AP537A

AP537A - Selective herbicidal composition.

Info

Publication number: AP537A
Application number: APAP/P/1994/000703A
Authority: AP
Inventors: Jutta Glock; Manfred Hudetz; Elmar Kerber
Original assignee: Ciba Geigy Ag
Priority date: 1993-12-08
Filing date: 1994-12-07
Publication date: 1996-09-16
Also published as: US5618774A; HUT69759A; RO110592B1; CZ306894A3; PL306126A1; EP0657100A2; AU8027994A; BG99238A; RU94042901A; SK150594A3; HU9403490D0; EE9400262A; AP9400703A0; EP0657100A3; ZA949745B; CA2137421A1; CN1106206A; BR9404895A; HRP940832A2

Abstract

A selective herbicidal composition.

Description

Selective herbicidal composition

The present invention relates to a selective herbicidal composition for controlling grasses and weeds in crops of cultivated plants, especially in crops of cereals, which composition comprises a herbicide and a safener (antidote) and protects the cultivated plants, but not the weeds, from the phytotoxic action of the herbicide, and to the use of said composition for controlling weeds in crops of cultivated plants.

When applying herbicides, the cultivated plants may also suffer severe damage owing to factors that include the concentration of the herbicide and the mode of application, the cultivated plant itself, the nature of the soil, and the climatic conditions such as exposure ΐ to light, temperature and rainfall.

To counteract this problem and similar ones, the proposal has already been made to use different compounds as safeners which are able to antagonise the harmful action of the herbicide on the cultivated plant, i.e. to protect the cultivated plant while leaving the herbicidal action on the weeds to be controlled virtually unimpaired. It has, however, been found that the proposed safeners often have a very specific action, not only with respect to the cultivated plants but also to the herbicide, and in some cases also subject to the mode of application, i.e. a specific safener will often be suitable only for a specific cultivated plant and a specific class of herbicide or a specific herbicide.

( Thus, for example, EP-A-0 094 349 discloses quinoline derivatives that protect cultivated plants from the phytotoxic action of herbicides, including phenoxypropionate herbicides, ( ureas, carbamates or diphenyl ethers. EP-A-0 558 448 discloses l-phenylazole-3-carboxylic acid derivatives for protecting cultivated plants from the phytotoxic action of sulfonylureas.

It has now been found that very special safeners selected from the classes of the quinoline derivatives and l-phenylazole-3-earboxylic acid derivatives are suitable for protecting cultivated plants from the phytotoxic action of a certain class of N-phenylsulfonyl-N'triazinylurea herbicides.

Accordingly, the invention provides a selective herbicidal composition comprising, in addition to inert formulation assistants such as carriers, solvents and wetting agents, as active component a mixture of kPlPi 94/00703

-2a) a herbicidally effective amount of a N-phenylsulfonyl-N'-triazinylurea of formula I

wherein

R₂ is hydrogen, fluoro, chloro, bromo, iodo, (X)_nR3, NO₂, NR₄R₅, — C=CR₆, —O-1-C= CR₆ or cyano;

R₇ n is 0 or 1;

R3 is Ci-C₄alkyl or C_t-C₄alkyl which is substituted by 1 to 4 halogen atoms, C₁-C₃alkoxy or Cj^alkylthio; C₂-C₄alkenyl or C₂-C₄alkenyl which is substituted by 1 to 4 halogen atoms,

R₄ is hydrogen, CH₃O, CH₃CH₂O or C₁-C₃alkyl;

R5 is hydrogen or C1-C3alkyl;

Rg is hydrogen, methyl or ethyl;

R7 is hydrogen or methyl;

Rg is Ci-C₄alkyl, CjX^alkoxy, Ci-C₄haloalkoxy, Ci-C₄haloalkyl, Ci-C₄haloalkylthio, CpC^alkylthio, halogen, C^-Csalkoxyalkyl, C^-Csalkoxyalkoxy, amino, C]-C₃ alkylamino or di(C₁-C₃alkyl)amino; and

R₉ is C_rC₄alkyl, C_rC₄alkoxy, C₁-C₄haloalkoxy, C_rC₄haloalkylthio, C_rC₄alkylthio, C₂-C5alkoxyalkyl, C^-Csalkoxyalkoxy, C^-Qalkylthioalkyl or cyclopropyl; with the proviso that Rg and R₉ are not OCHF₂ and SCHF₂;

and

b) as safener to antagonise the herbicide, an antidotally effective amount of either a quinoline derivative of formula Ila

AP. Ο Ο 5 3 7

-3χ₂

(Ha),

O-CH₂-C-O-R₁₀ wherein

R₁₀ is hydrogen, CpCgalkyl or Cj-Cgalkyl which is substituted by Cj-Cgalkoxy or C₃-C6alkenyloxy; and

X₂ is hydrogen or chloro; or of a l-phenylazole-3-carboxylic acid derivative of formula ( lib

Gib) wherein ( E is nitrogen or methine;

R_n is -CCI3, phenyl or halogen-substituted phenyl;

C Rl2 and R₁₃ are each independently of the other hydrogen or halogen; and Rj₄ is

Ci-C₄alkyl; with the proviso that R₂ is not hydrogen if the safener consists of a compound of formula lib.

The alkyl groups occurring the definitions of the substituents may be straight-chain or branched and are typically methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl or tert-butyl. The alkyl groups preferably contain 1 to 3 carbon atoms.

Halogen in the above definitions will be taken to mean fluoro, chloro, bromo and iodo. Fluoro, chloro and bromo are preferred.

AP/PZ 9 4 / 0 0 7 0 3

Alkenyl will be taken to mean straight-chain or branched alkenyl and is typically vinyl,

-4allyl, methallyl, 1-methylvinyl or but-2-en-l-yl. Alkenyl groups having a chain length of 2 to 3 carbon atoms are preferred.

Haloalkyl will typically be fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2,2,2-trifluoroethyl, 2-fluoroethyl, 2-chloroethyl and

2.2.2- trichloroethyl; preferably trichloromethyl, difluorochloromethyl, trifluoromethyl and dichlorofluoromethyl.

Alkoxy is typically methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy and tert-butoxy; preferably methoxy and ethoxy.

f Haloalkoxy is typically difluoromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy,

1.1.2.2- tetrafluoroethoxy, 2-fluoroethoxy, 2-chloroethoxy and 2,2-difIuoroethoxy. Difluoromethoxy, 2-chloroethoxy and trifluoromethoxy are preferred.

Alkylthio is is typically methylthio, ethylthio, propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio or tert-butylthio, preferably methylthio and ethylthio.

Typical examples of alkoxyalkoxy are: methoxymethoxy, methoxyethoxy, methoxypropoxy, ethoxymethoxy, ethoxyethoxy and propoxymethoxy.

Alkylamino is is typically methylamino, ethylamino, n-propylamino or isopropylamino. c ζ Dialkylamino is typically dimethylamino, methylethylamino, diethylamino or n-propylmethylamino.

c

The invention also embraces the salts which the compounds of formula I are able to form with amines, alkali metal and alkaline earth metal bases or quaternary ammonium bases.

Preferred alkali metal and alkaline earth metal hydroxides as salt formers are the hydroxides of lithium, sodium, potassium, magnesium or calcium, most preferably those of sodium or potassium.

Illustrative examples of amines suitable for forming ammonium cations are ammonia as well as primary, secondary and tertiary Cj-Cigalkylamines, Ci-C₄hydroxyalkylamines and C₂-C₄alkoxyalkylamines typically methylamine, ethylamine, n-propylamine, isopropylamine, the four isomeric butylamines, n-amylamine, isoamylamine, hexylamine,

AP. Ο Ο 5 3 7

-5heptylamine, octylamine, nonylamine, decylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, methyl ethylamine, methyl isopropylamine, methyl hexylamine, methyl nonylamine, methyl pentadecylamine, methyl octadecylamine, ethyl butylamine, ethyl heptylamine, ethyl octylamine, hexyl heptylamine, hexyl octylamine, dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, din-amylamine, diisoamylamine, dihexylamine, diheptylamine, dioctylamine, ethanolamine, n-propanolamine, isopropanolamine, Ν,Ν-diethanolamine, N-ethylpropanolamine, N-butylethanolamine, allylamine, n-but-2-enylamine, n-pent-2-enylamine, 2,3-dimethylbut-2enylamine, dibut-2-enylamine, n-hex-2-enylamine, propylenediamine, trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, triisobutylamine, tri-sec-butylamine, tri-n-amylamine, methoxyethylamine and ethoxyethylamine; heterocyclic amines such as pyridine, quinoline, isoquinoline, morpholine, piperidine, pyrrolidine, indoline, quinuclidine and azepine; primary arylamines such as anilines, methoxyanilines, ethoxyanilines, ο-, m- and p-toluidines, phenylenediamines, benzidines, naphthylamines and o-,m- and p-chloroanilines; but preferably triethylamines, isopropylamine and diisopropylamine.

Preferred compounds of formula I or salts thereof for use in the compositions of this invention are those wherein R_g is methyl and R₉ is methoxy.

Those compositions are also preferred which contain a safener of formula Ila. Among these safeners, those compounds are particularly preferred in which X₂ is chloro, and R]o is preferably the group -CH(CH₃)-C5H_n-n or -CH(CH₃)-CH₂-O-CH₂CH=CH₂. Very particularly preferred compositions of this invention contain a compound of formula He

(He)

AP/P/ 9 4 70 0 7 0 3 as safener.

Preferred compounds of formula I are listed in the following Table 1 as compounds of formula lb.

-6Table 1: Compounds of formula lb:

Cmpd. No.	r₂	r₈	r₉
1.01	H	ch₃	och₃
1.02	5-C1	ch₃	och₃
1.03	5-OCH₃	ch₃	och₃
1.04'	5-OC2H₅	ch₃	och₃
1.05	5-F	ch₃	och₃
1.06	4-F	ch₃	och₃
1.07	4-C1	ch₃	och₃
1.08	5-OCH₃	och₃	och₃
1.09	5-OCHF₂	ch₃	och₃	c

Preferred compounds of formula Ha are listed in the following Table 2:

AP. Ο Ο 5 3 7

-Ί Table 2: Compounds of formula Ila:

(Da), o-ch₂-c-o-r₁₀ o

Cmpd. No.	X₂	Rio
2.01	Cl	-CH(CH₃)-C₅H₁₁-n
2.02	Cl	-CH(CH₃)-CH₂OCH₂CH=CH₂
2.03	Cl	H
2.04	Cl	C^H^-n

Preferred compounds of formula lib are listed in the following Table 3:

Table 3: Compounds of formula Hb:

. AP/P/ 94/00703

Cmpd. No.	Rl4	Rl!	R12	R_n	E
3.01	ch₃	phenyl	2-C1	H	CH
3.02	ch₃	phenyl	2-C1	4-C1	CH
3.03	ch₃	phenyl	2-F	H	CH
3.04	ch₃	2-chlorophenyl	2-F	H	CH
3.05	c₂h₅	CC1₃	2-C1	4-C1	N
3.06	ch₃	phenyl	2-C1	4-CF₃	N
3.07	ch₃	phenyl	2-C1	4-CF₃	N

-8Preferred novel combinations of herbicide-safener are listed in Table 4:

Table 4: Preferred combinations of herbicide-safener:

	1.01 1.02 1.05 1.06 1.07	+ + + +	2.01 2.03 2.01 2.01 2.01	1.01 1.03 1.05 1.06 1.07	+ + + + +	2.02 2.03 2.02 2.02 2.02	1.01 1.04 1.05 1.06 1.07	+ + + + +	2.03 2.03 2.03 2.03 2.03	1.01 1.05 1.06 1.07	+ + + +	2.04 2.04 2.04 2.04
r	1.01	+	3.01	1.01	+	3.02	1.01	+	3.03	1.01	+	3.04
1.01	+	3.05	1.01	+	3.06	1.01	+	3.07
r	1.02	+	3.01	1.02	+	3.02	1.02	+	3.03	1.02	+	3.04
\	1.02	+	3.05	1.02	+	3.06	1.02	+	3.07
	1.03	+	3.02	1.03	+	3.03	1.03	+	3.04	1.03	+	3.06
	1.04	+	3.01	1.04	+	3.02	1.04	+	3.03	1.04	+	3.04
	1.04	+	3.05	1.04	+	3.06	1.04	+	3.07
	1.05	+	3.01	1.05	+	3.02	1.05	+	3.03	1.05	+	3.04
	1.05	+	3.05	1.05	+	3.06	1.05	+	3.07
	1.06	+	3.01	1.06	+	3.02	1.06	+	3.03	1.06	+	3.04
	1.06	+	3.05	1.06	+	3.06	1.06	+	3.07
	1.07	+	3.01	1.07	+	3.02	1.07	+	3.03	1.07	+	3.04
	1.07	+	3.05	* 1.07	+	3.06	1.07	+	3.07
c	1.02	+	2.01	1.02	+	2.02	1.02	+	2.04	1.03	+	2.01
	1.03	+	2.02	1.03	+	2.04	1.04	+	2.01	1.04	+	2.02
c	1.04	+	2.04	1.03	+	3.01	1.03	+	3.05	1.03	+	3.07

The compounds of formulae I, Ila and lib are known or they can be prepared by methods analogous to known ones. Compounds of formula I are disclosed, inter alia, in US-A-5 209 771.

The quinoline derivatives falling within the scope of formula Ila and the preparation thereof are known or can be prepared by methods analogous to known ones, inter alia those disclosed in EP-A-0 094 349. Compounds of formula lib are disclosed in EP-A-0 268 554 and EP-A-0 174 562.

The invention also relates to a method of selectively controlling weeds in crops of

AP. Ο Ο 5 3 7 cultivated plants, which comprises treating said cultivated plants, the seeds or seedlings or the crop area thereof, concurrently or separately, with a herbicidally effective amount of the pyrimidine of formula I and, to antagonise the herbicide, an antidotally effective amount of a safener of formula Ila or lib.

-9Suitable cultivated plants which can be protected by the safener of formula Ila or Hb against the harmful action of the aforementioned herbicides are preferably those important in the food or textile sector, typically sugar cane and, in particular, millet, maize, rice and cereals (wheat, rye, barley, oats). It is very particularly preferred to use the novel composition in crops of cereals.

The weeds to be controlled may be monocot as well as dicot weeds.

Crop plants or parts of said plants are typically those referred to above. Crop areas are the areas already under cultivation with the crop plants or seeds thereof, as well as the areas intended for cultivation with said crop plants.

Depending on the end use, a safener of formula Ila or lib can be used for pretreating seeds of the crop plants (dressing of seeds of seedlings) or it can be incorporated in the soil before or after sowing. It can, however, also be applied by itself alone or together with the herbicide pre- or postemergence. Treatment of the plant or the seeds with the safener can therefore in principle be carried out irrespective of the time of application of the ζ phytotoxic chemical. Treatment of the plant can, however, also be carried out by simultaneous application of the phytotoxic chemical and safener (tank mixture). The ( pre-emergence treatment includes treatment of the crop area before sowing as well as treatment of the crop area after sowing but before emergence of the plants.

The concentration of safener to be applied with respect to the herbicide will depend substantially on the mode of application. Where a field treatment is carried out either by using a tank mixture with a combination of safener and herbicide or by separate application of safener and herbicide, the ratio of safener to herbicide will usually be from 1:100 to 10:1, preferably from 1:20 to 1:1, and specifically 1:1. On the other hand, for seed dressing much lower concentrations of safener are required in comparison to the concentration of herbicide per hectare of cultivated area.

In field treatment, 0.001 to 5.0 kg/ha, preferably 0.01 to 0.5 kg/ha, of safener, will usually

AP/P/ 94/00703

- 10 be applied.

The concentration of herbicide is usually in the range from 0.001 to 2 kg/ha, but will preferably be from 0.05 to 1 kg/ha.

For seed dressing, 0.001 to 10 g of safener/kg of seeds, preferably 0.05 to 2 g of safener/kg of seeds, is usually applied. If the safener is used in liquid form shortly before sowing to effect soaking, then it is preferred to use safener solutions that contain the active ingredient in a concentration of 1 to 10 000 ppm, preferably of 100 to 1000 ppm.

For application, it is preferred to process the compounds of formula Π, or combinations of the compounds of formula Ha or Ub and the herbicides of formula I to be antagonised, together with the assistants conventionally employed in formulation technology, to coatable pastes, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granulates or and also encapsulations in e.g. polymer substances. As with the type of compositions, the methods of application such as spraying, atomising, dusting, scattering coating or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances.

The formulations, i.e. the compositions, preparations or mixtures containing the compound of formula Ila or lib or a combination of formula Ila or Ub with the herbicide of formula I to be antagonised and, where appropriate, a solid or liquid adjuvant, are prepared in known manner, e.g. by homogeneously mixing and/or grinding the active ingredients with extenders, typically with solvents, solid carriers and, in some cases, surface-active compounds (surfactants).

Suitable solvents may typically be: aromatic hydrocarbons, preferably the fractions containing 8 to 12 carbon atoms, for example xylene mixtures or substituted naphthalenes; phthalates such as dibutyl or dioctyl phthalate; aliphatic hydrocarbons such as cyclohexane or paraffins; alcohols and glycols and their ethers and esters, for example ethanol, diethylene glycol, 2-methoxyethanol or 2-ethoxyethanol; ketones such as cyclohexanone; strongly polar solvents such as N-methyl-2-pyrrolidone, dimethyl sulfoxide or dimethyl formamide; as well as vegetable oils or epoxidised vegetable oils such as epoxidised coconut oil or soybean oil; or water.

The solid carriers typically used for dusts and dispersible powders are usually natural

Ar .0 0 5 3 7

- 11 mineral fillers such as calcite, talcum, kaolin, montmorillonite or attapulgite. To improve the physical properties it is also possible to add highly dispersed silicic acid or highly dispersed absorbent polymers. Suitable granulated adsorptive carriers are porous types, including pumice, broken brick, sepiolite or bentonite; and suitable nonsorbent carriers are materials such as calcite or sand. In addition, innumerable pregranulated materials of inorganic or organic origin may be used, especially dolomite or pulverised plant residues.

Depending on the safener of formula Ila or lib to be formulated, and usually also on the herbicide, suitable surface-active compounds are nonionic, cationic and/or anionic surfactants having good emulsifying, dispersing and wetting properties. Surfactants will also be understood as comprising mixtures of surfactants.

Suitable anionic surfactants may be water-soluble soaps as well as water-soluble synthetic surface-active compounds.

Suitable soaps are the alkali metal salts, alkaline earth metal salts, ammonium salts or substituted ammonium salts of higher fatty acids (C₁₀-C2₂)> e.g. the sodium or potassium salts of oleic or stearic acid, or of mixtures of natural fatty acids which can be obtained, inter alia, from coconut oil or tallow oil. Further suitable soaps are also the fatty acid methyl taurin salts.

More often, however, so-called synthetic surfactants are used, especially fatty sulfonates, ( fatty sulfates, sulfonated benzimidazole derivatives or alkylarylsulfonates.

G The fatty alcohol sulfonates or sulfates are usually in the form of alkali metal salts, alkaline earth metal salts, ammonium salts or substituted ammonium salts, and they contain a Cg-C^alkyl radical which also includes the alkyl moiety of acyl radicals, e.g. the sodium or calcium salt of ligninsulfonic acid, of dodecylsulfate, or of a mixture of fatty alcohol sulfates obtained from natural fatty acids. These compounds also comprise the salts of sulfated and sulfonated fatty alcohol/ethylene oxide adducts. The sulfonated benzimidazole derivatives preferably contain two sulfonic acid groups and one fatty acid radical containing 8 to 22 carbon atoms. Illustrative examples of alkylarylsulfonates are the sodium, calcium or triethanolamine salts of dodecylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid, or of a condensate of naphthalenesulfonic acid and formaldehyde.

, AR/P/ 9 4 / 0 0 7.0 3

Corresponding phosphates, typically salts of the phosphoric acid ester of an adduct of

- 12p-nonylphenol with 4 to 14 mol of ethylene oxide, or phospholipids, are also suitable.

Nonionic surfactants are preferably polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols or of saturated or unsaturated fatty acids and alkylphenols, said derivatives containing 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon moiety and 6 to 18 carbon atoms in the alkyl moiety of the alkylphenols.

Further suitable nonionic surfactants are the water-soluble polyadducts of polyethylene oxide with polypropylene glycol, ethylenediaminopolypropylene glycol and alkylpolypropylene glycol containing 1 to 10 carbon atoms in the alkyl chain, which polyadducts contain 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups. These compounds usually contain 1 to 5 ethylene glycol units per propylene glycol unit

Illustrative examples of nonionic surfactants are nonylphenol polyethoxylates, polyethoxylated castor oil, polyadducts of polypropylene and polyethylene oxide, tributylphenol polyethoxylate, polyethylene glycol and octylphenol polyethoxylate.

Fatty acid esters of polyoxyethylene sorbitan are also suitable nonionic surfactants, typically polyoxyethylene sorbitan trioleate.

c

Cationic surfactants are preferably quaternary ammonium salts carrying, as N-substituent, ⁽ at least one Cg-C₂2alkyl radical and, as further substituents, unsubstituted or halogenated lower alkyl, benzyl or hydroxy-lower alkyl radicals. The salts are preferably in the form of halides, methyl sulfates or ethyl sulfates, for example stearyl trimethylammonium chloride or benzyl bis(2-chloroethyl)ethylammonium bromide.

The surfactants customarily employed in the art of formulation are described, inter alia, in Me Cutcheon’s Detergents and Emulsifiers Annual, MC Publishing Corp.,

Glen Rock,New Jersey, 1981, H. Stache, Tensid-Taschenbuch (Handbook of Surfactants), Carl Hanser Verlag, Munich/Vienna 1981.

The agrochemical compositions will usually contain from 0.1 to 99 % by weight, preferably from 0.1 to 95 % by weight, of safener of formula Ila or Hb or mixture of safener and herbicide, from 1 to 99.9 % by weight, preferably from 5 to 99.8 % by weight,

AP. Ο Ο 5 3 7

- 13 of a solid or liquid formulation assistant, and from 0 to 25 % by weight, preferably from

0.1 to 25 % by weight, of a surfactant.

Whereas it is preferred to formulate commercial products as concentrates, the end user will normally use dilute formulations.

The compositions may also contain further ingredients such as stabilisers, antifoams, viscosity regulators, binders, tackifiers, as well as fertilisers or other chemical agents for achieving special effects.

Different methods and techniques may suitably be used for applying the safeners of formula Ila or lib or compositions containing them for protecting cultivated plants from the harmful effects of herbicides of formula I, conveniently the following:

i) Seed dressing

a) Dressing the seeds with a wettable powder formulation of the compound of formula Ha or lib by shaking in a vessel until the safener is uniformly distributed on the surface of the seeds (dry treatment), using up to c. 1 to 500 g of compound of formula Ha or lib (4 g to g of wettable powder) per 100 kg of seeds.

b) Dressing seeds with an emulsifiable concentrate of the compound of formula Ila or Ob by method a) (wet treatment).

(

c) Dressing by immersing the seeds in a mixture containing 100-1000 ppm of compound

C of formula Ila or lib for 1 to 72 hours, leaving them wet or subsequently drying them (seed soaking).

Seed dressing or treatment of the germinated seedlings are naturally the preferred methods of application, as the safener treatment is fully concentrated on the target crop. Usually 1 to 1000 g, preferably 5 to 250 g, of safener is used per 100 kg of seeds. However, depending on the method employed, which also permits the use of other chemical agents or micronutrients, plus or minus deviations from the indicated limiting concentrations are possible (repeat dressing).

ii) Application from a tank mixture

A liquid formulation of a mixture of safener and herbicide (reciprocal ratio from 10:1 to £ 0 ΖΦ0/Λ 6/d/dV

- 141:100) is used, the concentration of herbicide being from 0.01 to 5.0 kg/ha. This tank mixture is applied before or after sowing.

iii) Application in the furrow

The safener formulated as emulsifiable concentrate, wettable powder or granulate is applied to the open furrow in which the seeds have been sown. After covering the furrow, the herbicide is applied pre-emergence in conventional manner.

iv) Controlled release of safener

A solution of the compound of formula Ha or lib is applied to mineral granulate substrates or polymerised granulates (urea/formaldehyde) and allowed to dry. A coating may additionally be applied (coated granulates) which permits controlled release of the safener over a specific period of time.

Formulation Examples for mixtures of herbicides of formula I and safeners of formula Ila or lib (throughout, percentages are bv weight)

FI. Solutions compound mixture

-methoxy-3-(3-methoxypropoxy)propane polyethylene glycol 400 N-methyl-2-pyrrolidone mixture of aromatic hydrocarbons C9-C12

a) %

% %

b) % 20 % %

%

c) % 20 % %

d) %

%

The solutions are suitable for use as microdrops.

F2. Wettable powders compound mixture sodium ligninsulfonate sodium laurylsulfate sodium diisobutylnaphthalene sulfonate octylphenol polyethoxylate (7-8 mol EO)

a) b) % 25 % %

% 3 %

c) d) % 80 % %

%

AP. Ο Ο 5 3 7

- 15 highly dispersed silica kaolin % 88 % % 5 % 10 % % 35 %

The compound mixture is throughly mixed with the adjuvants and this mixture is ground in a suitable mill to give wettable powders which can be diluted with water to give suspensions of any desired concentration.

F3. Coated granulates compound mixture highly dispersed silica inorganic carrier (0 0.1-1 mm) e.g. CaCO₃ or SiO₂

a) b) c)

0.1 % 5 % 15 %

0.9 % 2 % 2 %

99.0 % 93 % 83 %

The compound mixture is dissolved in methylene chloride, the solution is sprayed on to the carrier, and the solvent is removed under vacuum.

F4. Coated granulates

a) b) c) compound mixture polyethylene glycol 200 highly dispersed silica ( inorganic carrier (0 0.1 - 1 mm) ( e.g. CaCO₃ or SiO₂

0.1 % 5 % 15 % 1.0 % 2 % 3 % 0.9 % 1 % 2 %

98.0 % 92 % 80 %

AP/P/ 94/00703

The finely ground compound mixture is uniformly applied in a mixer to the kaolin moistened with polyethylene glycol. Non-dusty coated granulates are obtained in this manner.

F5. Extruder granulates compound mixture sodium ligninsulfonate carboxymethyl cellulose kaolin

a) b) 0.1 % 3 %

1.5 % 2 %

1.4 % 2 %

97.0 % 93 %

C) d) % 15 % % 4 % % 2 % % 79 %

- 16The compound mixture is mixed with the adjuvants and the mixture is moistened with water. This mixture is extruded and then dried in a stream of air.

F6. Dusts	a)		b)		c)
compound mixture	0.1	%	1	%	5
talcum	39.9	%	49	%	35
kaolin	60.0	%	50	%	60

Ready for use dusts are obtained by mixing the active ingredient with the carriers on a suitable mill.

F7. Suspension concentrates	a)	b)	c)	d)
compound mixture	3 %	10 %	25 %	50 %
ethylene glycol	5 %	5 %	5 %	5 %
nonylphenol polyethoxylate	-	1 %	2 %	-
(15molEO)
sodium ligninsulfonate	3 %	3 %	4 %	5 %
carboxymethyl cellulose	1 %	1 %	1 %	1 %
37% aqueous formaldehyde	0.2	% 0.2	% 0.2	% 0.2 %
solution
silicone oil emulsion	0.8	% 0.8	% 0.8	% 0.8 %
water	87 %	79 %	62 %	38 %

Q

The finely ground compound mixture is intimately mixed with the adjuvants to give a Q ♦ suspension concentrate from which suspensions of any desired concentration can be prepared by dilution with water.

The following Examples illustrate the ability of the safeners of formula Ila or lib to protect cultivated plants from the phytotoxic action of herbicides of formula I.

Biological Examples

Example Β1: Under greenhouse conditions, barley is cultivated in plastic pots to the 4-leaf stage. In this stage, the herbicide of Table 1 alone as well as the mixtures of the herbicide with the safener are applied to the test plants. Application is made in the form of an aqueous suspension of the test compounds in 5001 of water/ha. The rates of application of

AP. Ο Ο 5 3 7

- 17 the herbicide are 60, 30 and 15 g/ha, and of those of the test safeners are 125 g/ha. Percentage evaluation is made 3 weeks after application according to the rating:

100 % = test plant withered % = no phytotoxic action.

Examples showing that the damage caused by the safeners to barley and wheat can be markedly reduced are given in Table BI:

Table BI: Percentage phytotoxicity in barley with the herbicide of formula lb alone and in combination with the compounds of formulae Ila and lib at 125 g/ha

Herbicide Safener, Herbicide concentration in [g/ha]

	125 g/ha	60	30	15
1.03	—-	85	70	50
1.03	3.01	40	25	15
1.03	2.01	55	40	25

Examples B2 and B3: Under greenhouse conditions, barley is cultivated in plastic pots to the 4-leaf stage. In this stage, each of the herbicides 1.02, 1.03, 1.04, 1.05,1.08 and 1.09 alone as well as the mixtures of the herbicides with the test safeners 2.01 and 3.01 are ( ' applied to the test plants. Application is made in the form of an aqueous suspension of the test compounds in 5001 of water/ha. The rates of application of the herbicide are 250,125, (7 60» 30,15 and 8 g/ha, and those of the safener are 60 and 30 g/ha. Percentage evaluation is made 3 weeks after application according to the rating:

100 % = test plant withered % = no phytotoxic action.

Examples showing that the damage caused by the safeners to barley and wheat can be markedly reduced are given in Tables B2 and B3:

AP/P/ 9 4/0 0 7 a 3

- 18 Table B2: Percentage phytotoxicity in barley and wheat with the herbicide of formula lb alone and in combination with the safeners of formulae Ila and nb at 60 g/ha

Herbicide Safener Barley Wheat g/ha Herbicide concentration in [g/ha]

		250	125	60	30	15 8	250	125	60	30	15 8
1.05	—	20	10	0	0	-	30	10	0	0	-
1.05	3.01	0	0	0	0	-	10	0	0	0	-
1.05	2.01	10	0	0	0	-	10	0	0	0	-
1.03	___	.	98	95	65	60 -	•	20	0	0	0 -
1.03	3.01	-	85	15	0	0 -	-	0	0	0	0 -
1.03	2.01	-	90	75	30	0 -	.	0	0	0	0 -

Table B3: Percentage phytotoxicity in barley and wheat with the herbicide of formula lb alone and in combination with the safeners of formulae Ila and lib at 30 g/ha

Herbicide Safener Barley Wheat g/ha Herbicide concentration in [g/ha]

	125	60	30	15	8	125	60	30	15	8
1.04	—	80	60	25	15	10	65	35	10	0	0
1.04	3.01	45	35	5	0	0	5	0	0	0	0
1.04	2.01	80	60	25	5	0	5	0	0	0	0
1.08	___	55	45	30	10	5	5	0	0	0	0
1.08	3.01	20	10	5	0	0	0	0	0	0	0
1.08	2.01	35	25	15	5	0	0	0	0	0	0
1.02	—	65	40	5	0	-	25	10	5	0	-
1.02	2.01	45	10	0	0	-	15	5	0	0	-
1.09	...		90	80	45	40	.	98	85	55	35
1.09	2.01	-	90	55	30	0	-	75	45	0	0

Claims

1. A composition for the selective control of weeds in crops of cultivated plants, comprising, in addition to inert carriers and adjuvants, as active component a mixture of

a) a herbicidally effective amount of a N-phenylsulfonyl-N'-triazinylurea of formula I wherein

R₂ is hydrogen, fluoro, chloro, bromo, iodo, (X)_nR₃, NO₂, NR4R5, — C==CR₆, —O-j-(ί— CR₆ or cyano;

R₇ n is Oor 1;

R₃ is C_rC4alkyl or C^^alkyl which is substituted by 1 to 4 halogen atoms, C_rC₃alkoxy or C_rC₃alkylthio; C^^alkenyl or C₂-C₄alkenyl which is substituted by 1 to 4 halogen atoms;

R₄ is hydrogen, CH₃O, CH₃CH₂O or C_rC₃alkyl;

R5 is hydrogen or C_rC₃alkyl;

R₆ is hydrogen, methyl or ethyl;

R₇ is hydrogen or methyl;

R₈ is C_rC₄alkyl, C^^alkoxy, C₁-C₄haloalkoxy, Ci-C₄haloalkyl, C₁-C₄haloalkylthxo, C_rC4alkylthio, halogen, Qj-C^alkoxyalkyl, Cj-Csalkoxyalkoxy, amino, C₁-C₃alkylamino or di(C_rC₃alkyl)amino; and

R9 is C_rC₄alkyl, C₁-C₄alkoxy, Ci-C₄haloalkoxy, C₁-C₄haloalkylthio, C_rC₄alkylthio, C₂-C5alkoxyalkyl, C^-Csalkoxyalkoxy, C^-Cjalkylthioalkyl or cyclopropyl; with the

EOZOO/V6 /d/dtf

-20proviso that R₈ and R₉ are not OCHF₂ and SCHF₂; and

b) as safener to antagonise the herbicide, an antidotally effective amount of either a quinoline derivative of formula Ila (Ha),

O-CHo-C-O-Rio

II f o wherein

R₁₀ is hydrogen, CpCgalkyl or C_rC₈alkyl which is substituted by Cj-Qalkoxy or C₃-C₆alkenyloxy; and

X₂ is hydrogen or chloro; or of a l-phenylazole-3-carboxylic acid derivative of formula lib wherein

E is nitrogen or methine;

R_n is -CC1₃, phenyl or halogen-substituted phenyl;

R₁₂ and Rj₃ are each independently of the other hydrogen or halogen; and R_J4 is C₁-C₄alkyl; with the proviso that R₂ is not hydrogen when the safener consists of a compound of formula lib.

2. A composition according to claim 1, wherein R₈ is methyl and R₉ is methoxy.

AP.00537

-21

3. A composition according to claim 1, wherein the safener is a compound of formula Ila.

4. A composition according to claim 3, wherein X₂ is chloro.

5. A composition according to claim 3, wherein R₁₀ is the group -CH(CH₃)-C5H_n-n or -CH(CH₃)-CH₂-O-CH₂CH=CH₂.

6. A composition according to claim 1, which comprises a compound of formula He (lie) as safener.

7. A method of selectively controlling weeds and grasses in crops of cultivated plants, which comprises treating said plants, the seeds or the locus thereof, concurrently or separately, with an effective amount of a herbicide of formula I according to claim 1 and, ς to antagonise said herbicide, an antidotally effective amount of a safener of formula Ha or lib according to claim 1.

c

8. A method according to claim 7, which comprises treating crops of cultivated plants or areas intended for cropping with cultivated plants, with 0.001 to 2 kg/ha of a herbicide of formula I according to claim 1 and an amount of 0.001 to 0.5 kg/ha of a safener of formula Ila or lib according to claim 1.

p/p/ 9 4 / 0 0 ⁷ 0 3 «X

9. A method according to claim 7, wherein the cultivated plants are cereals.

-22Selective herbicidal composition

Abstract of the Disclosure

A selective herbicidal composition for controlling grasses and weeds in crops of cultivated plants, comprising, in addition to inert carriers and adjuvants, as active component a mixture of

a) a herbicidally effective amount of a N-phenylsulfonyl-N'-triazinylurea of formula I (D,

O wherein the substituents are as defined in claim 1, and

b) to antagonise the herbicide, an antidotally effective amount of a quinoline derivative of formula Ila

O-CH₂-C-O-R₁₀

II wherein

R₁₀ is hydrogen, C_rC₈alkyl or C_rC₈alkyl which is substituted by C_rC₆alkoxy or C₃-C₆alkenyloxy; and

AP.00537

-23 X₂ is hydrogen or chloro; or of a l-phenylazole-3-carboxylic acid derivative of formula lib wherein

E is nitrogen or methine;

R_n is -CCI3, phenyl or halogen-substituted phenyl;

R₁₂ and Rj3 are each independently of the other hydrogen or halogen; and R₁₄ is C₁-C4alkyl.