DE4116626A1 - New herbicidal compsn. esp. for use in fruit crops - contains one or more phosphinyl-butanoic acid cpds. and 3,5-di:chloro:benzamide deriv. - Google Patents

Abstract

Herbicidal compsn. comprises one or more phosphinoyl-butanoic acid derivs. of formula (I) in combination with N-(1,1-dimethyl-prop-2-yn-1-yl) -3,5-dichlorobenzamide (II): Z = OM', NHCHMeCONHCHMeCOOM' or NHCHMeCONHCH(i-Bu)COOM'; M, M' = H or an organic or inorganic cation. The wt. ratio of (I) to (II) is pref. 10:1-1:10. The compsn. comprises 1-95 (esp. 2-90) wt.% of herbicidal agents and 5-99 (esp. 10-98) wt.% of conventional formulation agents. The compsns. are formulated as granulates, emulsions or wettable powders, and are used in doses of 0.2-1 (esp. 0.5-1) kg/ha of (I) and 0.2-2.5 (esp. 0.5-2.0) kg/ha of (II). USE/ADVANTAGE - The compsn. may be used to treat grass weeds such as Agopynon, Cynodon, Impenata or Cirsium in crop cultures such as citrus, rubber, cotton, coffee, cacao and in fruit crops and vineyards. The active agents are more effective together than either (I) (esp. Glufosinate (Ia) useful as leaf herbicide in e.g. fruit crops) or (II) (also useful in fruit crops) alone. (I) are known from e.g. US4168936 or US4309208. (7pp Dwg.No.0/0)

Description

The invention relates to the technical field of Plant protection products that are a combination of two or contain several herbicide active ingredients.

The invention relates to herbicidal compositions which one or several compounds of formula (I)

wherein

Z is a radical of the formula -OM¹, -NHCH (CH₃) CONHCH (CH₃) COOM¹ or
-NHCH (CH₃) CONHCH [CH₂CH (CH₃) ₂] COOM¹ and
M, M¹ each independently represent hydrogen or an inorganic or organic cation,

in combination with a compound of formula (II)

contain.

The invention also relates to a method for Control of unwanted plant growth, thereby characterized in that compounds of formula (I) in Combination with the compound of formula (II) on the Plants or their acreage applied.  

The compounds of formula (I) are in US-A 41 68 936, US-A 43 09 208, S. Omura et al. in "The Japanese Journal of Antibiotics "Vol. XXXVIII-2 (1985), p. 542; H.S. Seto et al. in "The Japanese Journal of Antibiotics" Vol. XXXVI-1 (1983), s. 96-98. Formula (I) also affects everyone formally included stereoisomers including the possible ones pure enantiomers and their mixtures.

Preferred compounds of the formula (I) are 4- [hydroxy (methyl) phosphinoyl] butanoic acid (Ia), Common Name: Glufosinate, d. H. Formula (I) with M = H and Z = OH in the D, L or the enriched L form, and their salts, especially glufosinate ammonium (Ib), d. H. Formula (I) with M = H and Z = ONH₄, in the D, L or enriched L form; further preferred are bialaphos (Ic), i. H. formula (I) with and Z = NHCH (CH₃) CONHCH (CH₃) COOH and M = H, and their Salts. Compounds Ia and Ib are also in, for example "The Pesticide Manual", British Crop Protection Council, 8. Ed. 1987, page 448.

The compound of formula (II), i.e. H. N- (1,1-dimethyl-prop-2-yn-1-yl) -3,5-dichlorobenzamide, is also known (cf. "The Pesticide Manual" 8th Ed., The British Crop Protection Council 1987, page 720, substance no. 10240, Common Name: Propyzamide).

The salts of the compounds of Formulas (I) and (II) include those for agriculture usable salts. As such, for example usual alkali, alkaline earth, substituted or unsubstituted ammonium, phosphonium or sulfonium salts into consideration. Among the alkali metal and Alkaline earth metal salts are primarily the Na, K, Mg or to call Ca salts.

The commercial active ingredient glufosinate ammonium is often used as a leaf herbicide, for example  for the non-selective control of weeds in fruit and Viticulture, in tropical plantation crops, in vegetable growing sowing or transplanting, before direct sowing of Corn or soybean as well as on non-cultivated land such as Edges, industrial sites and railway facilities (see Z. PflKrankh.PlfSchutz, special issue IX, 431-440, 1981).

With the active ingredient, many annual plant species can combating botanical families excellently; at Perennial species, on the other hand, those that are over underground parts such as roots, rhizomes or tubers increase, often only the existing green Parts of plants destroyed, but the plants survive and sprout from their underground organs again. The Racemat is usually applied in doses that between 200 and 1000 g per hectare (in the form of formulated product with 200 g a.i./l), and it is effective in these dosages only if it is above green Plant parts is included. Since it is microbial in the soil is dismantled within a few days, it has none Permanent effect in the soil. The same applies to the related agents such as bialaphos.

The active ingredient propyzamide of formula (II) is called persistent soil herbicide in fruit and wine growing as well as in Vegetable growing used (cf. Proc. 3rd EWRC symposium new Herbicides, Paris 1969, 237-259). This ingredient will predominantly via underground parts of plants such as roots or Rhizomes ingested from the plant. He is known that it works very slowly, that it degrades only slowly, and that because of its low water solubility no danger there is a washout in the ground. Because of its high Vapor pressure is recommended in fruit and wine growing if possible during the winter, at the latest at the beginning of the To apply vegetation. In vegetable growing, it should if possible be worked into the soil to prevent evaporation prevent. The dosages are usually in the range around 2500 g / ha in permanent crops or around 500 g / ha in vegetable growing;  commercially available products in solid or liquid form contain z. B. 50% active ingredient. In usual doses in Permanent crops are particularly effective when used in good time good against perennial grasses.

It has now been found that when using the Combination of Active Ingredients (I) and (II) According to the Invention in particular the effect against grass was considerably stronger than expected. The herbicidal compositions according to the invention surprisingly showed clear, synergistic Increases in effectiveness.

The weight ratio of the active ingredients (I) to (II) can be in vary wide limits and is preferably from 10: 1 to 1:10, especially 4: 1 to 1: 4. When using Compound (Ib) is also 3: 1 to 1: 3 special prefers.

With the external conditions such as temperature, humidity, Bottom u. a. the required application rate varies. The Application rate for the active compounds of the formula (I) in the Combinations according to the invention is preferably 0.2 to 1 kg a.i./ha, in particular 0.5 to 1 kg a.i./ha. For the Compound of formula (II) is the application rate in the Combinations preferably 0.2 to 2.5 kg a.i./ha, in particular 0.5 to 2.0 kg a.i./ha.

The herbicidal compositions according to the invention can be used both as Mixed formulations of the components in the form of a Concentrates (active ingredients + formulation aids) are present, which are then diluted with water in the usual way be used, or as so-called Tank mixes by mixing the unformulated active ingredients and optionally aids or the separately formulated active ingredients and joint dilution with Water. If necessary, the Spraying agent before the application of further aids, for example, wetting agents.  

The herbicidal compositions can be formulated in various ways depending on which biological and / or chemical-physical Parameters are specified. As Formulation options are possible, for example: Wettable powder (WP), dusts, emulsifiable concentrates (EC) (limited), concentrated emulsions (EW), e.g. B. Oil-in-water or water-in-oil emulsions, sprayable solutions or emulsions, oil or water based dispersions, Dusts (DP), pickling agents, granules (G) such as floor or Scatter granules (FG) or water-dispersible granules (WDG), ULV formulations, microcapsules or waxes. SC, EW, WP and WDG formulations are preferred.

These individual types of formulation are known in principle and are described for example in: Winnacker-Küchler, "Chemical Technology", Volume 7, C. Hauser Verlag Munich, 4th edition 1986; van Valkenburg, "Pesticides Formulations", Marcel Dekker N.Y. 1973; K. Martens, "Spray Drying Handbook ", 3rd Ed. 1979, G. Goodwin Ltd., London.

The agents according to the invention can be used as usual additives especially contain those that are used to manufacture the special types of formulation are advantageous.

Spray powders are evenly dispersible in water Preparations containing one or more active substances and if necessary, diluents or inert substances Wetting agents, e.g. B. polyoxethylated alkylphenols, polyoxethylated fatty alcohols, alkane or Alkylarylsulfonates, fatty alcohol polyglycol ether sulfates and Dispersants, e.g. B. sodium lignosulfonate, 2,2'-dinaphthylmethane-6,6'-disulfonic acid Sodium, dibutylnaphthalenesulfonic acid sodium or also Contain oleoylmethyl tauric acid sodium. Typical festivities Inert substances or diluents are described in Watkins et al., "Handbook of Insecticide Dust Diluents and Carriers, "2nd Ed., Dorland Books, Caldwill, New Jersey, but also other solids, whether from  natural sources or manufactured industrially be used. More absorbent solids are for Spray powder preferred. The production takes place in the usual way Way, e.g. B. by grinding and mixing the components.

Emulsifiable concentrates can e.g. B. by dissolving the Active ingredients in an inert organic solvent, e.g. B. Cyclohexanone, xylene or higher-boiling aromatics or Hydrocarbons with the addition of one or more Emulsifiers are produced. With liquid active ingredients the solvent content can also be wholly or partially omitted. For example, emulsifiers can be used are: alkylarylsulfonic acid calcium salts such as Calcium dodecylbenzenesulfonate or nonionic emulsifiers such as fatty acid polyglycol esters, alkylaryl polyglycol ethers, Fatty alcohol polyglycol ether, propylene oxide-ethylene oxide condensation products (e.g. block polymers), fatty alcohol-propylene oxide-ethylene oxide condensation products, Sorbitan fatty acid esters, polyoxethylene sorbitan fatty acid esters or polyoxethylene sorbitol ester.

Typical liquid solvents or thinners for Wettable powder, emulsifiable concentrates, dispersions etc. are z. B. described in Marsden, "Solvents Guide" 2nd Ed., Interscience, New York, 1950; Emulsifiers, dispersants and Wetting agents are e.g. B. described in "McCutcheon's Detergents and Emulsifiers Annual ", MC Publishing Corp., Ridgewood, New Jersey or in Sisley and Wood, "Encyclopedia of Surface Active Agents ", Chemical Publishing Co., Inc., New York 1964.

Dusts can be obtained by grinding the active ingredients finely divided, solid substances, e.g. B. talc, natural Clays such as kaolin, bentonite, pyrophillite or diatomaceous earth receive. Suitable solid substances are e.g. B. in said "Handbook of Insecticide Dust Diluents and Carriers" described.  

Granules can either by spraying the active ingredients adsorbable, granulated inert material be or by applying active ingredient concentrates by means of binders, e.g. B. polyvinyl alcohol, polyacrylic acid sodium or mineral oils on the Surface of carriers such as sand, kaolinite or granulated inert material. Suitable active ingredients can also in the for the production of fertilizer granules usual way, if desired in a mixture with Fertilizers to be granulated. Plate, fluid bed, Extruder and spray granules can be made by conventional methods getting produced; see e.g. B. Procedure in "Spray Drying Handbook "3rd ed. 1979, G. Goodwin Ltd., London; J.E. Browning, "Agglomeration", Chemical and Engineering 1967, Pages 147ff; "Perry's Chemical Engineer's Handbook", 5th Ed., McGraw-Hill, New York 1973, pp. 8-57.

For more information on the formulation of Plant protection products see e.g. B. G. C. Klingman, "Weed Control as a Science, "by John Wiley and Sons, Inc., New York, 1961, pp. 81-96 and J.D. Freyer, S.A. Evans, "Weed Control Handbook ", 5th Ed., Blackwell Scientific Publications, Oxfort, 1968, pages 101-103.

The agents according to the invention generally contain 1 to 95 wt .-%, preferably 2 to 90 wt .-% of the herbicidal salts according to the invention (active ingredients).

The active ingredient concentration in wettable powders is e.g. B. 10 to 90 wt .-%, the rest of 100 wt .-% consists of usual formulation components. With emulsifiable Concentrates can have the active ingredient concentration about 1 to 80 % By weight. Contain dusty formulations usually 1 to 20 wt .-% of active ingredient, sprayable solutions about 0.2 to 20% by weight. With granules it depends Active ingredient content partly depends on whether the effective Connection is liquid or solid and which Granulation aids, fillers, etc. can be used.  

In addition, the active ingredient formulations mentioned contain where applicable, the usual liability, network, Dispersing, emulsifying, penetration, solvent, filling or carriers.

To be used in the commercial form existing concentrates, if necessary, in a customary manner diluted, e.g. B. with wettable powders, emulsifiable Concentrates, dispersions and sometimes also at Microgranules using water. Dusty and granular Preparations and sprayable solutions are made before Usually no longer used with other inert substances Diluted substances.

Mixtures or mixed formulations with others Active ingredients, such as B. insecticides, acaracides, herbicides, Fertilizers, growth regulators or fungicides possibly possible.

The active compound combinations according to the invention are in the Usually applied to areas covered with weeds.

The agents according to the invention cover a wide range Weed spectrum. For example, they are suitable for Control of annual and perennial weeds such as for example agropyron, cynodon, imperata, pennisetum, Convolvulus, Cirsium, Rumex and others.

The agents according to the invention can be used for selective Control of harmful plants in plantation crops such as Oil palm, coconut palm, rubber tree, citrus, pineapple, cotton, Coffee, cocoa and a. as well as in fruit and wine growing. Likewise, the combinations according to the invention in Agriculture in the so-called "no till" or "zero till" process be used. But they can also be non-selective on paths, squares, industrial plants etc. applied to these areas of unwanted Keep vegetation free.  

It is particularly suitable for use in fruit and wine growing, where grasses, especially perennial or perennial grasses, play a significant role as weeds.

With the active ingredient combinations used according to the invention can the drug doses compared to the Single application of the active ingredients can be reduced or can follow-up applications that are normally necessary to the plants weed-free during the growing season hold, be saved. Such combinations are also suitable for herbicides previously used in fruit and wine growing Basis diuron, aminotriazole or simazine, their use because of possible groundwater contamination or others undesirable side effects are increasingly restricted, to replace partially or completely.

In the following examples, percentages refer to the weight unless otherwise stated.

A) Formulation examples 1. WP wording

A water-dispersible, wettable powder get by

20% compound of formula (I) z. B. Compound (Ib),
25% compound of the formula (II),
10% synthetically precipitated silica (®Sipermat 22 S),
15% sodium lauryl sulfate (®Texapon K 12),
5% sodium alkylnaphthalenesulfonate (®Leonil DB),
4% polyvinyl alcohol (®Mowiol 18-88),
21% filler (®Omya chalk)

mixes and grinds in a pin mill.  

2. Spray dried WDG

A water-dispersible granulate is obtained by

16% compound of formula (I), e.g. B. (Ib),
20% synthetically precipitated silica,
20% compound of the formula (II),
15% alkyl ether sulfate (®Genapol LRO),
4% Na oleyl methyl tauride (®Hostapon T),
6% Na-alkylnaphthalenesulfonate (®Leonil DB),
6% sugar,
13% chalk

mixed with water, wet milled and spray dried.

3. EW wording

An oil-in-water emulsion is obtained from

8% compound of formula (I), e.g. B. (Ib), 10% compound of formula (II),
34% aromatic solvent mixture,
5% phosphated tristyrylphenyl polyglycol ether (®Soprophor FL) neutralized with dimethylamine,
2% sodium phenyl sulfonate (®Dispersant GN),
10% tributylphenol polyglycol ether (®Sapogenat T 110),
1% gelling agent based on magnesium montmorillonite,
30% water.

4. SC wording

An aqueous dispersion is obtained by

10.4% compound of formula (I), e.g. B. (Ib),
13.0% compound of the formula (II),
5.7% sodium lignin sulfonate,
2.4% sodium salt of polymerized substituted alkylbenzenesulfonic acids and inorganic suspending agents (®Darvan No. 3),
3.4% sodium salt of polymerized alkylnaphthalenesulfonic acids (®Darvan No. 1),
15.0% (C ₁₂ -C ₁₄ alkyl) diglycol ether sulfate sodium (®Genapol LRO),
0.1% polysaccharide based on xanthan (®Rhodopol 23) and
50.0% water

mixes in the usual way and wet milled.  

B) Biological examples

The following two examples are for the combination treatments the effect actually achieved after Colby (see Weeds 15, 20-22, 1967) expected effect juxtaposed. The expected effect is calculated according to the following formula:

in which

X is the effect (%) of herbicide A at x kg / ha application rate,
Y is the effect (%) of herbicide B at y kg / ha application rate,
E is the expected effect (%) of the combination of A and B at x + y kg / ha application rate.

The expected effect E is in the following tables given in combination treatments in brackets. If the effect actually found exceeds this Expected value, a synergism is assumed.

example 1

In an apple orchard, in which the rows of trees predominantly with Mercury (Agropyron repens) were contaminated, became two Appointments, namely end of March and end of April, each 20 m² large plots with the active ingredients Ib and II alone and in Combinations injected. Doing each of these Treatments repeated three times, d. H. each received three Plots of the same amount of active ingredient. The preparations were in commercial formulations and in practice Dosages used. The tests were evaluated in the form of a visual rating for percent effect (0% = without effect, 100% = complete destruction of the surface Plant parts) and is summarized in Table 1.  

As expected, the effect of preparation Ib was very soon visible after treatment: the green parts of the plant reacted very clearly with yellowing and to it following necrosis. The plants weren't killed, but soon recovered, so that 4 weeks after Treatment and later hardly any effect was visible. Conversely, the effect of Product II was very late, namely 8 weeks after treatment, visible after the Active ingredient had been absorbed through the root. The combination according to the invention initially showed one of the Effect of preparation Ib similar effect; after that took the Effect clearly and reached at the end of the Observation period, namely 8 weeks after treatment, a very high efficiency. If you put on the dates 4 and 8 weeks after treatment the one expected by Colby Effect of the actually achieved against, is a considerable difference in favor of the latter determine; there is therefore a synergism.

Table 1

Effect of preparations Ib and II alone and in combinations on mercury, rated as an effect in% 2, 4 and 8 weeks after application

Example 2

In a similar experiment in another orchard the active ingredients Ib and II were also alone and in Combination applied, but in much lower Application rates. Here, too, Quecke came into existence as a stock-forming agent Weed in front, next to it some other grasses in alternating Composition. The test results were analogous Example 1 obtained and are summarized in Table 2.

In this series of tests, product II was almost alone ineffective, while the active ingredient I similar to that in Example 1b described an easily visible, but did not have sufficient initial effect from which the plants mostly recovered soon. In combination Ib and II was the 4 weeks after treatment Effect significantly stronger than that calculated by Colby was also here at significantly lower doses Synergism before.

Table 2

Effect of preparations Ib and II alone and in combination on mercury and other grasses as a% effect 2, 4 and 8 weeks after application

Similar results can be achieved if the Active ingredients Ic and II combined.

Claims (12)

1. Herbicidal compositions which comprise one or more compounds of the formula (I) whereinZ is a radical of the formula -OM¹, -NHCH (CH₃) CONHCH (CH₃) COOM¹ or
-NHCH (CH₃) CONHCH [CH₂CH (CH₃) ₂] COOM¹ and
M, M¹ are each independently hydrogen or an inorganic or organic cation, in combination with a compound of the formula (II) contain. 2. Composition according to claim 1, characterized in that Z represents the formula -OH or -OM¹ and
M, M¹ are hydrogen or NH₄, where not both M and M¹ also mean NH zugleich. 3. Composition according to claim 1 or 2, wherein the Weight ratio of the compounds of the formulas (I) to (II) 10: 1 to 1:10. 4. Means according to claim 3, characterized in that the Weight ratio is 4: 1 to 1: 4.   5. Composition according to one or more of claims 1 to 4, characterized in that they contain 1 to 95 wt .-% herbicide active ingredients and 5 to 99% by weight more commonly Formulation aids included. 6. Composition according to one or more of claims 1 to 5, characterized in that they contain 2 to 90 wt .-% herbicide active ingredients and 10 to 98% by weight more commonly Formulation aids included. 7. Composition according to claim 5 or 6, characterized in that they are emulsions, wettable powders (wettable powders) or water-dispersible granules are formulated. 8. Procedures to combat unwanted Plant growth, characterized in that an effective Amount of an agent according to one or more of claims 1 up to 7 applied to the plants or their acreage. 9. The method according to claim 8, characterized in that the application rates for compounds of formula (I) 0.2 to 1 kg / ha and for the compound of formula (II) 0.2 to 2.5 kg / ha in the combinations of the compounds. 10. The method according to claim 9, characterized in that the application rates for compounds of formula (I) 0.5 to 1 kg / ha and for the compound of formula (II) 0.5 to 2.0 kg / ha in the combinations. 11. The method according to one or more of claims 8 to 10, characterized in that perennial grasses, possibly combated with annual grasses will. 12. Use of combinations of the compounds of the Formula (I) and (II) as defined in claim 1 or 2 are to combat unwanted plant growth.