap "Mikania sp.

^ ' ^iKO a) Single Compounds Compound la Compound Ha Compound Ha Compound III

b) known combinations on compounds Ia + Ha compounds Ia + IIa compounds Ia + IH

c) Compounds Compounds Ia + IIa + IIi Compounds Ia + IIa + III

0.4 1.2

0.6 0.4

0.4 + 1.2 0.4 + 0.6 0.4 + 0.4

0.4 + 0.6 + 0.4 0.3 + 0.45 + 0.3 95 90 10

99 90 90

(98) 99

80

95

80

99 95 90

(96) 96

after 10 weeks

Pura-Mikarla 8p »nia aρ

Leafy on d. Oil palm culture after 5 weeks

40

30 0

70 45

50

70

40

80

65 60

85 (58) 95 (73) -1: 1, 80 50 -5ΙΓ1

Claims (6)

2βο1.1933 AP A 01 Ν / 243 ο09 βΐ 372 12 Claims 1. Herbicides, dTorch indicates a content (A) a compound of formula i, 0 h, c ^ I! RO - CH ₀ - CE "- CH - C 2 * n ₂ O X (D wherein R = hydrogen, W ± _A , Na, K or ½ Ca, and X = OH or -NH-CH (CH ₃ ) -CONE-CH (CH ₃ ) -COOK, in combination with 'B) a compound of the formula II, Cl- wherein X = Cl or CH ₃ , and Y = hydrogen, alkali, NH ,,, NH ₃ -CH ₃ , 2IE ₂ (CpE, -) _? . NH ₂ (CH ₃ ) ₂ , IJH ₃ -CpH ₄ OOH, NH ₂ (C ₂ H ₄ , OH) ρ, NH (C ₂ H ,,. OH). or (C, -C) -alkyl, and (C) the compound of formula III O
ii OB ₃ (in: 2β.1ο1983 AP A 01 Ν / 243 609 61 372 12 or the compound of the formula IV Cl AA _n , c " ⁽ⁱⁿ η χι λτχ? 2. A herbicidal composition according to item 1, characterized in that the mixing ratio of the components of the formulas I: Il ϊ III. or = IV = 1: (1 to 4): (0.5 to 6) Herbicidal agent according to item 1, characterized in that the mixing ratio of the components of the formulas I: II: III or IV = 1: (1.5 to 2.5): (1 to 4) « 4 «Herbicidal agent according to items 1 to 3, characterized by a content of 2 to 95% by weight of a combination of active ingredients according to items 1 to 3s, wherein the remainder to 100 wt .-% consists of customary formulation auxiliaries. 5 · Use of the agents according to items 1 to 4 _}, characterized in that they are used for weed control, especially in tree, shrub or perennial permanent crops. 6. A method for controlling weeds, characterized in that applying to the affected areas of them drug combinations according to point 1 to 4'in amounts of 0.5 to 20 kg of active ingredient combination per hectare · »