WO1996029870A1

WO1996029870A1 - Herbicidal compositions

Info

Publication number: WO1996029870A1
Application number: PCT/EP1996/001086
Authority: WO
Inventors: Jutta Glock; Manfred Hudetz; Elmar Kerber
Original assignee: Ciba Geigy AG
Current assignee: Novartis AG
Priority date: 1995-03-30
Filing date: 1996-03-14
Publication date: 1996-10-03
Anticipated expiration: 1997-09-30
Also published as: IL117704A0; AU5108496A

Abstract

A selective herbicidal composition comprising, in addition to conventional formulation assistants, a mixture of a) a herbicidally effective amount of a herbicide of formula (I), or a salt or a stereoisomer of the compounds of formula (I), and b) to antagonise the herbicide, an antidotally effective amount of a safener of formula (IIa) of a compound of formula (IIb1), of a compound of formula (IIb2), of a compound of formula (IIc), of a compound of formula (IId), of a compound of formula (IIe), of a compound of formula (IIf), of a compound of formula (IIg), or of a compound of formula (IIh), wherein the substituents have the meanings claimed in claim 1.

Description

Herbicidal compositions

The present invention relates to a selective herbicidal composition for controlling grasses and weeds in crops of cultivated plants, especially in crops of maize and cereals such as rye, barley, oat and, in particular, wheat and rice, 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 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.

It has now been found that safeners disclosed in EP-A-492 366, WO 91/7874 and WO 94/987 are suitable for protecting cultivated plants from the phytotoxic action of a certain class of pyridine and pyrimidine herbicides. Such herbicides are disclosed, inter alia, in US-A-5 387 575, EP-A-517 215, EP-A-567 014 and EP-A-581 184.

Accordingly, the invention provides a selective herbicidal composition comprising, in addition to customary inert formulation assistants such as carriers, solvents and wetting agenus, a mixture of a) a herbicidally effective amount of a herbicide of formula I

,

wherein

Z is N or CH,

R₁ is cyano, halogen, hydroxy or -OR₇, wherein R₇ is C₁-C₄alkyl, C₂-C₄alkenyl,

C₂-C₄alkynyl, C₁-C₄haloalkyl or C₁-C₄cyanoalkyl,

R₂ and R₃ are each independently of the other hydrogen or C₁-C₄alkyl,

R₄ is 1-imidazolyl, a radical of formula -NHSO₂R₈, wherein R₈ is C₁-C₄alkyl,

C₃-C₁₀cycloalkyl, phenyl, phenyl which is substituted by C₁-C₄alkyl or halogen, pyridyl, pyridyl which is substituted by C₁-C₄alkyl, trifluoromethyl or halogen, or a radical of formula -NHSO₂NR₉R₁₀, wherein R₉ is hydrogen, C₁-C₆alkyl or C₁-C₆alkoxy, and R₁₀ is C₁-C₆alkyl, C₁-C₆alkenyl, C₂-C₆alkynyl, phenyl or benzyl, or R₉ and R₁₀, together with the linking nitrogen atom, form a piperazinyl or morphohnyl ring, or R₄ is hydroxy, -OM, wherein M is ammonium or an alkali metal, C₁-C₄alkoxy, C₁-C₄alkoxy which is substituted by C₁-C₄alkoxy or C₁-C₁₂alkylsilyl, C₂-C₄alkenyloxy, C₂-C₄alkynyloxy,

C₃-C₁₀cycloalkoxy, halo-C₃-C₁₀cycloalkoxy, phenoxy, benzyloxy, C₁-C₄alkylthio or phenylthio,

R₅ is C₁-C₄alkyl,

R₆ is C₁-C₄alkyl or C₁-C₄alkoxy, and

X is O or S,

or a salt or a stereoisomer of the compounds of formula I, and b) to antagonise the herbicide, an antidotally effective amount of a safener of formula IIa ,

wherein

R₀₁₀ is hydrogen, C₁-C₈alkyl or C₁-C₈alkyl which is substituted by C₁-C₆alkoxy or

C₃-C₆alkenyloxy, and

X₂ is hydrogen or chloro,

of a compound of formula IIb₁

,

wherein

E is nitrogen or methine,

R₁₁ is -CCl₃ or phenyl which is unsubstituted or substituted by halogen,

R₁₂ and R₁₃ are each independently of the other hydrogen or halogen, and

R₁₄ is C₁-C₄alkyl,

of a compound of formula IIb₂

,

wherein

R₁₂ and R₁₃ have the meanings given above, and R₆₆, R₆₇ and R₆₈ are each independently of one another C₁-C₄alkyl, of a compound of formula IIc

,

wherein

A₂ is a

R₂₅ and R₂₆ are each independently of the other hydrogen, C₁-C₈alkyl, C₃-C₈cycloalkyl,

, or C₁-C₄alkyl which is substituted by

; or R₁ and R₂ together form a C₄-C₆alkylene bridge

which may be interrupted by oxygen, sulfur, SO, SO₂, NH or -N(C₁-C₄alkyl)-,

R₂₇ is hydrogen or C₁-C₄alkyl;

R_aa is hydrogen, halogen, cyano, trifluoromethyl, nitro, C₁-C₄alkyl, C₁-C₄alkoxy, C₁-C₄alkylthio, C₁-C₄alkylsulfinyl, C₁-C₄alkylsulfonyl, -COOR_j; -CONR_kR_m, -COR_n,

-SO₂NR_kR_m or -OSO₂-C₁-C₄alkyl;

R_g is hydrogen, halogen, cyano, nitro, C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₄alkylthio, C₁-C₄alkylsulfinyl, C₁-C₄alkylsulfonyl, -COOR_j, -CONR_kR_m, -COR_n, -SO₂NR_kR_m,

-OSO₂-C₁-C₄alkyl, C₁-C₆alkoxy or C₁-C₆alkoxy which is substituted by C₁-C₄alkoxy or halogen, C₃-C₆alkenyloxy or halo-substituted C₃-C₆alkenyloxy, or C₃-C₆alkynyloxy, or

R_a and R_b together form a C₃-C₄alkylene bridge which may be substituted by halogen or C₁-C₄alkyl, or a C₃-C₄alkenylene bridge which may be substituted by halogen or

C₁-C₄alkyl, or a C₄alkadienylene bridge which may be substituted by halogen or

C₁-C₄alkyl;

R_bb and R_h are each independently of the other hydrogen, halogen, C₁-C₄alkyl, trifluoromethyl, C₁-C₆alkoxy, C₁-C₆alkylthio or -COOR_j;

R_c is hydrogen, halogen, nitro, C₁-C₄alkyl or methoxy; R_d is hydrogen, halogen, nitro, C₁-C₄alkyl, C₁-C₄alkoxy, C₁-C₄alkylthio, C₁-C₄alkylsulfinyl, C₁-C₄alkylsulfonyl,

-COOR_j or CONR_kR_m;

R_e is hydrogen, halogen, C₁-C₄alkyl, -COOR_j, trifluoromethyl or methoxy, or R_d and R_e together form a C₃-C₄alkylene bridge;

R_f is hydrogen, halogen or C₁-C₄alkyl;

R_x and R_y are each independently of the other hydrogen, halogen, C₁-C₄alkyl,

C₁-C₄alkoxy, C₁-C₄alkylthio, -COOR₂₈, trifluoromethyl, nitro or cyano;

R_j, R_k and R_m are each independently of one another hydrogen or C₁-C₄alkyl; or

R_k and R_m together form a C₄-C₆alkylene bridge which may be interrupted by oxygen, NH or -N(C₁-C₄alkyl)- ;

R_n is C₁-C₄alkyl, phenyl or phenyl which is substituted by halogen, C₁-C₄alkyl, methoxy, nitro or trifluoromethyl;

R₂₈ is hydrogen, C₁-C₁₀alkyl, C₁-C₄alkoxy-C₁-C₄alkyl, C₁-C₄alkylthio-C₁-C₄alkyl, di-C₁-C₄alkylamino-C₁-C₄alkyl, halo-C₁-C₈alkyl, C₂-C₈alkenyl, halo-C₂-C₈alkenyl,

C₃-C₈alkynyl, C₃-C₇cycloalkyl, halo-C₃-C₇cycloalkyl, C₁-C₈alkylcarbonyl, allylcarbonyl,

C₃-C₇cycloalkylcarbonyl, benzoyl which is unsubstituted or substituted at the phenyl ring by up to three identical or different members selected from the group consisting of halogen, C₁-C₄alkyl, halo-C₁-C₄alkyl, halo-C₁-C₄alkoxy or C₁-C₄alkoxy; or furoyl, thienyl; or C₁-C₄alkyl which is substituted by phenyl, halophenyl, C₁-C₄alkylphenyl, C₁-C₄alkoxyphenyl, halo-C₁-C₄alkylphenyl, halo-C₁-C₄alkoxyphenyl,

C₁-C₆alkoxycarbonyl, C₁-C₄alkoxy-C₁-C₈alkoxycarbonyl, C₃-C₈alkenyloxycarbonyl,

C₃-C₈alkynyloxycarbonyl, C₁-C₈alkylthiocarbonyl, C₃-C₈alkenylthiocarbonyl,

C₃-C₈alkynylthiocarbonyl, carbamoyl, mono-C₁-C₄alkylaminocarbonyl, di-C₁-C₄alkylaminocarbonyl; or phenylaminocarbonyl which is unsubstituted or substituted at the phenyl ring by up to three identical or different members selected from the group consisting of halogen, C₁-C₄alkyl, halo-C₁-C₄alkyl, halo-C₁-C₄alkoxy or C₁-C₄alkoxy or by one cyano or nitro, or dioxolan-2-yl which is unsubstituted or substituted by one or two C₁-C₄alkyl radicals, or dioxan-2-yl which is unsubstituted or substituted by one or two C₁-C₄alkyl radicals, or C₁-C₄alkyl which is substituted by cyano, nitro, carboxyl or C₁-C₈alkylthio-C₁-C₈alkoxycarbonyl,

of a compound of formula lid

,

wherein

E₂ is nitrogen or methine;

R₂₉ is -CCI₃, phenyl or halo-substituted phenyl;

R₃₀ and R₃₁ are each independently of the other hydrogen or halogen; and R₃₂ is

C₁-C₄alkyl,

of a compound of formula Ile

,

wherein

R₃₃ and R₃₄ are each independently of the other C₁-C₆alkyl or C₂-C₆alkenyl; or R₃₃ and

R₃₄ together are ;

R₃₅ and R₃₆ are each independently of the other hydrogen or C₁-C₆alkyl; or R₃₃ and R₃₄ together are ;

R₃₇ and R₃₈ are each independently of the other C₁-C₄alkyl, or R₃₇ and R₃₈ together are -(CH₂)₅- ;

R₃₉ is hydrogen, C₁-C₄alkyl or ;

or R₃₃ and R₃₄ together are or ;

R₄₀, R₄₁ , R₄₂, R₄₃, R₄₄, R₄₅, R₄₆, R₄₇, R₄₈, R₄₉, R₀₅₀, R₅₁ , R₅₂, R₅₃, R₅₄ and R₅₅ are each independently of one another hydrogen or C₁-C₄alkyl;

of a compound of formula IIf ,

wherein

R₆₃ is hydrogen or chloro, and

R₆₃ is cyano or trifluoromethyl,

of a compound of formula IIg ,

wherein

R₆₅ is hydrogen or methyl,

or of a compound of formula IIh

,

wherein R₆₆ is hydrogen, C₁-C₆alkyl, C₃-C₆cycloalkyl, C₃-C₆alkenyl or C₃-C₆alkynyl, and R₆₇, R₆₈ and R₆₉ are each independently of one another hydrogen, C₁-C₆alkyl,

C₃-C₆cycloalkyl or C₁-C₆alkoxy, and wherein one of the substituents R₆₇, R₆₈ and R₆₉ is different from hydrogen.

The invention also relates to a method of selectively controlling weeds in crops of 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 herbicide of formula I and, to antagonise the herbicide, an antidotally effective amount of a safener of formulae IIa to IIh.

Suitable cultivated plants which can be protected by the safeners of formula IIa to IIh against the harmful action of the aforementioned herbicides are preferably maize and cereals such as rye, barley, oat and, in particular, wheat and rice. Crops will also be understood to include those crops that have been made tolerant to herbicides or classes of herbicides by conventional breeding or genetic engineering methods.

The weeds to be controlled can be monocot as well as dicot weeds. Crop areas will be understood as meaning the areas already under cultivation with the cultivated plants or seeds thereof, as well as the areas intended for cropping with said cultivated plants.

The alkyl groups present in the substituent definitions of the compounds of formulae I and IIa to IIh may be straight-chain or branched and are typically methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl as well as pentyl, hexyl, heptyl, octyl, nonyl, decyl and branched isomers thereof. These alkyl groups can carry further substituents, for example halogen, preferably fluoro, chloro or bromo, alkoxy, thioalkyl, cycloalkyl, phenyl, amino, acyl (e.g. R₈CO-) or Oxo (O=). Suitable alkoxy, thioalkyl, haloalkyl and haloalkoxy groups are derived from the cited alkyl groups.

Typical examples of unsaturated substituent groups are ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, ethinyl, propinyl, butinyl, pentinyl, hexinyl, heptinyl, octinyl as well as isomers which differ in the position of the unsaturated bond or bonds in the molecule, isomers which contain branches, and, in the case of alkene, cis- and trans-isomers. A chloro-substituted propenyl, for example, can be present in the two forms and .

Accordingly, compounds of formula I which are substituted therewith are isomers which can be obtained and used in pure form or as mixture.

Typical examples of alkenyloxy groups and alkynyloxy groups can be derived from the cited alkyl groups.

Cycloalkyl groups typically include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl. Corresponding cycloalkenes can be mono- or polyunsaturated. Typical examples of suitable cycloalkoxy groups can be derived from the cited cycloalkyl groups.

Within the scope of this invention, the term "substituted" may mean monosubstitution as well as polysubstitution. The invention also embraces agronomically acceptable salts which can form the compounds of formula I with, for example, amines, alkali metal bases and alkaline earth metal bases or quaternary ammonium bases.

Among the alkali metal hydroxides and the alkaline earth metal hydroxides as salt formers, the hydroxides of lithium, sodium, potassium, magnesium or calcium merit special mention, in particular those of sodium or potassium. Illustrative examples of amines suitable for the formation of ammonium salt are ammonia as well as primary, secondary and tertiary C₁-C₁₈alkylamines, C₁-C₄hydroxyalkylamines and C₂-C₄alkoxyalkylamines, typically methylamine, ethylamine, n-propylamine, isopropylamine, the four isomeric butylamines, n-amylamine, isoamylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, methylethylamine, methylisopropylamine, methylhexylamine, methylnonylamine, methylpentadecylamine, methyloctadecylamine, ethylbutylamine, ethylheptylamine, ethyloctylamine, hexylheptylamine, hexyloctylamine, dimethylamine, diethylamine, di-n-propylamine, di-isopropylamine, di-n-butylamine, di-n-amylamine, di-isoamylamine, dihexylamine, diheptylamine, dioctylamine, ethanolamine, n-propanolamine, isopropanolamine, N,N-diethanolamine, N-ethylpropanolamine, N-butylethanolamine, allylamine, n-butenyl-2-amine, n-pentenyl-2-amine, 2,3-dimethylbutenyl-2-amine, dibutenyl-2-amine, n-hexenyl-2-amine, propylenediamine, trimethylamine, triethylamine, tri-n-propylamine, tri-isopropylamine, tri-n-butylamine, triisobutylamine, tri-sec-butylamine, tri-n-amylamine, methoxyethylamine and ethoxyethylamine; heterocyclic amines, typically pyridine, quinoline, isoquinoline, morpholine, piperidine, pyrrolidine, indoline, quinuclidine and azepine; primary arylamines, typically anilines, methoxyanilines, ethoxyanilines, o,m,p-toluidines, phenylenediamines, benzidines, naphthylamines and o,m,p-chloroanilines; preferably triethylamine, isopropyaamine and di-isopropylamine.

Preferred compositions according to this invention comprise as herbicide a compound of formula I, wherein R₄, if Z = N, is 1-imidazolyl, a radical of formula -NHSO₂R₈, wherein R₈ is C₁-C₄alkyl, phenyl or phenyl which is substituted by C₁-C₄alkyl or halogen, hydroxy, C₁-C₄alkoxy or benzyloxy, or

R₄, if Z = CH, is 1-imidazolyl, a radical of formula -NHSO₂R₈, wherein R₈ is C₁-C₄alkyl, phenyl or phenyl which is substituted by C₁-C₄alkyl or halogen, hydroxy, -OM, wherein M is ammonium or an alkali metal, C₁-C₄alkoxy, C₁-C₄alkoxy which is substituted by C₁-C₄alkoxy or C₁-C₁₂alkylsilyl, C₁-C₄alkenyloxy, C₁-C₄alkynyloxy, C₁-C₁₀cycloalkoxy, halo-C₁-C₁₀cycloalkoxy, phenoxy, benzyloxy, C₁-C₄alkylthio, phenylthio or

C₁-C₄alkylsulfonylamino.

Other preferred compositions according to this invention comprise as herbicide a compound of formula I, wherein R₁ is -OR₇ and wherein R₇ has the cited meaning, X is S and Z is CH.

Another group of preferred compositions comprises as herbicide a compound of formula I, wherein R₁ is -OR₇, X is S, Z is CH and R₄ is -NHSO₂R₈ and wherein R₇ and R₈ have the cited meaning.

Among these compositions those are particularly preferred which comprise as herbicide a compound of formula I, wherein R₈ is C₁-C₄alkyl.

Particularly important compositions are those comprising as herbicide a compound of formula I, wherein R₅ and R₆ are methoxy.

Preferred compositions comprise as safener a compound of formula IIa, IIb₁, IIb₂ or IIc.

Among these compositions those are particularly preferred which comprise the safeners of formulae IIb₁ and IIb₂, and also those comprising the safeners of formula IIa and, preferably, of formula IIa₁

.

Preferred compounds of formula I, i.e. the compounds of formula la, are listed in the following Table.

Safeners which are particularly suitable for use in the compositions of this invention are listed in the following Tables.

c-propyl is cyclopropyl.

The safeners listed in Tables 4 to 11 and their preparation are disclosed, inter alia, in EP-A-492 366, WO 91/7874 and WO 94/987.

Depending on the end use, a safener of formula IIa to IIh 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 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 herbicide. Treatment can, however, also be carried out by simultaneous application of the phytotoxic chemical and safener (e.g. as tank mixture).

The concentration of safener 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 1:1, preferably from 1 :50 to 1 :5.

In field treatment it is usual to apply 0.001 to 5.0 kg/ha, preferably 0.001 to 0.5 kg/ha, of safener.

The concentration of herbicide is usually in the range from 0.001 to 2 kg/ha, but will preferably be from 0.005 to 1 kg/ha.

The compositions of this invention are suitable for all methods of application commonly used in agriculture, including preemergence application, postemergence application and seed dressing.

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 safeners of formula II, or mixtures of the safeners of formula II and the herbicides formula I, usefully together with the assistants conventionally employed in formulation technology to emulsifiable concentrates, coatable pastes, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granulates or microcapsules. The formulations are prepared in known manner, conveniently by homogeneously mixing or grinding, or mixing and grinding, the active ingredients with liquid or solid formulation assistants, typically solvents or solid carriers. Surface-active compounds (surfactants) may additionally be used for preparing the formulations.

Suitable solvents may typically be: aromatic hydrocarbons, preferably the fractions containing 8 to 12 carbon atoms such as 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 such as 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 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, 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 natural fatty acid mixtures 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.

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 C₈-C₂₂alkyl 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. IIIustrative examples of alkylarylsulfonates are the sodium, calcium or triethanolamine salts of dodecylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid, or of a condensate of naphthalenesulfonic acid and formaldehyde. Corresponding phosphates, typically salts of the phosphoric acid ester of an adduct of p-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.

Cationic surfactants are preferably quaternary ammonium salts carrying, as N-substituent, at least one C₈-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 "Mc Cutcheon's Detergents and Emulsifiers Annual", Mc Publishing Corp., Ridgewood, New Jersey, 1981, H. Stache, "Tensid-Taschenbuch" (Handbook of Surfactants),

Carl Hanser Verlag, Munich/Vienna 1981, and M. and J. Ash, "Encyclopedia of

Surfactants", Vol I-III, Chemical Publishing Co., New York, 1980-81. The agrochemical compositions will usually contain from 0.1 to 99 % by weight, preferably from 0.1 to 95 % by weight, of safener or mixture of safener and herbicide, from 1 to 99.9 % by weight, preferably from 5 to 99.8 % by weight, 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.

Different methods and techniques may suitably be used for applying the safeners of formula IIa to IIh 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 formulae 13a to IIh 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 II (4 g to 2 g of wettable powder) per 100 kg of seeds. b) Dressing seeds with an emulsifiable concentrate of the compound of formulae Ha to IIh by method a) (wet treatment). c) Dressing by immersing the seeds in a mixture containing 100-1000 ppm of compound of formulae IIa to IIh 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 as a tank mixture

A liquid formulation of a mixture of safener and herbicide (reciprocal ratio from 10:1 to 1:100) is used, the concentration of herbicide being from 0.005 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 IIa to IIh 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.

The invention is illustrated in more detail by the following non-limitative Examples.

Formulation Examples for mixtures of herbicides of formula I and safeners of formula IIa to IIh (throughout, percentages are by weight)

Emulsions of any desired concentration can be prepared by diluting such concentrates with water.

The solutions are suitable for use as microdrops.

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.

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

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.

The 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.

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

The finely ground compound mixture is intimately mixed with the adjuvants to give a 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 IIa to IIh to protect cultivated plants from the phytotoxic action of herbicides of formula I.

Biological Examples

Example B1: Post-emergence applications of compositions of a herbicide of formula I with a safener of formulae IIa to IIh on cereal

Wheat is raised under greenhouse conditions in plastic pots to the 3-4-leaf stage. To the test plants are applied at this stage on the one hand the herbicide of formula I by itself and, on the other hand, the mixtures of the herbicide with a safener of formula IIa to IIh.

Application is made with an aqueous suspension of the test substances (formulation Example F7) prepared with 500 1/ha of water (with 0.2% of wetting agent (X-77)). The rates of application for the herbicide are 250/125/60g/ha and the rates of application for the safener are determined according to the ratios 2:1 and 5:1. 20 days after application, evaluation is carried out on a percentage scale. 100% = plant withered, 0% = no phytotoxic action. The results obtained in this test (see the following Tables B1a to B1c) show that the damage caused to wheat by the herbicide of formula I is markedly reduced with the safeners of formulae IIa to IIh.

The same results are obtained by formulating the compound of formula I according to Examples F1 to F6 and F8.

Example B2: Post-emergence applications of mixtures of a herbicide of formula I with a safener of formulae IIa to IIh on rice

The test plants are sowed or planted under greenhouse conditions in plastic tubs in standard soil. Water is then added up to the surface level of the soil. After 3 days the water level is raised by 2 cm and the test substances are applied in the form of a wettable powder (WP20 for herbicide; WP25 for safener) in the dosage rates listed in the following Table. The test plants are then further cultivated in the greenhouse under optimum conditions. Evaluation is carried out 18 days after application on a percentage scale from 0 to 100% (0% = no damage; 100% = total damage).

The same results are obtained by formulating the compound of formula I according to Examples F1., F2. and F4. to F7. .

Claims

What is claimed is

1. A selective herbicidal composition comprising, in addition to customary inert formulation assistants, a mixture of

a) a herbicidally effective amount of a herbicide of formula I

,

wherein

Z is N or CH,

C₂-C₄alkynyl, C₁-C₄haloalkyl or C₁-C₄cyanoalkyl,

R₂ and R₃ are each independently of the other hydrogen or C₁-C₄alkyl,

C₃-C₁₀cycloalkyl, phenyl, phenyl which is substituted by C₁-C₄alkyl or halogen, pyridyl, pyridyl which is substituted by C₁-C₄alkyl, trifluoromethyl or halogen, or a radical of formula -NHSO₂NR₉R₁₀, wherein R₉ is hydrogen, C₁-C₆alkyl or C₁-C₆alkoxy, and R₁₀ is C₁-C₆alkyl, C₁-C₆alkenyl, C₂-C₆alkynyl, phenyl or benzyl, or R₉ and R₁₀, together with the linking nitrogen atom, form a piperazinyl or morpholinyl ring, or R₄ is hydroxy, -OM, wherein M is ammonium or an alkali metal, C₁-C₄alkoxy, C₁-C₄alkoxy which is substituted by C₁-C₄alkoxy or C₁-C₁₂alkylsilyl, C₂-C₄alkenyloxy, C₂-C₄alkynyloxy,

R₅ is C₁-C₄alkyl,

R₆ is C₁-C₄alkyl or C₁-C₄alkoxy, and

X is O or S,

wherein

C₃-C₆alkenyloxy, and

X₂ is hydrogen or chloro,

of a compound of formula IIb₁

,

wherein

E is nitrogen or methine,

R₁₁ is -CCl₃ or phenyl which is unsubstituted or substituted by halogen,

R₁₄ is C₁-C₄alkyl,

of a compound of formula IIb₂

,

wherein

R₁₂ and R₁₃ have the meanings given above, and

R₆₆, R₆₇ and R₆₈ are each independently of one another C₁-C₄alkyl, of a compound of formula IIc ,

wherein

A₂ is a

C₃-C₆alkenyl, , or C₁-C₄alkyl which is substituted by

; or R₁ and R₂ together form a C₄-C₆alkylene bridge

R₂₇ is hydrogen or C₁-C₄alkyl;

R_aa is hydrogen, halogen, cyano, trifluoromethyl, nitro, C₁-C₄alkyl, C₁-C₄alkoxy, C₁-C₄alkylthio, C₁-C₄alkylsulfinyl, C₁-C₄alkylsulfonyl, -COOR_j, -CONR_kR_m, -COR_n,

-SO₂NR_kR_m or -OSO₂-C₁-C₄alkyl;

C₁-C₄alkyl;

-COOR_j or CONR_kR_m;

R_f is hydrogen, halogen or C₁-C₄alkyl;

R₂₈ is hydrogen, C₁-C₁₀alkyl, C₁-C₄alkoxy-C₁-C₄alkyl, C₁-C₄alkylthio-C₁-C₄alkyl, di- C₁-C₄alkylamino-C₁-C₄alkyl, halo-C₁-C₈alkyl, C₂-C₈alkenyl, halo-C₂-C₈alkenyl,

C₃-C₈alkynylthiocarbonyl, carbamoyl, mono-C₁-C₄alkylaminocarbonyl, di-C₁-C₄alkyl aminocarbonyl; or phenylaminocarbonyl which is unsubstituted or substituted at the phenyl ring by up to three identical or different members selected from the group consisting of halogen, C₁-C₄alkyl, halo-C₁-C₄alkyl, halo-C₁-C₄alkoxy or C₁-C₄alkoxy or by one cyano or nitro, or dioxolan-2-yl which is unsubstituted or substituted by one or two C₁-C₄alkyl radicals, or dioxan-2-yl which is unsubstituted or substituted by one or two C₁-C₄alkyl radicals, or C₁-C₄alkyl which is substituted by cyano, nitro, carboxyl or C₁-C₈alkylthio-C₁-C₈alkoxycarbonyl,

of a compound of formula lid

,

wherein

E₂ is nitrogen or methine;

R₂₉ is -CCI₃, phenyl or halo-substituted phenyl;

C₁-C₄alkyl,

of a compound of formula Ile

,

wherein

R₃₄ together are ;

R₃₅ and R₃₆ are each independently of the other hydrogen or C₁-C₆alkyl;

or R₃₃ and R₃₄ together are ;

R₃₉ is hydrogen, C₁-C₄alkyl or ;

or R₃₃ and R₃₄ together are or ;

R₄₀, R₄₁, R₄₂, R₄₃, R₄₄, R₄₅, R₄₆, R₄₇, R₄8, R₄₉, R₀₅₀, R₅₁, R₅₂, R₅₃, R₅₄ and R₅₅ are each independently of one another hydrogen or C₁-C₄alkyl;

of a compound of formula IIf ,

wherein

R₆₃ is hydrogen or chloro, and

R₆₃ is cyano or trifluoromethyl,

of a compound of formula IIg ,

wherein

R₆₅ is hydrogen or methyl,

or of a compound of formula IIh

,

C₃-C₆cycloalkyl or C₁-C₆alkoxy and wherein one of the substituents R₆₇, R₆₈ and R₆₉ is different from hydrogen.

2. A composition according to claim 1, which comprises as herbicide a compound of formula I, wherein R₄, if Z = N, is 1-imidazolyl, a radical of formula -NHSO₂R₈, wherein R₈ is C₁-C₄alkyl, phenyl or phenyl which is substituted by C₁-C₄alkyl or halogen, hydroxy, C₁-C₄alkoxy or benzyloxy, or

C₁-C₄alkylsulfonylamino.

3. A composition according to claim 1, which comprises as herbicide a compound of formula I, wherein R₁ is -OR₇ and wherein R₇ has the meaning claimed in claim 1, X is S and Z is CH.

4. A composition according to claim 1, which comprises as herbicide a compound of formula I, wherein R₁ is -OR₇, X is S, Z is CH, and R₄ is -NHSO₂R₈, and wherein R₇ and R₈ have the meaning claimed in claim 1.

5. A composition according to claim 4, which comprises as herbicide a compound of formula I, wherein R₈ is C₁-C₄-alkyl.

6. A composition according to claim 1, which comprises as herbicide a compound of formula I, wherein R₅ and R₆ are methoxy.

7. A composition according to claim 1, which comprises as safener a compound of formula IIa, IIb₁, IIb₂, IIc or IIh.

8. A composition according to claim 7, which comprises as safener a compound of formula IIb₁ or IIb₂.

9. A composition according to claim 7, which comprises as safener a compound of formula IIa.

10. A composition according to claim 9, which comprises as safener a compound of formula IIa₁ .

11. A method of selectively controlling weeds and grasses in crops of cultivated plants, which comprises treating said plants, the seeds or seedlings or the locus thereof, concurrently or separately, with an effective amount of a herbicide of formula I and, to antagonise said herbicide, an antidotally effective amount of a safener of formula IIa to IIh.

12. A method according to claim 11, 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 and an amount of 0.001 to 0.5 kg/ha of a safener of formula IIa to IIh.

13. A method according to claim 11, wherein the cultivated plants are maize, rye, barley, oat, wheat or rice.

FD 4.5