NZ202035A

NZ202035A - Synergistic herbicidal mixture

Info

Publication number: NZ202035A
Application number: NZ202035A
Authority: NZ
Inventors: P Langeluddeke; K Albrecht; R Heinrich
Original assignee: Hoechst Ag
Priority date: 1981-10-01
Filing date: 1982-09-29
Publication date: 1985-02-28
Also published as: DD210196A5; AU8890682A; ZA827171B; GR77663B; EP0076470A1; JPS5867609A; DE3139060A1; OA07221A; DK434582A; CA1188533A; BR8205721A; PH18242A; IL66874A0; KR840001242A; PT75632A

Description

<div class="application article clearfix" id="description"> New Zealand Paient Spedficaiion for Paient Number £02035 20203 m i Priority Dst®{s): . ,L'.!?< <?! 3Q Q ■K'rL Comp5«t« Specification Filed; ... i»» Rq/M3^|^ 2 8 FEB 1985 Puh-Sso&tioft .»• ■ ■ - • * ■ »■■■•■•• ■ P.O. Jotrrr.sS, fio: ...... J ,i~l»• ■ • ■ NEW ZEALAND N.Z. No. Patents Act 1953 COMPLETE SPECIFICATION "HERBICIDAL AGENTS" r 29 '.•V'N stP\9» a»iL iw_ r,P J*/<f We, HOECHST AKTIENGESELLSCHAFT, a corporation organized under the laws of the Federal Republic of Germany, c£ D-6230 FrankfurtXMain 80, Federal Republic of Germany, do hereby declare the invention, for which we pray that a Patent may be granted to us, and the :method by which.it is to be performed,to be particularly described in and by the following statement:- 202035 - 2 - —KLUiMPWLi tiU: The present invention relates to herbicidal agent uh i ch conta i n (A) a compound of the formula I H3C\H , P - CHn - CH_ - CH - C (I) / 2 2 I \ RO I ^ y ° . • NH? X 5 in which R denotes hydrogen, N H 4 ✓ Ma, K or 1/2 Ca and X denotes OH or -NH-CH(CH3)-C0NH-CH(CHs)-C00H, in combination with (B) a compound of the formula II. (II) OY X 10 in which X denotes CI or CH3 and Y denotes hydrogen, an alkali metal, N H ^ ^ 'HH3 — CHj, NH2 (02^5)2./-NH2CCH3)2/ NH3-C2H4eOM, NH2(C2lH •OH)2✓ NHCC^H^oOH)^ or ( C -C4)-a I k y I , and ( C ) the compound of the formula III \\ 0113 15 CI—(( )) NH - C - (III) 7=^ ^ch3 el or the compound of the formula IV <x.. - 3 - 202035 ci I (IV) C2H5-NH NH-C2H5 The compound of the formula I in which R = hydrogen and X = -OH has also been disclosed under the name Phosphinotricin. 5' The compound of the formula I in which R = NH^ and X = -OH (= compound la, the ammonium salt of Phosphino-tricin) is particularly preferred. It is described, for example, in New Zealand Patent Specification No.184101 3cani be employed both as the racemate and as the optically 10 active L-form. Compounds of the formula I in which X = -NH-CH(CHj>-CONH-CH(CHj)-COOH, such as are described, for example, i n Australian Patent Specification No.514686 are also preferred. Compounds of the formula II in which X denotes 15 either chlorine (= compound Ila, common name: 2,4-D) or methyl (= compound lib, common name: MCPA) are already known as growth regulators. Both are described, for example, in the "Pesticide Manual", edited by C.R. Worthing (1979), page 145 (Ila) and page 326 (lib). They are pre-20 ferably used in the form of alkali metal (sodium or potassium) or magnesium or amine salts, and in some cases also as esters (Y = (C^-C^-a Ikyl), for example as propyl or isobutyl esters, The compounds of the formula III (common nai 25 diuron) and of the formula IV (common name: simazine) ar- 202035 - 4 - already known as herbicides. Both are described, for example, in the "Pesticide Manual", edited by C.R. Worthing <1979), page 224 (III) and page 474 (IV). At dosages of, preferably, 0.5 to 1.5 kg/hectare 5 of active compound, compounds of the formula I combat annual and perennial weeds belonging to various botanical families, and the after-effects can, in some cases, be considerable in the case of perennial species. In the case of perennial gramineae, however, the effect is not 10 always satisfactory in some cases. Although a relatively rapid, short-term "burning-off effect" is achieved on the green parts of the plants (stalks and leaves), a prolonged effect of longer duration is frequently not achieved. Compounds of the formula II ma-ke it possible to 15 combat numerous bread-leaved species of weeds, specifically both annual and perennial species. They are frequently employed in cereal crops at dosages of less than 1 kg/hectare of active compound. Another main area of use is in application in perennial crops, above all tree-20 like or shrub-like crops, such as vines, fruit trees or citrus trees and various tropical plantation crops, such as rubber, coffee, cocoa and the like, or in bush-like crops, such as sugar cane or bananas. The dosages here, when used alone, are in most cases more than 1 kg/hectare, 25 in some cases more than 2 kg/hectare, of active compound. In these crops, owing to the lower volatility and the lower risk of possible damage to the crop plants caused thereby, it is preferable to use the salts of the compounds of the formula II, and the corresponding esters only to a 202035 5 small extent. The said active compounds of the formula II are absorbed via the leaf and are transported within the plant both towards the roots and towards the tips of the shoots 5 The compounds of the formulae III and IV are also employed in the permanent plantations mentioned above, specifically in a wide range of dosage which can be between 0.5 and 5 kg/hectare of active compound, depending on the crop. Although they have a certain action on the weed 10 flora present, they do not prevent, above all through their long-term action in the soil, the new emergence of weeds from seeds, while they have only a slight effect on re-sprouting from surviving parts of plants below ground (roots, tubers and rhizomes). 15 It has also been disclosed that combinations of compounds of the formula I with compounds of the formulae III or IV, and also, on the other hand, combinations of compounds of the formula I with compounds of the formula II, exhibit a synergistic herbicidal action (cf., for 20 example, Australian patent specification Nos 527,466 and 524 ,653). known mixtures of compounds of the formulae I and II with compounds of the formulae III or IV, as well as combin-25 ations of compounds of the formula II with the known mixtures of compounds of the formulae I and III or I and IV It has now been found that combinations of, the exhibit a surprising additional synergistic herbici>cJal action. This surprising additional synergism of VrH^le 202035 combinations according to the invention can also be confirmed, for example, by using the calculation formulae of S.R. Colby which are customary in connection with the discovery of synergism, by comparing the action found 5 experimentally (in X of damage) of a triple combination with the calculable total action of the individual effects of the components. If the latter is less than the former, synergism is indicated. / / ' The ratios by weight of the components (I) : (II) : 10 (III) or (IV) in the combinations according to the invention can vary within wide limits, but are preferably within the range comprising 1 : (1 to 4) : (0.5 to 6), especially within the range comprising 1 : (1.5 to 2.5) : (1 to 4). The triple combinations according to the invention 15 can be used particularly advantageously to combat in a lasting manner an existing broad spectrum of weeds composed of annual and perennial species, and at the same time to keep the treated areas free for a prolonged period from weeds which emerge later (long-term prolonged 20 effect). Depending on the dosage and on the proportion of the individual components, they can be employed in tree-like shrub-like crops of the temperate and tropical zones, for example in vines, citrus fruit, apples, pears, plums, cherries, soft fruit shrubs, rubber, oil 25 palms, coffee or cocoa; in addition they can also be used in bush-like crops, such as bananas or sugar cane.. The combinations according to the invention can be applied either as tank mixtures in which the individually formulated active compound components are only mixed 202035 with one another immediately before application, or as finished mixtures. As finished mixtures, they can be formulated, for example, in the form of emu I sifiab I e concentrates or preferably, for example, in the form of wet-5 table powders, and they then contain, if appropriate, the customary formulation auxiliaries, such as, for example, wetting agents, adhesives, emulsifiers, dispersing agents, solid inert substances, grinding auxiliaries and solvents. ! ' The concentrations of the active compound combin- 10 ations according to the invention in the formulations to be used can vary. In general, they are 2 to 95% by weight, preferably 5 to 80% by weight. The invention also relates, therefore, to herbi-cidal agents containing 2 to 9^% by weight, preferably 15 5 to 80% by weight, of an active compound combination composed of compounds of the formulae I + II + III or IV and also customary formulation auxiliaries. In the wettable powders, the total concentration of active compound (I + II + III or IV) varies within the 20 range from about 10 to 80% by weight; the remainder up to 100% by weight is composed of customary formulation additives. For application, the active compound concentrates according to the invention are, if appropriate, diluted 25 in a customary manner, for example with water in the case of wettable powders and emulsion concentrates. The required application rate of the agents according to the invention also varies with the external conditions, such as temperature, humidity and other conditions. It can 202035 vary within wide limits and is generally between 0.5 and 20 kg/hectare of triple combination of active compounds, 0 preferably 1 to 10 kg/hectare. A. Formulation examples 5 Wettable powders containing triple combinations, according to the invention, of active compounds are preferably prepared by vigorously mixing, with the exclusion of moisture, advantageously in a hammer mill, the active compounds which are sparingly soluble in water, such as, * 10 for example, the compound III (= diuron) in a finely ground form and already formulated as a wettable powder, with the water-soluble active compounds, such as, for example, the compound la (= ammonium Phosphinotricin) and ' the sodium salt or dimethylamine salt of the compound lib 15 (= MCPA) or Ila (= 2,4-0) and with the necessary wetting agents and dispersing agents. As a result of this the watei—soluble active compounds are very vigorously homogenized with the active compounds which are sparingly soluble in water and with, the su r f a c e-a c t i ve compounds, so 20 that it is possible to achieve optimum wettability and suspendabiIity in the resulting wettable powders. In order to increase the free-flowing properties of the wettable powders, the latter can advantageously contain, as carriers, for example, fine synthetic silica, 25 kiesel9uhr clay or bentonite powder. Examples of suitable dispersing agents are sodium dinaphthylmethanedisulfonate, lignin sulfonates, condensation products of a IkyInaptha l-enesulfcnic acids with cresols, sodium sulfite and formaldehyde, oleoyl-N-methyltaurides, polyvinyl alcohols or 20203 5 - 9 - polyvinylpyrrolidones, while examples of suitable wetting agents are sodium dibutylnaphthalenesulfonate, sodium alkylnaphthalenesulfonates, alkylsulfates, preferably, for example, alkali metal salts and ammonium salts of 5 the sulfuric acid half-ester of aliphatic CC-j2~>— alcohol polyglycol ethers containing 2-6 units of ethylene oxide (= wetting agent FES). Liquid or low-melting surface-active substances are advantageously first absorbed on adsorptive silica 10 to give pulverulent dry concentrates and are mixed into the wettable powder in the form of powder. Suitable anti-foaming agents, if required, are sodium or potassium salts of fatty acids and also silicones. Example 1 15 Preparation of a wettable powder having 53.2% by weight of a triple combination of active compounds, containing 10% by weight of compound la + 16.6% by weight of sodium compound lib + 26.6% by weight of compound III. 1.1 The formulation of a wettable powder containing 20 80% by weight of compound III: A mixture of 80.0% by weight of compound III, 12.0% by weight of synthetic silica, 6.0% by weight of sodium dinaphthyI methanedisuIfonate, 1.8% by weight of a sodium a IkyInaphthalenesulfonate and 0.2% by weight of 25 sodium oleoyI-N-methy11auride was ground on a high-speed pinned-disk millto give a fine powder of particle size less than 4 4 microns. 1.2 The forrnulati on of a wetting agent adsorption concentrate composed of a pasty, aqueous sodium (C^-, 2020 3 5 - 10 - fatty alcohol polyglycol ethei—sulfate C= FES) and adsorp-tive synthetic silica: 60 parts by weight of a 70% by weight FES paste and 40 parts by weight of colloidal synthetic silica were 5 vigorously mixed at a stirrer speed of approximately 150 r.p.m. in a high-efficiency mixer containing a stirrer shaft fitted with circulating paddles, whereby a pulverulent adsorbate containing 42% by weight of FES active substance was<>btained. 10 1.3 Preparation of the wettable powder containing 53.2% by weight of the triple combination of active compounds: 33.25 parts by weight of 80% strength wettable powder of compound III, prepared in accordance with 1.1 15 and containing 26.6 parts by weight of compound III, 10.00 parts by weight of compound la, 16.60 parts by weight of the sodium salt of compound lib, 23.80 parts by weight of FES adsorbate wetting agent, prepared in accordance with 1.2 and containing 10 parts by weight of FES, 20 5.15 parts by weight of sodium dinaphthyImethanedisulfonate, 2.00 parts by weight of sodium dibutylnaphthalenesulfonate, 1.00 part by weight of soap flakes and 8.20 parts by weight of synthetic silica weremixed with exclusion of moisture and were then ground on a cross-hammer mill 25 to give a finely pulverized product. Example 2 Preparation of a wettable powder having 40% bv weight of a triple combination of active compounds, containing 10% by weight of compound la + 20% hy up.i.ght ai_ 202035 - 11 - sodium compound Ila + 10% by weight of compound III. 12.5 parts by weight of an 80% strength wettable powder of compound III, prepared in accordance with Example • t 1.1 and containing 10 parts by weight of compound III, 5 10.0 parts by weight of compound la, 20.0 parts by weight of the sodium salt of compound Ila, 23.8 parts by weight of FES adsorbate wetting agent, prepared in accordance with Example 1.2 and containing 10 parts by weight of FES, 5.7 parts by weight of sodium dinaphthylmethanedisulfon-10 ate, 3.0 parts by weight of sodium dibutylnaphthalene-sulfonate, 2.0 parts by weight of soap flakes and 13.0 parts by weight of synthetic silica were mixed with exclusion of moisture in a high-efficiency mixer analogously to Example 1, and the mixture was then ground on a cross-15 hammer mill to give a finely pulverized product. B. Biological examples In the biological examples I to IV which follow, a distinction is drawn, for the active compound combinations tested, between the calculated degree of action 20 and the degree of action found, on the weeds mentioned. The degree of action is calculated using the formulae of S.R.Colby: Calculating synergistic and antagonistic responses of herbicide combinations (Weeds 1_5, pages 20-22, 1967) from the effects of the constituents of the 25 combinations when the latter are applied individually. Formula (1) for the combination of 2 active compounds is as follows: X . Y E = X + Y - (1) 100 2020 3 5 - 12 - in uhich X denotes % damage caused by herbicide A a't an application rate of x kg/hectare, Y demotes % damage caused by herbicide B at an application rate of y kg/hectare and E denotes the expected damage caused by the herbicides 5 A + B at application rates of x + y kg/hectare. For the combination of 3 active compounds, formula (2) is given in the same publication for calculating the degree of action: (XY + X2 + YZ) XY2 E = X + Y+ Z- * (2) 100 10,000 10 in which Z denotes % damage caused by herbicide C at an application rate of z kg/hectare and X and Y have the same meanings as in formula (1). If the actual damage, ie. the damage determined experimental Iy, is greater than that calculated, the 15 action of the combination is more than additive, ie. a r synergistic effect is present. In the biological examples which follow, this evidence is presented for the combinations according to the invention, the values of action calculated from the above formulae being also shown in 20 brackets in each case for the treatments with combinations according to the invention, while the action actually achieved against the particular weeds mentioned is listed after these figures. In biological examples I to IV, comparison is 25 made not only ' of the action of the combination 1 + II -5- J.II or IV with that of the 3 individual active compounds, but also with the action of the combinations I + II and I + III or IV, which are already known. These 5 1 10 •15 20 25 202035 - 13 - use examples relate to field tests which were carried out under various climatic conditions. The results are shown in summary form in Tables I to IV. All the tests were carried out in plots of area 10 to 20 Example 1 In a test under tropical conditions on the weed Mikania cordata in a rubber plantation, the individual compounds la, Ila and III were tested alongside one another, as was the known combination la + III. Both when compared with the individual products and when compared with the known combination, combinations according to the invention, composed of these three active compounds, produced a considerable increase in the action, significantly exceeding the degree to be expected. The action of the triple combinations can, accordingly, be designated synergistic. The result is shown in summary form in Table I below-Table I Combating Mikania cordata in a rubber plantation. T reatment with active compound Dosage of act i ve compound, kg/hectare Action (% damage) on Mikania cordata (field test) 5 weeks after: treatment calculated found a) Individual active compounds: Compound la Compound Ila Compound Ila Compound III b) Known combination Compounds la + III 0.4 0.8 0.4 0.4 0.4 + 0.4 c) Combinations according to the invention Compounds Ia+IIa+III Compounds Ia+IIa+III 0.4*0.4+0.4 0.4+0.8+0.4 (73*/82**) (82*/88**) 50 60 40 10 70 90 1:1:1 96 1:2:1 . "202035 * calculated from the action of the individual products ** calculated from the action of the known combination and Ila. Example II 5 Table II shows the results with three weeds,which are difficult to combat, from a series of tests in vine and apple plantations which was drawn up in accordance with a uniform test plan; in particular, side by side tests were carried out with the compound lib and the known com-10 binations la + III and la + IV and also the combinations, according to the invention, la + lib + III and la + lib + IV. The herbicidal action of the triple combinations mentioned was distinctly better than would have been expected from the calculations of the Colby formula, the known 15 combinations being rated in each case as single treatments, which signifies a synergistic increase in the action. The result is shown in summary form in Table II below. Combating weeds which are difficult to combat in vine and apple plantations Treatment with active compound Dosage of active compound kg/hectare Action (% damage) on the following weeds (field test) Plantago lanceolata Cirsium arvense in an apple plantation in a vine (4 weeks after treatment) plantation (6 weeks after treatment) Convolvulus arvensis in a vine plantation (6 weeks after treatment) Compound lib Compounds la + III Compounds la + IV 1.0 0.5 + 2.0 0.5 + 2.0 Combinations according to the invention Compounds Ia+IIb+III Compounds Ia+IIb+IV 0.5 + 1.0 + 2.0 0.5 + 1.0 + 2.0 50 60 55 (80) 93 (77.5) 98 75 30 30 (77.5) 92 (77.5) 90 80 50 50 (90) 100 (90) 100 i Ul I N> O 1s> O u Ul 202035 Example III The known combination la + lib uas tested as a mixture uith the compound III in a further test on the weed Rumex acetosa in a cherry plantation. An increase 5 in action which markedly exceeded the amount to be expected was found in the case of the triple combination according to the invention, ie. a synergistic increase in action is present. The result is shown in summary form in Table III below. 10 Table III Combating Rumex acetosa in a cherry plantation 15 Treatment with active compound CompoundsIa+IIb Compound III Compounds Ia+IIb+III Dosage of active compound kg/hectare 0.5+1.25 2.0 0.5+1.25+2.0 Action (% damage) on Rumex acetosa (field test) 6 weeks after treatment calculated (84) found 80 20 95 20 25 1 : 2.5 : 4 ExampIe IV The preparations la, Ila and III were tested on their own and also in the known combinations 1a + Ila and la + III and also in triple combinations according to the invention, in a young plantation of oil palms in which the rows of trees were very severely infested with Mikania cordata, pueraria sp. and various grasses, principally Paspalum conjugatum. The action on the weeds and also the damage to crop plants were assessed after 5 and 10 weeks. In the case of the action on Paspalum it was 202035 found that the compound la at 0.4 kg/hectare of active compound sufficed completely, as such,, to achieve a 100% action on the weed plants present. However, after 10 weeks numerous Paspalum plants had re-emerged from seeds 5 present in the soil, since the compound la has no effect on the soil. On the other hand, in plots which had been treated with compound III the plants which had re-emerged from seeds had been destroyed, whereas the weed plants already present were only slightly damaged. However, the 10 plots which had been treated with combinations according to the invention were similarly free from old plants, ie. plants present at the time of application, and also from freshly germinated plants. In the case of Pueraria and Mikania, all the treatments with the compounds la or Ila 15 had an initial action which was in some cases very good, but the after-effect 10 weeks after the treatment was completely unsatisfactory. The known combinations were also no longer adequately effective at this point in time. Using the triple combinations according to the inven-20 tion, however, it was found that, above all, the aftereffect was particularly good, an effect which would not have been expected to be so marked and which must therefore be designated as synergistic. A good after-effect could admittedly also be achieved using the known cornbi-25 nation la + Ila at 0.4 + 1.2 kg/hectare; however, in this case distinct damage caused by growth substances (leaf twisting) was found on young trees which had come into contact with the spray liquor on the bark or on parts of the palm frond. On the other hand, in the case of the 202035 - 18 - combination according to the invention, in which the proportion of the substance Ila had been reduced markedly, this leaf damage could no longer be observed. The dosage of the combination could even be reduced by one quarter in 5 order to reduce the risk of leaf damage still further, without the action against weeds, in particular the aftereffect 10 weeks after treatment, being reduced to a considerable extent (cf. Table IV, last line). Triple com- i binations according to the invention thus make it possible 10 to ensure that the use of the herbicide becomes more reliable and that a markedly increased and thus sufficiently long after-effect is achieved at the same time; the result of this under practical conditions is that the time of the next treatment with herbicide can be postponed; this also 15 effects a saving in the costs of labor and products, amongst other things. The result is shown in summary form in Table IV below. \ </div>

Claims

<div class="application article clearfix printTableText" id="claims"> Table IV Combating weeds in a young plantation of oil palms Treatment with active compound Dosage of active compound kg/hectare Action (% damage) on the following weeds (field test) after 5 weeks Pueraria sp. Mikania sp. after 10 weeks Pueraria sp. Mikania sp. Leaf damage in th oil palm plantation after 5 weeks §2_lQdlyidual_comgounds . Compound la 0.4 Compound Ila 1.E Compound Ila 0.6 Compound III 0.4 bl_Kriown_cgmbi nations Compounds la+IIa 0.4+1.2 Compounds la+IIa 0.4+0.6 Compounds Ia+III 0.4+0.4 85 95 90 10 99 98 90 c2_Combinations_according_to_the_inyention Compounds Ia+IIa+III Compounds Ia+IIa+III 0.4+0.6+0.4 0.3+0.45+0.3 100 (98) 99 80 95 80 0 99 95 90 100 (96) 96 40 60 30 0 85 70 45 85 (53) 80 50 70 40 0 80 65 60 95 (79) 90 NO I Is> O N) O U\ 202035 - 20 - WHAT WE CLAIM IS:

1. A synergistic herbicidal agent which contains

(A) a compound of the formula I

lUC

3\||

HO

/P " CH2

- CH„ -

CH

I

NH.

O

(I)

in which R denotes hydrogen, nh4, Na, K or 1/2 Ca and X denotes OH or -NH-CH<CH3)-cONH-CH(Ch3)-C00H, in combination with

(B) a compound of the formula II

o - CH2 - C

\

O

OY

UI)

in which X denotes CI or CH3 and Y denotes hydrogen, an alkali metal, NH^, nh3-ch3, NH2(C2H5)2,

nh2(ch3)2, nh3-c2h4*oh, nh2(c2h4.oh)2,

NH(C2H4»0H)j or C C-j-C^)-a I ky I , and (C) the compound of the formula III

O

II

NH - C - N.

CH.

'CH.

(Ill)

or the compound of the formula IV

-v .

- 21 -

202035

(IV)

'2 "5

nh-c2h5

A synergistic herbicidal agent as claimed in claim 1,

- by weight of the components of the formulae

2. A synergistic herbicidal agent as claimed in claim 1, wherein the mixing ratio by weight of the components of'the formulae I : II : III or IV is 1 : (1 to 4) : (0.5 to 6).

3 .

wherein the mixing ratio I : II : III or IV is 1 : (1.5 to 2.5) : (1 to 4).

4. A synergistic herbicidal agent which contains 2 to 95% by weight of an active compound combination as claimed in any of claims 1 to 3, the remainder up to 100% by weight being composed of customary formulation auxiliaries.

5. The use of the agents as claimed in any of claims 1 to 4 for combating weeds, in tree-like, shrub-like or bush-like permanent plantations.

6. A process for combating weeds, which comprises applying active compound combinations as claimed in any

/

of'claims 1 to 4 to the areas infested by the weeds, in quantities of 0.5 to 20 kg of active compound combination per hectare.

7. A synergistic herbicidal agent according to claim 1 substantially as herein described.

HOECHST AKTIENGESELLSCHAFT By Their Attorneys HENRY HUGHES LIMITED By:

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