DD285280A5 - HERBICIDE MEDIUM - Google Patents

Abstract

The present invention relates to herbicidal agents which are characterised by an effective content of a compound of the formula I, a salt thereof, or a stereoisomer thereof, <IMAGE> in which R<1> represents a heterocyclic radical of the formulae <IMAGE> R<2> represents H, (substituted) alkyl or (C2-C4)alkynyl, R<3> represents Cl or CF3, R<4> represents H or Cl and R<5> represents F or Cl, in combination with a compound of the formula II or a salt thereof <IMAGE> in which R<6> represents a radical of the formula <IMAGE> (substituted) phenyl or (substituted) thienyl, R<7> and R<8> represent alkyl or alkoxy, R<9> represents alkyl or H, and X represents CH or N.

Description

The invention relates to herbicidal compositions which have a particularly high activity in the crops wheat, rye, barley and rice.

Characteristic of the known state of the art

The individual components of the formulas I and II and their use as herbicides is known.

Cfl., 0 0

In Il

0-CH-C-OR ² (I) RS-NH-C-N / (VX (II)

Il Il ^Λ

»0 0

Some compounds of the type of formula I are e.g. For example, in DE-PS 35 36 035 or GB-PS 1 599 121 described. Of the compounds of the formula I, the herbicides 2- (4- (6-chlorobenzoxazol-2-yloxy) -phenoxy) -propionic acid ethyl ester (Ia, common name: fenoxaprop-ethyl) are of particular importance according to the invention. 4- (5-trifluoromethyl-2-pyridyloxy) -phenoxy) -propionic acid butyl ester (Ib; common name: fluazifopbutyl) or mixtures containing in excess the D-enantiomers of fluazifopbutyl, 2- (4- (3-chloro-5 -trifluoromethyl-2-pyridyloxy) phenoxy) propionic acid methyl ester (Ic, common name: haloxyfop-methyl) and the corresponding ethoxyethyl ester (Id, common name: haloxyfopethoxyethyl) and ethyl 2- (4- (6-chloro-2-quinoxalyloxy) phenoxy) propionate (Ie: common name: quizalofop-ethyl). The

ogeniertes by (C Cn) A] kyj, halogen, ha] (CC ^) -alkoxy or (C ₁ -C ₁₎ Alkoxycarbonyi substituted 1st, or thienyl, which is substituted by (C _i -C.) alkoxycarbonyl,

R, R = independently of one another (C.-C.) alkyl or

₁ R ^ = (C ₁ -Ct ₁ ) A] kyl or hydrogen,

1 Λ J. M

R ^υ = (C ₁ -Cg) AlCl y, (C ₃ -C ₆ ) A] kenyl, (C ₃ -C ₆ ) alkynyl or (C ₁ -C ₆ ) alkyl, represented by (C ₁ -C 4) alkoxy or (C ₁ -C ₁ ) alkoxycarbonyl is substituted,

R ¹¹ = H, (C ₁ -Cg) AlCli, (C ₃ -C ₆ ) alkenyl, (C ₃ -C ₆ ) alkynyl or cyclohexyl and

X = CH or N

The herbicide combinations according to the invention have strikingly high efficacies, which are surprisingly much stronger than expected from the effects of the individual components.

The individual components of the formulas I and II and their use as herbicides is known.

Some compounds of the type of formula I are e.g. For example, in DE-PS 35 36 035 or GB-PS 1 599 121 described. Of the compounds of the formula I, the herbicides 2- (4- (6-chlorobenzoxazol-2-yloxy) -phenoxy) -propionic acid ethyl ester (Ia, common name: fenoxaprop-ethyl) are of particular importance according to the invention. Butyl 4- (5-trifluoromethyl-2-pyridyl oxy) phenoxy) propionate (Ib; common name: fluazifopbutyl) or mixtures containing the D-enantiomer of fluazifopbutyl in excess, 2- (4- (3-chloro-5-) trifluoromethyl-2-pyridyloxy) phenoxy) propionic acid methyl ester (Ic, common name: haloxyfop-methyl) and the corresponding ethoxyethyl ester (Id, common name: haloxyfopethoxyethyl) and 2 - (^ - (6-chloro-2-quinoxalyloxy) phenoxy) ethyl propionate (Ie: common name: quizalofop-ethyl). The

-3-

Conference Reports "British Crop Protection Conference Weeds", Brighton, 1985 (compound lic: report 1985 / 2-5 / S · 49; connection Hf: report 1985 / 2-6 / pages 55, 56; Report 1985 / 2-4 / S, 43), from the Conference Report 1985 of the "Asian-Pacific Weed Science Society" (Hh) and from The Pesticide Manual, 8th Edition 1987, p. 182, (Hd and he) known.

ρ The compounds of the formula I can form salts in the case of R = H. Likewise, the compounds of formula II are capable of salt formation on a free NH group. Suitable salts of the compounds of the formula I and II are all customary salts which can be used in agriculture. These include, in particular, alkali (Na, K) salts, alkaline earth (Ca, IvIg) salts and ammonium salts, it being possible for ammonium to be substituted one to four times by organic radicals, in particular alkyl or hydroxyalkyl.

Object of the invention

The Ilerbizidkoinbinationsen invention have strikingly high activities, which are surprisingly v / eentlich stronger than expected from the effects of the individual components.

With the help of the compositions of the invention can be numerous harmful plants in Nutzpflanaenkulturen such. These harmful plants include in particular monocotyledonous weeds such as Alopecurus myoxuroides, Avena fatua or Setaria viridis and dicotyledonous weeds such as Matricaria sp., Galium aparine, Sinapis arvense or Polygonum

2 8 5 2 6

-4-

Presentation of the V / esena of the invention

The invention has for its object to provide a herbicidal agent with high efficiency.

The present invention provides herbicidal compositions which are characterized by an effective content of a compound of the formula I, its salt or its stereoisomers

, -0-GH-C-OR ²

,1

wherein R = a heterocyclic radical of the formulas

R-

- N

or

R = H, (C ₁ -C) -alkyl which may be substituted by (C ₁ -C) -alkoxy or (C ₉ -C,) -alkynyl,

IT = Cl or

A>

R ^ = H or Cl and

R = F or Gl,

in combination with a sulfonyl urea compound of the formula

II or its salt

-4a-

R ⁷ Ν- ζ

or

in which "

R = a rust of the formula R ¹¹ -NSR ¹⁰ or phenyl, da3

If

is substituted by (C ₁ -G.) alkyl, halogen, halogenated ₃ (C ₁ -C or (C ₁ -G.) alkoxycarbonyl, or thienyl which is substituted by (C ₁ -G.) alkoxycarbonyl,

R, R = independently of one another (C ₁ -C ₄ ) AlCl yI or (C -C ₄ ) -

alkoxy,

R ⁹ = (C ₁ -C) alkyl or hydrogen, R ^IU = (C ₁ -C ₆ ) AlCl y, (C _? -C _? ) Alkenyl, (Cg-GgMlkinyl or (C ₁ -C ₆ ) AlCl y), which is substituted by (C ₁ -Cj) alkoxy or (C ₁ -C ₄ ) alkoxycarbonyl, R ¹¹ = H, (C ₁ -C ₆ ) AlCl y, (C ₂ -C ₆ ) alkenyl, (C ₂ -C ₆ ) alkynyl or cyclohexyl and

X = CE or N mean.

It has now been found that the combinations according to the invention are distinguished by a surprisingly high superadditive activity, in particular in the wheat, rye, barley and rice crops.

The components of the combinations according to the invention can be mixed within wide limits without the high

2 8 5 2 a

-4b-

V / efficiencies are lost. The mixing ratios of the compounds of the formula I to the compounds of the formula II can generally vary between 15: 1 to 1: 1, in particular between 10: 1 and 5: 1.

With the aid of the compositions according to the invention, it is possible to combat numerous harmful plants in crops of useful plants.

Another object of the present invention is also a method for controlling harmful plants in Nutzplfanzenkultüren, especially in wheat, rye, barley and rice, dan is characterized in that on the crops or cultivated areas an effective amount of a compound of formula (I) in combination with a compound of formula (II) applied.

The combinations according to the invention can each be used in a dosage in the range from 0.05 to 2 kg of active substance / ha. The application rates vary in particular between 0.05 and 1.0 kg / ha.

The herbicidal combinations according to the invention can be used either as tank mixes in which the active ingredients are mixed together only immediately before the application or as finished formulations. As finished formulations they may be formulated in the form of wettable powders, emulsifiable concentrates, versprübaren solutions, dusts or granules and contain the usual formulation auxiliaries such as wetting agents, adhesives, dispersants, solid or liquid inert materials and grinding aids or solvents.

Wettable powders are preparations which are uniformly dispersible in water and which, in addition to the active ingredient (s), are still conventional wetting agents, such as polyoxyethylated alkylphenols, polyvinyl alcohol, polyoxyethylated oleyl- or stearylamines, alkyl- or alkylphenylsulfonates, and customary dispersing aids such as lignosulfonic acid sodium, potassium or calcium, 2,2'-dinaphthyl-methane-6,6'-disulfonic acid sodium or oleoylmethyltaurine acid.

Emulsifiable concentrates are prepared by dissolving the active ingredient (s) in an organic solvent such as

2 8 5 2 3

-6-

Butanol, cyclohexanone, dimethylformamide, xylene or higher-boiling aromatics and addition of a nonionic wetting agent, for example a polyoxyethylated alkylphenol, a polyoxyethylated oleyl or stearylamine or an alkyl or alkyl phenyl sulfonate. Granules can be prepared either by spraying the active ingredient (s) on adsorptive, granulated inert material or by applying active substance concentrations by means of adhesives of polyvinyl alcohol, polacrylic acid sodium or else mineral oils to the surface of carrier substances. ie sand, kaolinite or granulated inert material.

Dusts are obtained by grinding the active ingredient with finely divided, solid substances, eg. Talc, natural clays, kaolin, bentonite, pyrophillite or diatomaceous earth.

The concentrations of the active ingredients in the commercial formulations may be different. In wettable powders, the total active agent concentration varies between about 20 % and 90 %, the remainder being the formulation additives given above. For emulsifiable concentrates, the active ingredient concentration is about 10 % to 80 %,

For use, the commercial concentrates are optionally diluted in a conventional manner, for. B. wettable powders and emulsifiable concentrates by means of water »

Embodiments Formulation Examples Example 1

A dust is obtained by mixing a) 10 CT (GT) ingredients with 90 GT talcum or other inert material and comminuting in a hammer mill, or b) 60 GT active ingredients, 35 GT

Talcum and 5 GT adhesives, e.g. As a polysaccharide homogenized in the same vise.

Example 2

A wettable powder readily dispersible in water is obtained by mixing 25 parts by weight of active ingredient 64 GT of kaolin-containing quartz as inert substance, 10 parts by weight of potassium lignosuccinate and 1 part by weight of sodium oleoylmethyl laurate as wetting and dispersing agent and to mill in a pin mill. a formulation containing 5% active ingredient content may be composed as follows: / irkstoffe 5% V, 6% of a sulfonated Naphthalinformaldehydkondensats (eg.

Dispersogen A from HOECHST AG), 2 % of a Na salt of a

Cr)

Cr)

Alkylnaphthalenesulphonic acid (for example D, ^v Leonil DB from HOECHST AG), 5 % of a mixture of polypropylene glycol and SiO.sub.2

(R) (eg ^y Acrotin 3Hl from HOECHST AG), 25 % SiO ₂ and

57 % kaolin.

Example 3

A dispersion concentrate readily dispersible in water is obtained by mixing 20 parts by weight of active compound with 6 parts by weight of an alkylphenol polyglycol ether, 3 parts by weight of isotridecanol polyglycol ether (8 ethylene oxide units) and 71 parts by weight of paraffinic mineral oil (boiling range about 255 to more than 377 ^° C.) and in a ball mill to a fineness of less than 5 μm.

Example ² I

An emulsifiable concentrate is obtained from 15 GT active ingredients, 75 GT cyclohexanone as solvent and 10 GT ethoxylated nonylphenol (10 ethylene oxide units) as emulsifier.

Biological examples

The following experiments were carried out under greenhouse conditions.

In all cases, a distinction was made in the combinations between the calculated and the found efficiency. The calculated, theoretically expected degree of effectiveness of a combination is determined according to the formula of S.R. Colby: Calculation of cynergistic and antagonistic responses of herbicidal combinations, Weeds 15 (1967) 20-22.

This formula is:

X. Y

E = X + Y -

100

X = % damage from herbicide A at χ kg / h ?. Application rate;

Y = % damage by herbicide B at y kg / ha application rate;

E = the expected damage from the Herblzide A + B at χ + y kg / ha

If the actual damage is greater than the mathematical expected, the effect of the combination is more than additive, i. H. there is a synergistic effect effect.

Experimental Procedure

The test plants were grown in the greenhouse in pots. Tie application of the active ingredients was carried out alone or in combination (tank mixtures) in dosages d = n indicated as the wheat (Triticum aestivum) the Ί - 5 leaf stage and Galium aparine 5-10 egg, stature height had reached.

3 weeks after the application, the herbicidal activity was assessed by scoring the plants. The information relates

on damage. values. The results are shown in the table below, with the values in brackets corresponding to the expected values calculated according to the Colby formula.

table dose damage in % of ΪΚ AS / hal Gal ium Triticurr active substance 15 aparine aestivum 30 0 0 Ia 50 0 0 75 0 0 100 0 0 125 0 0 150 0 0 5 0 0 10 20 0 Ha 12.5 30 0 15 34 0 25 37 0 50 13 0 5 70 0 10 32 0 hb 12.5 38 · 0 15 43 0 25 50 0 50 63 0 89 0

ίο

Damage in % of

Active ingredient (s) dose 7.5 Ga] ium Triticurr 10 aparine aestivum hc fg AS / hal 15 20 0 7.5 10 23 0 10 15 30 0 15 20 35 0 20 15 ill 0 25 25 65 0 hd 50 50 0 0 5 0 0 7.5 0 0 10 0 0 15 15 0 20 20 0 Ia + Hc 25 50 (20) 0 75 + 65 (23) 0 100+ 73 (30) 0 150+ 55 (23) 0 50+ 68 (30) 0 75 + 75 (35) 0 100+ 60 (30) 0 30+ 78 (Hl) 0 50+ 95 (65) 0 100+

11

Damage in % of

Active Ingredient (s) dose Galium TriticuF [g AS / hal aparine aestivum Ia + Ha 50 - 62 (20) 0 100 - 82 (30) 0 150 -ι 88 (37) 0 50 - 83 (30) 0 75 η 87 (37) 0 125 η 95 (13) 0 25 ^ 75 (3D 0 50 η 90 (13) 0 100 h 100 (70) 0 Ia + Hb 50 η 75 (32) 0 100 h 90 (38) 0 150 H 100 (50) 0 50 i 85 (38) 0 75 H 95 (50) 0 125 ^ 100 (63) 0 25 ^ 80 (13) 0 50 4 100 (63) 0 100 -ι 100 (89) 0 ι- 5 l × 10 l · 15 I-10 15 25 H 12.5 l · 25 l × 50 ^ 5 H 10 - 15 t 10   15   25 • 12.5   25   50

Damage in % of

Active Ingredient (s) dose Gal ium (0) Triticum fg AS / hal aparlne (0) aestivum Ia + Hd 50 + 5 30 (0) 0 100 + 10 45 (0) 0 150 + 15 52 (0) 0 50 + 10 40 (15) 0 75 + 15 48 (0) 0 100 + 20 55 (0) 0 15 + 7.5 30 (20) 0 30 + 15 37 0 50 + 25 50 0

[g AS] = amount of active substance

Ia = ethyl 2- (4- (6-chlorobenzoazol-2-yloxy) phenoxy) propionate

Ha = 3- (4,6-dimethoxy-2-pyrimidinyl) -1- [(N-methyl-N-methylsulfonyl) aminosulfonyl] urea

Hb = 3- (4,6-dimethoxy-2-pyrimidinyl) -1- [(N-methyl-N-ethylsulfonyl) aminosulfonyl] urea

Hc = methyl] -3 - [(1-methoxy-6-methyl-1,3,5-triazin-2-yl) -aminocarbonyl-aminosulfonyl] -2-thiophenearboxylate

Hd = methyl 2 - [(4-methoxy-6-methyl-1,3,5-triazin-2-yl) -aminocarbonylaminosulfonyl] benzoate

Claims (6)

13 HOE 87 / F 199 claims 1. A herbicidal composition, characterized by an effective content of a compound of formula I, their salt or their stereoisomers R-O- CH 0 l 311 2 -CH-C-OR (D wherein R = a heterocyclic radical of the formulas or R = H, (C ₁ -C ₁ ) alkyl substituted by (C ₁ -C ₁₁ ) alkoxy or may be (C -C _ü) alkynyl, R ³ = Cl or CF _3, R ⁴ = H or Cl and 5
R = F or Cl, in combination with a sulfonylurea compound of formula II or its salt O Ν- / 6 «/ V-Vv R -SS-NH-C-N - <() v 0 OR ^ (ID where 0 6 11 "in R = a radical of the formula R ^x _n-SR ^x "or phenyl, the O by (C ₁ -Cj) alkyl, halogen, halogenated or substituted (C ₁ -C _li) alkoxycarbonyl -14- or thienyl substituted by (C .. -C.) alkoxycarbonyl, R, R = independently of one another (C ₁ -C ₄ ) alkyl or (C ₁ -C 4) -alkoxy, R ⁹ = (C, -C.) Alkyl or hydrogen, R ^IU = (C ₁ -C ₆ ) AlCl 4, (C ₂ -C ₆ ) alkenyl, (C ₁ -C ₆ ) -cycloyl or (C ₁ -C ₆ ) -alkyl, which is represented by (C ₁ -C ₆ ) -alkoxy or (C ₂ -C ₄ ) -cycloalkyl. -C.) Alkoxycarbonyl is substituted, R ¹¹ = H, (C ₁ -C ₆ ) AlCli, (C ₃ -C ₆ ) alkenyl, (C ₃ -C ₆ ) alkynyl or cyclohexyl and
X = · CH or H, in addition to conventional HiIfs- and Trägerstofßn. 2. A herbicidal composition according to claim 1, characterized in that they contain 2- (4- (6-chlorobenzoxalzol-2-yloxy) phenoxy) propionsäureethylester in addition to conventional auxiliaries and carriers as the compound of formula I. 3. A herbicidal composition according to claim 1 or 2, characterized in that it is a compound of the formula II, wherein R ⁶ = -NR ¹¹ (SO ₀ R ¹⁰ ), R ⁷ , R ⁸ = CH ₀ or OCH., , r ", R ^iu = (C ₁ -C ₆ ) AIlCyI and X = CH mean or a compound of the group methyl-3 - /" - (4-methoxy-6-methyl-1,3,5-triazine-2 yl-aminocarbonyl-amino-8-sulfonyl-7-2-thiophenecarboxylate, methyl 2 - / "'(4-methoxy-6-methyl-1,3,5-triazin-2-yl) aminocarbonyl-aminosulfonylbenzoate, 2-chloro-N- ( (4-methoxy-6-methyl-1,3,5-triazin-2-yl) -aminocarbonyl) -benzenesulfonamide, 2- (2-chloro-ethoxy) -N - ((4-methoxy-6-methyl-1,3) 5-triazin-2-yl) aminocarbonyl) -benzenesulfonamide, methyl 2 - ((3- (4-methoxy-6-methyl-1, 3ti5-triazin-2-yl) -3-methylaminocarbonyl) am3 _n nosulfonyl) benzoate or I, ethyl-2 - / "" (4,6-dimethoxypyrirnidin-2-yl) -aminocarbonyl-aminosulfonylmethyl / benzoate in addition to conventional excipients and carriers. 4. Herbicidal agents according to one or more of the claims 3 to 3 characterized in that the 15 Violation of the compounds of the formula I to that of the compounds of the formula II varies between 15: 1 and 1: 1. 5. A herbicidal composition according to one or more of claims 1-4, characterized in that the Gewichtsverhäatnis the compounds of formula I to that of the compounds of formula II between 10: 1 and 5: 1 varies. 6. A method for controlling harmful plants in crops, characterized in that applying to the harmful plants or the acreage an effective amount of an agent according to one or more of claims 1-5.