DD247822A5 - HERBIC MEDICINE AND ITS USE - Google Patents

Abstract

A herbicidal composition which contains as active ingredient at least one urea herbicide and diflufenican in addition to a conventional carrier or dismutating agent and optionally further additives, is particularly suitable for controlling a wide range of grassy and broadleaf weeds in cereal crops. The two active ingredients can also be applied in succession, at intervals of a few minutes.

Description

R ¹ N (R ² JCON (R ³ JR ⁴ II

wherein R ^{1 is} an optionally substituted cyclic hydrocarbon group or an aromatic heterocyclic group, R ^{2 is} a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms, R ^{3 is} a linear or branched alkyl group having 1 to 6 carbon atoms or is an optionally substituted cyclic hydrocarbon group and R ^{4 is} a hydrogen atom or a linear or branched alkyl or alkoxy group having 1 to 6 carbon atoms.

5. Composition according to item 4, characterized in that in the given formula R ¹ either a phenyl group, optionally substituted in 3- and / or 4-position, based on the nitrogen atom, by a chlorine or bromine atom or by an optionally halogenated substituted linear or branched alkyl or alkoxy group with 1 to

6 carbon atoms or by a like, optionally substituted phenoxy group, or the benzothiazol-2-yl group.

6. Composition according to item 4 or 5, characterized in that in the given formula R ^{2 is} a hydrogen atom or the methyl group and R ^{3 is} the methyl group.

7. Composition according to one of the items 4 to 6, characterized in that in the given formula R ^{2 is} a hydrogen atom and R ^{3 is} the methyl group and

(i) R ^{1 is} the phenyl, 3-trifluoromethylphenyl or 4-chlorophenyl group and R ^{4 is} the methyl group, or (ii) R ^{1 is} the 4-chlorophenyl group and R ^{4 is} the methoxy group, or

(iii) R ^{1 is} the S-chloro-methylphenyl or 4-isopropylphenyl group and R ^{4 is} the methyl group, or (iv) R ^{1 is} the 3,4-dichlorophenyl group and R ^{4 is} a methyl, methoxy or butyl group, or that in the given formula

R ^{1 is} the benzothiazol-2-yl group, R ² and R ^{3 are} each methyl and R ^{4 is} a hydrogen atom.

8. Use of the agent according to any one of items 1 to 7, characterized in that it is used in an application rate of 150g to 10kg / hafür the urea herbicide and from 25 to 750g / ha diflufenican.

Use according to item 8, characterized in that the composition according to any one of items 1 to 7 is used to control one-year broadleaf weeds and grass weeds in grain by pre-emergence or postemergence application of (a) a urea herbicide selected from chlortoluron, isoproturon , Linuron, methabenzthiazuron and neburon or mixtures thereof, and (b) diflufenican at rates of from 500 to 3500g / ha urea herbicide and 50 to 250g / ha diflufenican in a weight ratio of 70: 1 to 20: 1.

10. Use according to items 8 and 9, characterized in that the active ingredients of the composition according to one of the items 1 to

7 simultaneously, separately or successively applies.

For this 5 pages drawings

Field of application of the invention

The invention relates to a novel herbicidal composition which is useful as a pre- or post-emergence herbicide, especially in cereal crops.

Characteristic of the known technical solutions

GB-A 2087887 discloses N- (2,4-difluorophenyl) -2- (3-trifluoromethylphenoxy) nicotinamide of the formula I.

described as pre-emergence and / or post-emergence herbicide, as well as its use in agriculture. It is also known that the extensive use of urea herbicides and their mixtures, by which certain weed species such as Galium aparine, Veronica hederifolia, Veronica persica and Viola arvensis, are only little destroyed, to an increased occurrence of Galium aparine, Veronica and Viola so that these weeds are now a serious problem in grain bakers.

Object of the invention

The aim of the invention is a herbicidal composition having a broader spectrum of activity than the known urea herbicides.

Explanation of the essence of the invention

It has now been found that through the use of the compound N- (2,4-difluoro-phenyl) -2- (3-trifluoromethylphenoxy) nicotinamide, hereinafter referred to simplifies with diflufenican, in combination with a urea herbicide, the spectrum of activity on the effective control of Galium aparine, Veronica spp. and Viola spp. can be extended. As a result, this combined use represents an important technological advantage. Surprisingly, it has additionally been found that the combined herbicidal activity of diflufenican and a urea herbicide is much greater than expected for certain weed species when used in combination before emergence or after emergence be, for. B. as pre-emergence or post-emergence spray. In other words, the herbicidal activity of diflufenican together with a urea derivative shows an unexpected and remarkable degree of synergism as reported by P.M. LTammes, Netherlands Journal of Plant Pathology, 70 (1964), p.73-80 in an article entitled "Isobolees, a graphic representation of synergism in pesticides" and by Limpel, L E., PH Schuldt and D. Lamont, 1962, Proc.NEWCC 16: 48-53 defined using the formula

~ E = X + Y

in E the expected percentage growth inhibition by a mixture of two herbicides at defined doses, X the percentage growth inhibition by the herbicide A at a defined dose and Y the percentage growth inhibition by the herbicide B at a defined dose.

If the observed effect is greater than expected, the combination is synergistic.

The remarkable synergism with Galium aparine and Avena fatua allows improved reliable control of two of the most abundant crops in cereal crops and results in a significant reduction in the amount of weed control herbicide used.

A high degree of control of these weed species is desirable to prevent (a) crop loss due to competition or difficulties in harvesting and seed cleaning, and (b) the return of unwanted weed seeds to the soil.

By "urea herbicide" is meant in the present specification also mixtures of urea herbicides, if the Kontaxt permits this .. Preference is given to mixtures of isoproturon and neburon in a weight ratio of 2: 1 to 1: 2, in particular in a weight ratio of 1: 1 ,

Accordingly, the invention makes it possible to control the growth of weeds, i. H. undesired vegetation, at a point of occurrence, by application to the location of the presence of quantities of (a) a urea herbicide, preferably a compound of the general formula

R ¹ N (R ² ) CON (R ³ ) R ⁴

wherein R ^{1 is} an optionally substituted cyclic hydrocarbon group, preferably an aromatic group such as the phenyl group, or an aromatic heterocyclic group such as the benzothiazol-2-yl group, R ^{2 is} a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms or an optionally substituted cyclic hydrocarbon group such as the 2-methylcyclohexyl group, and R ^{4 represents} a hydrogen atom or a linear or branched alkyl or alkoxy group having ί to 6 carbon atoms, and (b) diflufenican which are herbicidally effective in combination with each other. For this purpose, the urea herbicide and diflufenican are usually used in the form of herbicidal agents, ie in combination with compatible diluents or carriers and / or surface-active agents which are suitable for use in herbicidal compositions, for example as described below. Preferred compounds of the general formula II are those in which R ^{2 is} a hydrogen atom or methyl group and R ^{3 is} the methyl group.

Compounds of the general formula II, in which R ¹ denotes a phenyl group, optionally in the 3- and / or 4-position, relative to the nitrogen atom, by a chlorine or bromine atom or an optionally halogen-substituted linear or branched alkyl or alkoxy group is substituted with 1 to 6 carbon atoms or by a similarly optionally substituted phenoxy ', or the benzothiazol-2-yl group, are also preferred. Particular preference is given to compounds of the general formula II in which R ^{2 is} a hydrogen atom, R ^{3 is} the methyl group and either (1) R ^{1 is} the phenyl, 3-trifluoromethylphenyl or 4-chlorophenyl group and R ^{4 is} the methyl group, or (2) R ^{1 is} the 4-chlorophenyl group and R ^{4 is} the methoxy group; these compounds are known as fenuron, fluometuron, monuron and monolinuron. Very particular preference is given to compounds of the general formula II in which R ^{2 is} a hydrogen atom and R ^{3 is} the methyl group and (3) R ^{1 is} the 3-chloro-4-methylphenyl group or the 4-isopropylphenyl group and R ^{4 is} the methyl group, or (4) R ^{1 is} the 3,4-dichlorophenyl group and R ^{4 is} a methyl, methoxy or butyl group, or (5) R ^{1 is} the benzothiazol-2-yl group, R ² and R ^{3 are} each a methyl group and R ^{4 represents} a hydrogen atom; These compounds are known as Chlortoluron, Isoproturon, Diuron, Linuron, Neburon and Methabenzthiazuron.

The application rates of urea herbicide and diflufenican vary according to the nature of the weeds, the agents used, the time of use, climatic conditions and soil conditions and, when used to control weed growth in crop growing areas, the nature of the crops. When applied to a crop-growing area, the application rate should be sufficient to combat weed growth, without the crops are noticeably and permanently damaged. In general, taking into account these factors with application rates of 150 g to 10 kg urea herbicide and 25 g to 750 g diflufenican each per hectare good results. However, greater or lesser amounts may be used, depending on the particular problem of weed control. The application rates for the urea herbicide are preferably 500 g up to 10 kg / ha and for diflufenican 50 g to 750 g / ha. The combination of urea herbicide and diflufenican may be used for selective weed control, for example to control the following weed species, by targeted or untargeted pre-run or post-emergence application, d. H. by targeted or non-targeted spraying on a weed-infested site used or to be used for growing crops, for example cereals such as wheat, barley, oats, rye, corn and rice, soybeans, field and pea beans, peas, alfalfa , Cotton, peanuts, flax, onions, carrots, turnip rape and sunflowers, existing or sowed grassland, before or after sowing the crop or before or after emergence of the crop. For selective weed control in weed-infested areas and for planting crops, eg. As the above, or should be used, are application rates of 150 to 3500g urea herbicide and from 25 to 250g Diflufenican per ha particularly suitable.

According to one feature of the invention, weed control by pre-emergence or post-emergence application is a combination of (a) urea herbicide selected from chlorotoluron, isoproturon-linuron, methabenzthiazuron and neburon, or mixtures thereof, preferably 2: 1 to 1: 2 w / w. Mixtures, for example 2: 1 to 1: 2Gew./Gew.-Gemischen, and in particular the 1: 1 wt./wt. Mixture of isoproturon and neburon, and of (b) diflufenican at application rates of 500 to 3500 g / ha , preferably 500 to 2,500 g / ha, (a) and from 50 to 250 g / ha (b) in proportions of (a) to (b) from 70: 1 to 2: 1 and preferably 50: 1 to 2: 1 wt To eradicate a very wide range of annual broadleaf weeds and grassy weeds in cereal crops, such as wheat, barley, oats and rye, without appreciable permanent damage to crops. The combination described above exhibits both leaf activity and residual activity (soil activity) and, as a result, can be applied over a long period of crop development, i. in the period from before emergence of the weeds and before emergence of the crops until after emergence of the weeds and after emergence of the crops. The herbicides are preferably used for controlling weeds in autumn-seeded (winter) crops.

In the use described above, the combined use of (a) is a urea herbicide selected from chlorotoluron, isoproturon and neburon, or 2: 1 to 1: 2 w / w. Mixtures thereof and from (b) diflufenican in a ratio of 20: 1 to 4: 1 w / w. (a) to (b) preferred.

The combination of urea herbicide and diflufenican can also be used to control weeds, especially the weed species listed below, by pre-emergence or postemergence application in orchards and other tree-covered areas, for example in forests, forests and parks, and in plantations, for example Sugar cane, oil palm, rubber plantation plantations. For this purpose, it can be targeted or untargeted, z. B. by targeted or non-targeted sprayer the weeds are applied or on the ground, on which weeds probably grow, before or after planting the trees or plantations at application rates of 1000 to 5000g urea herbicide and 100 to 500g diflufenican per ha ,

The combination of urea herbicide and diflufenican may also be used for weed control, especially to control the weed species listed below, in locations that are not crop growing areas but in which weed control is desirable. Examples of such crop non-cropping areas are airports, industrial areas, railways, road embankments, river banks, irrigation systems, and the like. Waterways, bushland and fallow land or uncultivated land, especially when weed control is desired to reduce fire hazards. For such purposes, where an overall herbicidal effect is often desired, the active ingredients are usually employed in higher dosages than in the crop plant cultures described above. The exact dosage depends on the nature of the treated vegetation and the desired effect. Preemergence or postemergence application and preferably pre-emergence application in a targeted or non-targeted manner, for example by targeted or non-targeted spraying, with application rates of 2500g to 10kg urea herbicide and 200 to 750g diflufenican per ha are particularly suitable for this purpose.

The term "pre-emergence application" refers to the application to the soil of the weed seeds or seedlings before they appear on the soil surface. "Postemergence treatment" refers to application to airborne or exposed areas of the weeds above the soil Floor surface called. "Leaf Activity" means the herbicidal activity produced by application to the overground or exposed parts of the weeds.

By "residual activity" is meant the herbicidal activity caused by application to the soil in which the weed seeds or seedlings are above the soil surface prior to emergence, thereby eliminating the seedlings present at the time of application, or the germinate seeds from the soil after application.

Weed species that can be fought in this way include:

Veronica persica Spergulaarvensis

Veronica hederifolia Cerastium holosteoides

Stellaria media Arenaria serpyllifolia

Lamium purpureum Silenevulgaris

Lamium ampuleule Legousiahybrida

Aphanesarvensis Geranium molle

Galium Pararine Geranium dissectum

Alopecurus myosuroides Erysimumcheiranthoides

Matricaria inodora Descurainea sophia

Matricaria matricoides Montiaperfoliata

Anthemisarvensis Anagallis arvensis

Anthemiscotula myosotis arvensis

Papaverrhoea's Chenopodium album

Poaannua Polygonumaviculare

Aperaspicaventi Polygonum convolvulus

Phalaris paradoxa Galeopsis tetrahit

Phalaris minor · Chrysanthemum segetum

Avena fatua

Loliumperenne

Loliummultiflorum

Bromussterilis

Poatrivialis.

The sustained release efficacy patterns of the urea herbicide and diflufenican also allow for a time-delayed application of separate formulations.

Typically, a tank mix is prepared prior to use by combining separate formulations of the individual herbicidal components.

embodiments

The invention is explained in more detail by the following experiments:

Trial 1

The following greenhouse experiment demonstrated the synergistic activity in the combined use of isoproturon and diflufenican in the control of certain weeds.

Greenhouse experiment showing the nature of the biological synergism between isoproturon and diflufenican. An experiment with 25 individual treatments was performed to monitor the interaction of isoproturon and diflufenican in a wide dose range, i. of 0.125, 250.500 and 1000g of active ingredient per ha of isoproturon plus O, 125.250, 500 and 1000g of active ingredient per ha diflufenican, as shown in the table below.

Isoproturon g / ha

treatment

(D 0

(11) 250

(16) 500

(2) (7) (12) (17) (22) 125 250 500 1000 125 + + + +

Diflufenican g / ha

(3) (8th) (13) (18) (23) 125 250 500 1000 250 + + + + 250 250 250 250 (4) (9) (14) (19) (24) 125 250 500 1000 500 + + + + 500 500 500 500

(5) (10) (15) (20) (25) 125 250 500 1000 1000 _1_

1000

1000

All treatments were carried out in an appropriate volume of water by adding appropriate amounts of a commercial isoproturon concentrate, ie a 50% w / v. aqueous suspension, and the formulated to a wettable powder or spray powder for experimental purposes (Example 1 below) Diflufenican, the 50% w / w. Contained active ingredient, so as to obtain the above-mentioned dose rates / hectare in a spray volume of 260 l / ha. All treatments were performed with a laboratory sprayer equipped with a Spraying Systems Teejet SS 8003E operating at 2.1 daN / cm ² (kgf / cm ² ). In each case 10 to 15 seeds of Galium aparine or Avena fatua were treated, which had been planted 1 to 2cm deep in the loamy soil in plastic pots with a diameter of 9cm. For each treatment, three pots were provided in an arbitrarily distributed block arrangement. The pots were watered after treatment from above and from below. The visual evaluation of weed killing was done 21 days after treatment using a 0 to 10 scale, where 0 means no activity and 10 100% kill compared to untreated plants.

The mean percent weed kill was calculated for each species and is tabulated below for each treatment of the above 25 treatments. ^ ---

Galium

Avena

0 0 0 0 0 0 43 50 67 70 47 80 87 90 93 50 70 83 90 93 70 90 100 100th 100 80 90 93 97 100 80 100 100 100 100 90 97 97 100 100 100 100 100 100 100 95 100 100 100 100

Using these results, the 90% effective dose (ED ₉₀ ) was calculated in grams of active ingredient per ha for diflufenican alone and for isoproturon alone and for mixtures of diflufenican and 125g or 250g, 500g and 1000g isoproturon, respectively dose response curves.

Galium (ED ₉₀ g / ha)

Diflufenican alone · 484

Diflufenican + 125 g / ha isoproturon 209

Diflufenican + 250 g / ha isoproturon 136

Diflufenican + 500 g / ha isoproturon 125

Diflufenican + 1 000g / ha isoproturon 106

Isoproturon alone no effect

Avena (ED ₉₀ g / ha)

Diflufenican alone 538

Diflufenican + 125 g / ha isoproturon 275

Diflufenican + 250 g / ha isoproturon 199

Diflufenican + 500 g / ha isoproturon 122

Diflufenican + 1 000 g / ha isoproturon 107

Isoproturon alone 5668

The values listed above were then used to record the ED ₉₀ isoboles for

a) a "one-sided effect" (Tammes p.74, Fig. 1) in Galium, which was resistant to isoproturon, as indicated in the following Fig. (1)

b) a "two-sided effect" (Tammes p.75, Fig. 2) in Avena, in contrast, both compounds were effective, as indicated in the following Fig. (2).

Figures (1) and (2) clearly show type II and III isoboles characteristic of synergism.

The ED ₉₀ values were used for the preparation of the isoboles because 90% represents the desired level of weed control in agricultural applications (see Isobole for Amitrole / Atrazine Synergism, Tammes, Fig. 5, p.77).

Trial 2

A similar experiment as described in experiment 1 ₍ carried out with chlorotoluron and diflufenican against Avena fatua, with the following results:

Diflufenican alone

Diflufenican + 125 g / ha Chlortoluron Diflufenican + 250 g / ha Chlortoluron Diflufenican + 500 g / ha Chlortoluron Diflufenican + 1 000 g / ha Chlortoluron Chlortoluron alone

ED ₉₀ , g / ha

586 g / ha

450 g / ha

300 g / ha

95 g / ha

75 g / ha

2186 g / ha

These results, shown in Fig. (3) for a "two-sided effect" (Tammes, p.75 Fig. 2) clearly show a type i isobolic feature of synergism.

Trial 3

Greenhouse trial showing the biological synergism between Neburon and Diflufenican.

A trial of 43 individual treatments was performed to investigate the interaction of Neburon and Diflufenican in a wide dose range, i. H. Neburon in a D

Doses of 0.125, 250, 500, 000, 2000 and 4000 g / ha plus diflufenican at a dose of 0.31, 25, 62, 5, 125, 250, 500, 1000 and 1000 g / ha as indicated in the table below:

treatments:

Neburon g / ha

Diflufenican g / ha

(D O (2) 125 (2) 250 (4) 500 (5) 1000 (2) (7) 4000 (8) 31.25 (9) 125 (10) 250 (11) 500 (12) 1000 (13) 2000 31.25 31.25 31.25 31.25 31.25 (14) 62.5   (15) 125 (16) 250 (17) 500 (18) 1000 (19) 2 000 62.5 62.5 62.5 62.5 62.5 (20) 125 (21) 125 (22) 250 (23) 500 (24) 1000 (25) 2000 125 125 125 125 125 (26) 250 (27) 125 (28) 250 (29) 500 (30) 1000 (31) 2 000 250 250 250 250 250 (32) 500 (33) 125 (34) 250 (35) 500 (36) 1000 (37) 2 000 500 500 500 500 500 (38) 1000 (39) 125 (40) 250 (41) 500 (42) 1000 (43) 2 000 1000 1000 1000 1000 1000

All treatments were carried out with an appropriate volume of water to obtain the above dosages per ha in a spray volume of 290 l / ha. Neburon was used as a wettable powder for experimental purposes at 25% w / w. Active ingredient (Example 9 below) was prepared. The diflufenican stood as an aqueous suspension concentrate for experimental purposes (Example 2 below) with 50% w / v. Active ingredient available. All treatments were performed with a laboratory sprayer equipped with a Spraying Systems Teejet SS 8003 E operating at 2.95daN / cm ² (kgf / cm ² ).

The treatments took place after Galium aparine had accumulated and reached the 2-moth growth stage. The plants were grown in non-sterile clayey-loamy soil in 7cm square plastic pots. Each experiment was performed in quadruplicate and the respective pots were distributed in an arbitrary block arrangement in the greenhouse. The pots were then watered after treatment from above and from below.

A visual evaluation of the weed distribution according to a scale of 0 to 100 was made 22 days after the treatment. The mean percent weed kill was calculated for each treatment and for each species. From these results, the 90% herbicidally effective dose, ED ₉₀ , in g / ha for diflufenican alone, for neburone alone and for diflufenican + 125, 250, 500, 2000 and 2000 g / ha neburone was calculated from the response curves for Galium aparine.

Galium (ED _9O g / ha) 459 Diflufenican alone 218 Diflufenican + 125g / ha Neburon 127 Diflufenican + 250g / ha Neburon 49 Diflufenican + 500g / ha Neburon 22 Diflufenican + 1 000 g / ha Neburon 15 Diflufenican +2 000g / ha Neburon 5185 Neburon alone

With the help of the ED ₉₀ values, the isoboles with bilateral effect for Galium of the following FIG. (4) was applied. The isoboles belonged to the type III, which clearly indicates synergism (Tammes, p.75, Fig.2).

Trial 4

Greenhouse trial showing the biological synergism between Linuron and Diflufenican.

A similar experiment was performed as described in experiment 3, with linuron and diflufenican at a dose of 0.250, 500, 000 and 2000 g / ha of linuron, formulated as wettable powder with 50% w / w of active ingredient (commercial product). plus 31,125,500 and 1000g / ha diflufenican. From the results, the following ED _go values were calculated.

ED ₉₀ g / ha 684 201 69

Diflufenican alone Diflufenican + Linuron 250 g / ha Diflufenican + Linuron 500 g / ha Diflufenican + Linuron 1 000 g / ha Diflufenican + Linuron 2 000 g / ha

The results plotted in the following figure (5) for a "two-sided effect" (Tammes, p.75, Figure 2) clearly show a type III isobole characteristic of synergism.

Trial 5

Greenhouse trial showing the biological synergism between Diuron and Diflufenican.

A similar experiment was performed as described above under Ver'such 3 with diuron and diflufenican using 0 and 187.5 g / ha diuron prepared as a wettable powder at 80% w / w. Active ingredient (commercial product) plus 31, 63,125, 250 and 500g / ha diflufenican.

The observed results in weed control were in line with the Limpel formula

compared to expected results.

% Exterminating Diuron g / ha expected (E) 187.5 - observed 78 60 87 93 89 100 93 100 94 100 99

Diflufenican g / ha

31

63

125

250

500

43 68 73 83 85

Since the observed results for the mixtures were significantly higher than the expected (calculated) results, this combination is clearly synergistic.

Trial 6

The efficacy of these synergistic mixtures for broad spectrum weed control in cereal crops has been demonstrated in a series of small scale field trials comparing mixtures of diflufenican (see Example 2 below) and isoproturon with isoproturon alone.

The treatments were carried out before or after emergence three times each on 6m χ 3m arbitrarily arranged plots in a total of 21 field layers in a volume of 141 l / ha using a motorized small plot spraying machine equipped with 6 χ 80015 Spraying Systems Teejets. The mixtures were obtained by dividing the plots with _f

each component was separately sprayed within minutes of each other, d. H. with a total volume of

Weed kill was evaluated 3 months later by counting the number of weeds in 2 χ 0.5 m ² squares per plot. The cereal plants were evaluated for any visual detectable phytotoxicity which occurred on a 0-100 scale, where 0 means no damage and 100 means 100% eradication rate.

The results are summarized in Table 1 below.

Table 1

mean percent weed kill

treatment a) b At the Pa ga vp Vh Va Lp sm Wed. pr aa Ba Whe Isoproturon 2000 g / ha a) b) 93 ^'31 88 "" 84 ' " 31 (4) ₀ (2l 24 '«60« ⁴¹ 13 ' ¹⁾ ₂₅ (5) 31 (2) 83 ^liters 100 ' ² ' 99 ' ³ ' 100 ' ² ' 100 ' ¹ '. 100 ' ¹ ' 2 (4) 2 (4) 1 (6) 1 (2) Isoproturon 1500 g / ha + Diflufenican 125 g / ha a) b) 100 ' ³ ' 93 ' ³ ' 99 < ⁵ > 83 "" 86 ' ² 100 ⁽⁶⁾ 100 "" 100 ' ¹ ' 98 < ⁵¹ 100 ' ² ' ₁₀₀ (6) 100 ^'21 ₁₀₀ (3) 100 ^'21 100 ' ¹ ' 100 ' ¹ ' 4 <5) 3 "» 2 (6) 1 (2) Isoproturon 1 500 g / ha + Diflufencian 250 g / ha ₁₀₀ (3) 93 ^'31 100 ' ⁶ ' 99 ' ⁴ ' 99 ^'41 100 ' ⁶ ' 100 ⁽⁴⁾ 100 ' ¹ ' 95 ' ⁵ ' 99 ' ² ' 1 ₀₀ (6) 100 ^{l 2)} 100 ' ³ ' 100 ' ² ' 100 ' " 100 "» ₈ (4) ₄ (4) 5 (6), ₂ (2)

* mean percentage grain phytotoxicity (highest values detected) Ba = barley Wh = wheat

Numbers in brackets = number of occurrences

Am = Alopecurus myosuroides Va = Viola arvensis

Pa = Poaannua Lp = Lamium purpureum

Ga = Galiumaparine Sm = Stellaria media

Vp = Veronica persica Mi = Matricariainodora

Vh = Veronica hederifolia Pr = Papaverrhoeas

Aa = Aphanesarvensia

(a) = pre-emergence

(b) = postemergence

Trial 7

The efficacy of these synergistic mixtures in broad spectrum weed killing in the corn has been demonstrated in a series of small plot field trials by comparing tank mixes of diflufenican (Example 2 below) and chlortoluron with diflufenican alone.

Treatments were made prior to emergence to each of three 6m χ 3m arbitrarily distributed plots in six field plots in a volume of 261 l / ha using a motorized small plot spraying machine equipped with 6 x 8004 Spraying Systems tea jets.

Weed eradication was evaluated in the spring following the fall application by counting the number of weeds in 3 χ 0.5m ² squares per plot. The grain was evaluated for visually detectable phytotoxicity, corresponding to a scale from 0 to 100, where 0 means no damage and 100 means 100% damage

 The results are summarized in the following Table 2.

Table 2

mean percent weed kill

Treatment An.a Aa

ace

Ca

La

pr

rr

sm

Wed.

vp

Winter Wh Ba Rye

Chlorotoluron 1500g / ha

Diflufenican 62.5 g / ha

100 ^m 100 ° '99 ⁽¹⁾ 99 ^nl

99 ^:

99 ⁿ⁾

99

99 ^{| 2)} 99

Π)

5.7

(4)

Diflufenican 125g / ha

100 ^nl

99 ^(1> 72 ¹²¹ 100 ^nl 99 ⁽³¹ 99 ^KI 99 ^I1)

3.7 ⁽⁴⁾

* mean percentage grain phytotoxicity (detected highest values) Wh = Wheat Ba = Barley Rye = Rye

Numbers in brackets = number of occurrences

An.a = Anagallis arvensis ace = Arenaria serpyllifolia Cs = Chrysanthemum segetum La = Lamiumamplexicaule rr = Raphanusraphanistrum

Aa = Aphanes arvensis Pr = Papaverrhoeas Sm = Stellaris media Mi = Matricarisinodora Vp = Veronica persica

Trial 8

Field trials were conducted in Belgium with tank mixes of diflufenican (Example 2 below) and isoproturon / neburon 1: 1 or with methabenzothiazuron. The treatments were carried out in the autumn pre-emergence to each of 30 m ² plots in order to destroy a range of broad-leaved weeds and grass weeds in winter wheat and winter barley in a volume of 500 l / ha using a hand-sprayer. The evaluation of weed killing took place in the following spring. Crop phytotoxicity was recorded during the winter and spring and the maximum damage observed is reported with the results in Table 3 below.

Table 3

mean phytotoxicity At Pa (1) 100 Wed. sm ga V spp detected maximum phytotoxicity to wheat or barley 125 g / ha 800 g / ha (3) 95 (2) 100 (3) 100 (D 100 (D 100. (4) 8 800 g / ha 200 g / ha

Diflufenican Neburon

Isoproturon diflufenican

93

99 ⁽

₁₀₀ <3>

100 ^MI

97 ^{| 2)}

100

' ¹ '

Methabenzthiazuron 1750g / ha

Numbers in brackets = number of occurrences

V spp = Veronica spp

₁₀ I4)

These experiments clearly demonstrate the broad spectrum of weed control including Galium aparina, Veronica and Viola obtained with the mixtures.

The herbicidal compositions of the invention comprise (a) a urea herbicide and (b) together with a commonly used agricultural diluent or carrier and / or surface active agent diflufenican in a weight ratio of from 400: 1 to 1: 5, preferably from From 70: 1 to 2: 1, and more preferably from 20: 1 to 4: 1, each (a) to (b) combined with, and preferably homogeneously dispersed in, one or more herbicidally acceptable diluents or carriers and / or surface-active agent (s), ie Diluents or carriers or surfactants of the type generally used for herbicidal agents which are compatible with the urea herbicide and diflufenican. By "homogeneously distributed" is meant also those agents in which the urea herbicide and diflufenican are dissolved in the other components. "Herbicides" in the broadest sense means not only ready-to-use agents but also concentrates which must be diluted before use Preferably, the agents contain 0.05 to 90% by weight of urea herbicide and diflufenican. Preferably, the urea herbicide is a compound of general formula II given above.

The herbicidal compositions may contain both a diluent or a carrier and a surfactant, for example a wetting agent, dispersant or emulsifier. The surfactants used in the

herbicidal agents may be ionic or nonionic, for example, sulforicinoleates, quaternary ammonium derivatives, condensation products of ethylene oxide and nonyl or acyl phenols or carboxylic acid ester of anhydrosorbites, which have been rendered soluble by etherification of the free hydroxy groups with ethylene oxide, alkali and alkaline earth salts of sulfuric acid esters and sulfonic acids such as dinonyl and dioctyl sodium sulfono-succinates and alkali and alkaline earth salts of high molecular weight sulfonic acid derivatives such as sodium and calcium lignosulfonates. Examples of suitable solid diluents or carriers are aluminum silicate, talc, calcined magnesia, diatomaceous earth, tricalcium phosphate, cork powder, activated charcoal and clays such as kaolin and benotnit. The solid agents which take the form of dusts, granules or wettable powders or gums. Spray powders are preferably prepared by grinding the urea herbicide and diflufenicans with solid diluents or by impregnating the solid diluents or carriers with solutions of the urea herbicide and diflufenicans in volatile solvents, evaporating the solvents and optionally grinding the resulting products into one Powder. Granules can be prepared by absorbing the urea herbicide and diflufenican, dissolved in volatile solvents, from the solid diluents or carriers in granular form and evaporating the solvents, or by granulating pulverulent compositions which have been obtained as described above _(. Solid herbicidal compositions, especially wettable powders or wettable powders may contain wetting or dispersing agents, for example of the types described above, which, when solid, may also serve as diluents or carriers.

Liquid compositions of the invention may take the form of aqueous, organic or aqueous-organic solutions, suspensions and emulsions which may contain a surfactant. Suitable liquid diluents for the preparation of these liquid agents are water, acetophenone, cyclohexanone, isophorone, toluene, xylene and oils of mineral, animal or vegetable origin and mixtures thereof. Surfactants which may be present in the liquid agents may be ionic or nonionic, for example of the types described above and, when liquid, may also serve as diluents or carriers.

Wettable powders and concentrate-form liquid agents can be diluted with water or other suitable diluents, such as mineral oils or vegetable oils, especially if they are liquid concentrates, where the diluent or carrier is an oil to obtain ready-to-use agents , If desired, the liquid agents of the urea herbicide and diflufenicans may be used in the form of self-emulsifying concentrates containing the active ingredients dissolved in the emulsifying agents or in solvents containing emulsifying agents or emulsifiers compatible with the active ingredients; simply adding water to such concentration gives the ready-to-use agents.

Liquid concentrates in which the diluent or carrier is an oil can be applied without further dilution by electrostatic spraying.

Herbicidal agents according to the invention may also contain, if desired, conventional additives such as adhesives, protective colloids, thickeners, penetrants, stabilizers, scavengers, anticaking agents, dyes and corrosion inhibitors. These additives can also serve as carriers or diluents.

Preferred herbicidal compositions according to the invention are aqueous suspension concentrates containing 10 to 70% w / v. Urea herbicide and diflufenican, 2 to 10% w / v. Surfactant, 0.1 to 5% w / v. Thickener and 15 to 87.9Vol .-% water; wettable powders or spray powders containing 10 to 90% w / w Urea herbicide and diflufenican, 2 to 10% w / w surfactant and 10 to 88% w / w. solid diluent or carrier; liquid water-soluble concentrates containing 10 to 30% w / v. Urea herbicide and diflufenican, 5 to 25% w / v. surfactants and 45 to 85% by volume of water-miscible solvent, for example dimethylformamide; liquid emulsifiable suspension concentrates containing 10 to 70% w / v. Urea herbicide and diflufenican, 5 to 15% w / v. Surfactant, 0.1 to 5% w / v. Thickening agent and 10 to 84.9% by weight of organic solvent; Granules containing 2 to 10% w / w. Urea herbicide and diflufenican, 0.5 to 2% w / w. surfactant and 88 to 97.5% w / w. granular carriers and emulsifiable concentrates containing 0.05 to 90% w / v, preferably 1 to 60% w / v. Urea herbicide and diflufenican, 0.01 to 10% w / v. and preferably to 10% w / v. surfactant and 9.99 to 99.94%, preferably 39 to 98.99% by volume of organic solvent.

Herbicidal agents according to the invention may also contain the urea herbicide and diflufenican, in combination with and preferably homogeneously dispersed, in one or more other pesticidal compounds and, if desired, one or more compatible pesticidal-diluents or carriers, surfactants and usual additives, as described above. Examples of other pesticidally active compounds which are present in the herbicides of the invention. For example, to broaden the spectrum of weed species being combated, include alachlor = a-chloro-2,6-diethyl-N (methoxymethyl) acetanilide, asulam = methyl ^ -aminobenzenesulfonyl-carbamate, alloxydim-Na = Na-salt of 2- (1-allyloxyaminobutyl-1-J-S, -dimethyl) -methoxycarbonylcyclohexane-IS-dione, atrazine = (2-chloro-4-ethylamino-6-isopropylamine) -1,3, 5-triazine, barban = 4-chlorobut-2-ynyl-N- (3-chlorophenyl) carbamate, benzoyl-propyl = ethyl-N-benzoyl-N- (3,4-dichlorophenyl) -2-aminopropionate, especially bromoxynil 3,5-dibromo-4-hydroxybenzonitrile, butachloro = N- (butoxymethyl) -o: -chloro-2,6-diethylacetanilide, butylate = S-ethyl-N, N-diisobutyl (thiocarbamate), carbetamide = DN-ethyl -2- (phenylcarbamoyloxy) propionamide, chlorophenpropmethyl = methyl-2-chloro-2- (4-chlorophenyl) -propionate, chloropropham = isopropyl-N-fS-chlorophenylcarbamate, cyanazine = 2-chloro-4- (1-cyano -l-methylethylamino) -6-ethyl amine o-1,3,5-triazine, cycloate = N'-cyclohexyl-N-ethyl-s-ethyl-1-thiocarbamate), 2,4-D = 2,4-dichlorophenoxyacetic acid, dalapon = 2,2-dichloropropionic acid, 2, 4-DB = 4 (2,4-dichlorophenoxy) butyl acid, Desmedipham = 3- (ethoxycarbonylamino) phenyl-N-phenylcarbamate, dialate = S-2,3-dichloroallyl-N, N-diisopropyl (thiocarbamate), dicamba = S ^ Dichloro-methoxybenzoic acid, dichloroprop = (±) -2- (2,4-dichlorophenoxy) -propionic acid, difenzoquat = i-dimethyl-S, -diphenyl-pyrazolium salts, dinitramine = N ¹ , N ¹ -diethyl-2,6 -dinitro-4-trifluoro-methyl-m-phenylenediamine, EPTC = S-ethyl-N 1 -dipropy-kthiocarbamate), ethofumesate = 2-ethoxy-2,3-dihydro-3,3-dimethyl-benzofuran-5-yl-methylsulfonate, flamprop-isopropyl isopropyl (±) -2- (N-benzoyl-3-chloro-4-fluoroaniline) propionate, flampropymethyl = methyl (±) -2- (N-benzoyl-3-chloro-4-fluoroaniline) propionate , in particular loxynil = 4-hydroxy-3,5-diiodobenzonitrile, MCPA = 4-chloro-2-methylphenoxyacetic acid, MCPB = 4- (4-chloro-2-methylphenoxy) -butyric acid, in particular mecoprop = (±) -2- (4-chloro-2-methyl-phenoxy) -propionic acid, metamitron = A- amino-3-methyl-6-phenyl-1,2,4-triazine-5 (4H) -one, metribuzin = 4-amino -6-t-butyl-3- (methylthio) 1,2,4-triazine-5- (4H) -one, molinate

S-ethyl N, N-hexamethylene (thiocarbamate), oxadiazone = 3- (2,4-dichloro-5-isopropoxyphenyl) -5-t-butyl-1,3,4-oxadiazolin-2-one, paraquat = 1, 1'-dimethyl-4,4'-bipyridylium salts, pebulate = S-propyl-N-butyl-N-ethyl (thiocarbamate), Phenmedipham = 3- (methoxycarbonyl-aminolphenyl-N-methylphenylcarbamate, Prometryn = 4, 6-bisisopropylamino-2-methylthio-1,3,5-triazine, propachloro = a-chloro-N-isopropyl-acetanilide, propanil = N (3,4-dichlorophenyl) -propionamide, propam = isopropyl-N-phenylcarbamate, pyrazone = 5-amino-4-chloro-2-phenylpyridazine-3 (2H) -one, simazine = 2-chloro-4,6-bisethylamino-1,3,5-triazine, TCA = trichloroacetic acid, thiobencarb = S- (4 -Chlorobenzyl) -N, N-diethylthiolcarbamate, triallate = S-2,3,3-trichloroallyl N, N-diisopropyl (thiocarbamate) and trifluralin = 2,6-dinitro-N, N-dipropyl-4-trifluoromethylaniline; insecticides, such as Carbaryl = naphth-1-yl-N-methylcarbamate; synthetic pyrethroids such as permethrin and cypermethrin; and fungicides such as 2,6-dimethyl-4-tridecylmorpholine, methyl N- (1-butylcarbamoyl-b enzimidazol-2-yl) carbamate, 1,2-bis (3-methoxycarbonyl-2-thioureido) benzene, isopropyl 1-carbamoyl-3- (3,5-dichlorophenyl) hydantoin and 1- (4-chloro phenoxy) -3,3-dimethyl-1- (1,2,4-triazol-1-yl) -butan-2-one. Other biologically active substances which may be included in or used in the herbicidal compositions of the invention are plant growth regulators such as succinic acid (succinamicacid), (2-chloroethyl) trimethylammonium chloride and 2-chloroethane. phosphonic acid; or fertilizers containing, for example, nitrogen, potassium and phosphorus, as well as trace elements essential for the good growth of plants, such as iron, magnesium, zinc, manganese, cobalt and copper.

Pesticidal compounds and other biologically active substances which may be incorporated in or used in the herbicidal compositions of the present invention, for example those mentioned above and which are acids, may, if desired, be in the form of common derivatives, for example alkali salts and Amine salts and esters, are used.

The compositions of the present invention may be provided as an article of manufacture containing the urea herbicide and diflufenican and optionally other pesticidal compounds as described above or, as preferred, as a herbicidal agent as described above, and preferably as a herbicide Concentrate which must be diluted before use, comprising the urea herbicide and diflufenican within a container for the aforesaid urea herbicide and diflufenican and said herbicidal agent, and instructions associated with and indicating said container in which The urea herbicide mentioned therein and diflufenican or herbicidal weed control agents should be used. The containers are generally conventional containers for the storage of chemical substances which are solid at normal ambient temperatures and of herbicidal agents, in particular in the form of concentrates, for example cans and canisters made of metal, which may be internally lacquered, or which consist of plastic , Glass and plastic bottles, and if the contents of the container is a solid, for example a granular herbicidal agent, boxes, for example of cardboard, plastics and metal or bags. The containers are generally spacious enough to accommodate amounts of active ingredients or herbicidal compositions sufficient to treat at least 4,047 m ² Land for the purpose of weed control, but should not exceed the appropriate methods for the normal handling size. The instructions are physically attached to the container, for example printed directly on it, or on a sticker, or a tag. The instructions usually indicate that the contents of the container, optionally after dilution, should be used to control the growth of the weeds, in effort doses of 150 g to 10 kg, preferably 500 g to 10 kg urea herbicide and from 25 g to 170 g, preferably 50g to 750g diflufenican per ha, in the manner described above and for the purposes described above.

The herbicidal compositions of the present invention comprise (a) a urea herbicide and (b) diflufenican as a combined preparation for simultaneous, separate or sequential use for weed control at a site of infestation. Preferably, the urea herbicide is a compound of general formula II given above.

embodiments

The following examples illustrate the herbicidal compositions of the invention.

example 1

A spray powder was produced from:

Diflufenican 50% w / w.

Neukai BX (sodium alkyl naphthalene sulfonate) 10% w / w.

Sodium lignosulfonate 3% w / w.

SoproponT36 (sodium polycarboxylate) 0.5% w / w.

Hymod AT (Bindeton) ad 100% w / w

Example 2

An aqueous suspension concentrate was prepared from:

Diflufenican 50% w / v

Ethylan BCP (a nonylphenol ethylene oxide

Condensation product containing 9 mol

Ethylene oxide per mole of phenol) 0.5% w / v.

Soprophor FL (triethanolamine salt of a

oxyethylated polyarylphenol phosphate) 1.0% w / v.

SoproponT36 (sodium polycarboxylate) 0.5% w / v

Antifoam FD 0.1% w / v

Rhodigel23 (xanthan gum) 0.2% w / v

Na-dichlorophen solution, 40% w / w. 0.25% w / v

Water ad 100Vol .-%

Example 3

A (20: 1) wettable powder was prepared from:

Isoproturon. 40% w / w

Diflufenican 2% w / w

Arylan S (Na-dodecyl-benzenesulfonate) 2% w / w.

Darvan No. 2 (Na lignosulfonate) 5% w / w.

Aerosil (microfine SiO ₂ ) 5% w / w.

Celite PF (synthetic magnesium silicate, carrier) 46% w / w.

by mixing the ingredients and grinding the mixture in a hammer mill into a wettable powder which is diluted with water and applied at a rate of 6.25 kg / ha in 200 l spraying liquid per ha to control a wide range of grass and broadleaf (dicotyle) weeds including Avena fatua and Galium aparine can be used by pre- or post-emergence treatment of winter wheat.

Example 4

A 4: 1 aqueous suspension concentrate was prepared from:

Isoproturon 40% w / v

Diflufenican 10% w / v

Ethylan BCP (a nonylphenol-ethylene oxide condensate)

tion product containing 9 moles of ethylene oxide per mole of phenol) 2% wt. / Vol.

Antifoam FD (silicone emulsion antifoam) 0.5% w / v

Pluronic L62 (ethylene oxide / propylene oxide block copolymer) 2% w / v

SoproponT36 (Na salt of a polycarboxylic acid) 0.5% w / v

Attagel 50 (attapulgite expanded clay) 0.5% w / v

Water ad 100Vol .-%

by intimately mixing the components and grinding in a ball mill for 24 hours. The concentrate thus obtained may be dispersed in water and applied to barley at rates of 2 l / ha before or after emergence to eliminate a wide range of broadleaf weeds including galium aparins.

Example 5

A 20: 1 water-dispersible granule was prepared by granulating the components set forth in Example 3 with water in a granulator pan into particles of diameter 0.1 to 2 mm. This granulate could then be applied in an amount of 6.25 kg in 200 liters of water per hectare to control a wide range of grass and broadleaf weeds by subsequent or early application to winter wheat.

Example 6

A 50: 1 emulsifiable suspension concentrate was prepared from:

Isoproturon 50% w / v

Diflufenican 1% w / v

EthylanTU (a nonylphenol / ethylene oxide condensation reaction)

product containing 10 moles of ethylene oxide per mole of phenol) 10% by weight / vol.

Benton 38 (organic derivative of a special magnesium

montmorillonite thickener) 0.05% w / v

Aromasol H (aromatic solvent predominantly

isomeric triethylbenzenes). ad 100% vol.%

by intimately mixing the ingredients and grinding in a ball mill for 24 hours. The emulsifiable suspension concentrate obtained can be diluted with water and applied at a rate of 51 emulsifiable suspension concentrate in 100 l spraying liquid per ha in order to combat or prevent the growth of Alopecurus myosuroides, Viola arvensis and Veronica persica before emergence in winter wheat.

Example 7

A 1: 2 tank mix of (a) aqueous suspension concentrate of diflufenican (Example 2) and (b) a commercial isoproturon formulation, 50% w / v, was prepared by adding 0.51 (a) to 11 (b) were given in 200I of water. The obtained spray liquid was applied to 1 ha of wheat soon after emergence of the seeds and the weeds to eradicate Galium aparine, Viola arvensis, Veronica hederifolia, Veronica persica, Stellaria media and Matricaria inodora.

Example 8

A 1:70 tank mix of (a) aqueous suspension concentrate of diflufenican (Example 2) and (b) a commercial chlorotoluron formulation, 50% w / v, was prepared by adding 0.11 (a) to 71 (b) in 200 l of water were added. The obtained spray liquid was applied to 1 ha of wheat soon after emergence of the seeds and the weeds to eradicate Avena fatua, Alopecurus myosuroides, Stellaria media, Matricaria, inodora, Veronica persica and Viola arvensis.

Example 9

The following wettable powder was prepared:

Neburon 25% w / w

NekalBX (sodium alkylnaphthalene sulfonate) 10% w / w.

Sodium lignosulfonate 3% w / w

SoproponT36 (sodium polycarboxylate) 0.5% w / w.

Silica filler ad 100% w / w.

Example 10 '

A 1.25: 16 tank mix of (a) aqueous suspension concentrate of diflufenican (Example 2) and (b) a commercial formulation of isoproturon / neburon 1: 1, 50% w / w, was prepared by adding 0.251 (a) 3.2 kg (b) were given in 2001 water. The obtained spray liquid was applied to 1 ha of wheat soon after emergence of the seeds and the weeds to control Avena fatua, Alopecurus myosuroides, Stellaria media, Matricaria inodora, Veronica persica and Viola arvensis.

Example 11

A 1: 8.75 tank mix of (a) aqueous suspension concentrate of diflufenican (Example 2) and a commercial, 70% w / w, formulation of methabenzothiazuron (b) was prepared by adding 0.41 (a) to 2, 5kg (b) in 200l of water. The obtained spray liquid was applied to 1 ha of wheat soon after sowing of the seeds and the weeds to control Avena fatua, Alopecurus myosuroides, Stellaria media, Matricaria inodora, Veronica persica and Viola arvensis.

In the herbicide mixtures of the preceding examples, the urea herbicide may be replaced by another urea herbicide or a mixture of urea herbicides.

Claims (4)

Invention claim: A herbicidal composition comprising (a) a urea herbicide and / or (b) N- (2,4-difluorophenyl) -2- (3-trifluoromethylphenoxy) nicotinamide (diflufenican) as active ingredient, together with a conventional diluent or carrier and / or surfactant. 2. Composition according to item 1, characterized in that it contains (a) and (b) in a weight ratio of 400: 1 to 1: 5, in particular from 70: 1 to 2: 1. 3. Composition according to item 1 or 2, characterized in that it contains 0.05 to 90 wt .-% urea herbicide and diflufenican. 4. Composition according to one of the items 1 to 3, characterized in that the urea herbicide is a compound of the general formula