WO1994000987A2 - Selective herbicidal composition - Google Patents

Abstract

A selective herbicidal composition for the control of grasses and weeds in crops of useful plants comprises (a) a herbicidally effective amount of a pyrimidine of formula (I), wherein the substituents are defined in claim 1 and (b) as safener a herbicide-antagonistically effective amount of a quinoline derivative of formula (IIa), wherein R24 is hydrogen or C1-C8alkyl and X2 is hydrogen or chlorine; or of an N-acylsulfamoylphenylurea of formula (IIb), wherein the substituents are defined in claim 1, or of a 1-phenylazole-3-carboxylic acid derivative of formula (IIc), wherein the substituents are defined in claim 1, or of a chloroacetamide of formula (IId), wherein the substituents are defined in claim 1, or of an oxime of formula (IIh), wherein the substituents are defined in claim 1, or of a phenylpyrimidine of formula (IIi), wherein the substituents are defined in claim 1.

Description

Selective herbicidal composition

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

When herbicides are used, considerable damage may be caused to the crop plants depending on such factors as the concentration of herbicide and the mode of application, the species of crop plant, the nature of the soil and climatic conditions, for example period of exposure to light, temperature and rainfall. In particular, severe damage can be caused if, in the course of crop rotation, crop plants that are resistant to the herbicides are followed by other crop plants that have no or only insufficient resistance towards the herbicides.

In order to counter that problem, various compounds have already been proposed that are capable of specifically antagonising the damaging effect of the herbicide on the crop plant, that is to say of protecting the crop plant without at the same time significandy affecting the herbicidal action against the weeds to be controlled. It has been found that the proposed safeners are often very species- or type-specific both as regards the crop plants and as regards the herbicide and in some cases also as a function of the mode of application, that is to say a specific safener is often suitable only for a specific crop plant and a specific class of herbicidal compound.

For example, EP-A-0094349 discloses quinoline derivatives that protect crop plants from the phytotoxic action of herbicides of specific classes of compounds, such as phenoxy- propionic acid ester herbicides, ureas, carbamates or diphenyl ethers.

It has now been found that very specific safeners selected from the classes of the N-acylsulfamoylphenylureas, quinoline derivatives, chloroacetamides and 1-phenylazole- 3-carboxylic acid derivatives are suitable for protecting crop plants from the phytotoxic action of a specific class of pyrimidine herbicides.

There is therefore proposed according to the invention a selective herbicidal composition that comprises as active component, in addition to inert additives such as carriers, solvents and wetting agents, a mixture comprising a) a herbicidally effective amount of a pyrimidine of formula I

wherein

X is oxygen or sulfur or, when W is W₅, may also be NH, NC(O)H or NC(O)R₆₂;

Y is -COOH, or an organic or inorganic salt of that acid, ,

or

,

, or the possible salts of these groups;

R is -OR_{1 1};

R₁ is one of the groups (a), (b) and (c)

R₂ is hydrogen, methyl or the group Q"

wherein

Q₁ is hydrogen, methyl or, together with Q₄, is -(CH₂)₂-, -(CH₂₎₃-, -CH₂CH(OH)CH₂- or -CH₂SCH₂-;

Q₂ is hydrogen or methyl;

Q₃ is hydrogen, trifluoromethyl, ethynyl, vinyl, phenyl, cyano or C_{1 -4}alkoxycarbonyl, C_{1 -4}alkyl, or C_{1 -4}alkyl substituted by hydroxy, C_{1 -4}alkoxy, mercapto, C_{1 -4}alkylmercapto, vinyl, phenyl, 4-hydroxyphenyl, 4-imidazolyl, 3-indolyl, hydroxycarbonyl, C_{1 -4}alkoxycarbonyl, 2-propenyloxycarbonyl, cyano or by carbamoyl; and

Q₄ is hydrogen, methyl, hydroxymethyl, formyl or cyano;

or R₂ together with R₇ is -(CH₂)_p-, -CH₂SCH₂- or -CH₂CHOHCH₂-;

R₃ is hydrogen, C_{1 -4}alkyl, phenyl, or phenyl mono- or di-substituted by fluorine,

chlorine, bromine, methyl, trifluoromethyl, methoxy or by nitro;

R₄ is hydrogen or methyl;

R₅ is C_{1 -6}alkyl, C_{1 -6}haloalkyl, phenyl, benzyl, or phenyl substituted by fluorine,

chlorine, bromine, methyl, trifluoromethyl, methoxy, nitro, cyano, carboxy or by C_{1 -3}alkoxycarbonyl;

R₆ is hydrogen, hydroxymethyl, formyl, cyano, hydroxyimino, C_{1 -4}alkoxyimino,

phosphono, phosphino, methylphosphino or a group COX₁;

R₇ is hydrogen; C_{1 -4}alkyl or C_{1 -4}alkyl substituted by hydroxy, C_{1 -4}alkoxy, mercapto, acylmercapto, C_{1 -4}alkylthio, vinyl, phenyl, 4-hydroxyphenyl, 4-imidazolyl,

3-indolyl, hydroxycarbonyl, C_{1 -4}alkoxycarbonyl, 2-propenyloxycarbonyl, cyano, carbamoyl, methylphosphino or by methylsulfoximino; trifluoromethyl; ethynyl; vinyl or vinyl substituted by chlorine or by methoxy; phenyl or phenyl substituted by fluorine, chlorine, methyl, trifluoromethyl or by methoxy; or cyano or C_{1 -4}alkoxycarbonyl;

R₈ is hydrogen or methyl;

A is oxygen, sulfur or -NH-; m is 1, 2 or 3;

n is 0, 1, 2 or 3;

p is 2 or 3;

X₁ is hydroxy, C_{1 -4}alkoxy, C_3-4alkenyloxy, mercapto, C_{1 -4}alkylthio, amino, C_{1 -4}alkylamino, C_2-4dialkylamino or C_{1 -4}alkoxyamino; or C_{1 -4}alkoxy, C_3-4alkenyloxy, mercapto, C_{1 -4}alkylthio, amino, C_{1 -4}alkylamino, C_{1 -4}dialkylamino or C_{1 -4}alkoxyamino each substituted by phenyl, benzyloxy or by C_{1 -2}alkoxy, or is one of the groups (d), (e) and (f)

wherein

A₁ is oxygen, sulfur or -NH-;

R₉ is hydrogen, C_{1 -4}alkyl or benzyl;

R₁₀ is hydroxymethyl, cyano or a group COQ';

Q is hydroxy, C₁-C₄alkoxy, 2-propenyloxy, benzyloxy, amino or the group (d); and

Q' is hydroxy, C₁-C₄alkoxy, 2-propenyloxy, benzyloxy, amino or the group (d);

R₁₁ is hydrogen, C₁-C₁₀alkyl, C₁-C₄alkoxy-C₁-C₄alkyl, C₁-C₄alkylthio-C₁-C₄alkyl, diC₁-C₄alkylamino-C₁-C₄alkyl, halo-C₁-C₈alkyl, C₂-C₈alkenyl, halo-C₂-C₈alkenyl, C₃-C₈alkynyl, C₃-C₇cycloalkyl, halo-C₃-C₇cycloalkyl, C₁-C₈alkylcarbonyl,

C₁-C₄alkylcarbonyloxy-C₁-C₂alkyl, allylcarbonyl, C₃-C₇cycloalkylcarbonyl, benzoyl that is unsubstituted or substituted at the phenyl ring by up to three identical or different substituents selected from halogen, C₁-C₄alkyl, halo-C₁-C₄alkyl, halo- C₁-C₄alkoxy and C₁-C₄alkoxy; or is furoyl or thienyl; or C₁-C₄alkyl 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-C₈alkynylt--iocarbonyl, carbamoyl, mono-C₁-C₄alkylaminocarbonyl, di-C₁-C₄alkylaminocarbonyl, tri-C₁-C₆alkylsilyl or by

di-C₁-C₆alkyl-phenylsilyl; or phenylaminocarbonyl that is unsubstituted or substituted at the phenyl by up to three identical or different substituents selected from halogen, C₁-C₄alkyl, halo-C₁-C₄alkyl, halo-C₁-C₄alkoxy and C₁-C₄alkoxy or is monosubstituted by cyano or by nitro; or dioxolan-2-yl that is unsubstituted or substituted by one or two C₁-C₄alkyl radicals; oxetan-3-yl or dioxan-2-yl that are unsubstituted or substituted by one or two C₁-C₄alkyl radicals; or C₁-C₄alkyl substituted by cyano, nitro, carboxy or by C₁-C₈alkylthio-C₁-C₆alkoxycarbonyl; or the groups -N=C(CH₃)₂ or -CH₂CH₂ON=C(CH₃)₂;

W is

or W and Y together form a group W₄

or W and Y together form a group W₅

or W and Y together form a group W₆

E is nitrogen or -CR₁₂;

R₁₂ is hydrogen, halogen, hydroxy, C₁-C₄alkoxy, phenyl or benzyl; or phenyl substituted by C₁-C₄alkyl, C₁-C₄alkoxy, C₁-C₄haloalkyl or by halogen; benzyl substituted by C₁-C₄alkyl, C₁-C₄alkoxy, C₁-C₄haloalkyl or by halogen; -COR₁₃, ,

-S(O)_qR₁₆, (4,6-dimethoxy-pyrimidin-2-yl)-oxy; C₁-C₄alkyl that is unsubstituted or substituted by halogen; ethenyl that is unsubstituted or substituted by C₁-C₄alkyl, phenyl, halogen, cyano or C₁-C₄alkoxycarbonyl; ethynyl that is unsubstituted or substituted by halogen, C₁-C₄alkyl or phenyl; phenoxy or phenylthio that are unsubstituted or substituted by C₁-C₄alkyl, C₁-C₄alkoxy, C₁-C₄haloalkyl or halogen; R₁₃ is C₁-C₄alkyl, halo-C₁-C₄a-kyl, C₁-C₄alkoxy-C₁-C₄alkyl; amino, C₁-C₄alkylamino, di-C₁-C₄alkylamino, C₂-C₄haloalkylamino, di-C₂-C₄haloalkylamino, C₁-C₄alkoxyalkylamino, di-C₁-C₄alkoxyalkylamino, C₃-C₄alkenylamino, diallylamino,

-N-pyrrolidino, -N-piperidino, -N-morpholino, -N-thiomorpholino, -N-piperidazino, -O-N=C(CH₃)-CH₃ or -O-CH₂-CH₂-O-N=C(CH₃)-CH₃;

R₁₄ is hydrogen, C₁-C₁₀alkyl that is unsubstituted or substituted by acyl or by cyano;

C₁-C₄alkoxy-C₁-C₄alkyl, C₁-C₄alkylthio-C₁-C₄alkyl, C₁-C₄alkylsulfonyl- C₁-C₄alkyl, C₁-C₄alkylsulfιnyl-C₁-C₄alkyl, or phenyl that is unsubstituted or substituted at the phenyl ring by up to three identical or different substituents selected from halogen, C₁-C₄alkyl, halo-C₁-C₄alkyl, halo-C₁-C₄alkoxy and

C₁-C₄alkoxy;

R₁₅ is hydroxy, C₁-C₁₀alkyl that is unsubstituted or substituted by halogen; C₁-C₆alkoxy that is unsubstituted or substituted by halogen, benzyloxy, C₁-C₆alkoxycarbonyl, C₃-C₆cycloalkyl, acyl, di-C₁-C₄alkylamino or by C₁-C₆alkoxy; phenyl, phenoxy or benzyloxy each of which is unsubstituted or substituted at the phenyl ring by up to three identical or different substituents selected from halogen, C₁-C₄alkyl, halo- C₁-C₄alkyl, halo-C₁-C₄alkoxy and C₁-C₄alkoxy; C₂-C₈alkenyl, halo-C₂-C₈alkenyl, C₃-C₈alkynyl, C₃-C₇cycloalkyl, halo-C₃-C₇cycloalkyl, C₁-C₄alkoxyamino,

C₁-C₄alkylamino, phenylamino, -OSi(CH₃)₃, C₂-C₈alkenyloxy or C₃-C₈alkynyloxy; q is the number 0, 1 or 2;

R₁₆ is Cj-Cjoalkyl that is unsubstituted or substituted by halogen; phenyl that is

unsubstituted or substituted by up to three identical or different substituents selected from halogen, C₁-C₄alkyl, halo-C₁-C₄alkyl, halo-C₁-C₄alkoxy and C₁-C₄alkoxy; C₂-C₈alkenyl, halo-C₂-C₈alkenyl, C₃-C₈alkynyl, C₃-C₇cycloalkyl or halo- C₃-C₇cycloalkyl;

R₁₇ is hydrogen, C_{1 -6}alkyl, C_3-6cycloalkyl, C_1-6alkyl that is monosubstituted by chlorine or mono- to hexa-substituted by fluorine; phenyl or thienyl, or phenyl mono- or disubstituted by fluorine, chlorine, methyl or by methoxy;

R₁₈ is hydrogen, methyl or, together with R₁₇, is -(CH₂)₂-, -(CH₂)₃-, -(CH₂)₄- or

-(CH₂)₅- ;

R₁₉ is hydrogen, methyl, fluorine, chlorine, bromine, C_1-6alkoxy, C_3-6alkenyloxy,

C_3-6alkynyloxy, C_{3 -4}cycloalkyl-C_1-2alkoxy, C_4-6cycloalkoxy, or C_{1 -4}alkoxy that is monosubstituted by cyano, C_1-2alkoxy or by chlorine or mono- to hexa-substituted by fluorine; C_1-6alkylthio or cyano;

R₂₀ is hydrogen, C_{1 -4}alkyl, C_1-3alkylthio or, together with R₂₁, is -(CH₂)₄-, -(CH₂)₅-,

-S(CH₂)₂S- or -S(CH₂)₃S- ;

R₂ι is C_{1 -4}alkyl, C_2-6alkenyl, C_3-6cycloalkyl, C_{1 -6}haloalkyl, C_1-3alkoxy, C_1-3alkylthio, formyl, C_{1 -5}alkylcarbonyl, carboxy, C_{1 -4}alkoxycarbonyl, phenyl, or phenyl substituted by fluorine, chlorine, methyl, trifluoromethyl, methoxy or by nitro; or is 2-, 3- or 4-pyridyl, 2- or 3-furyl or 2- or 3-thienyl;

R₂₂ is hydrogen, C₁-C₆alkyl, C₃-C₆cycloalkyl, C₁-C₆haloalkyl, C₃-C₆alkenyl,

C₃-C₆alkynyl, C₃-C₆haloalkenyl, C₃-C₆haloalkynyl, phenyl or benzyl, or phenyl substituted by C₁-C₄alkyl, C₁-C₄alkoxy, C₁-C₄haloalkyl or by halogen; benzyl substituted by C₁-C₄alkyl, C₁-C₄alkoxy, C₁-C₄haloalkyl or by halogen; halogen, hydroxy, -CHO, -COOH, phenoxy, cyano, phenylthio, -CONH₂, -OCHO,

C₂-C ₅alkanoyloxy, C₂-C₅alkoxycarbonyloxy, C₂-C₃alkylcarbamoyloxy,

di(C₁-C ₂alkyl)carbamoyloxy or di(C₁-C₂alkoxy)phosphonyl;

R₂₃ is hydrogen, C₁-C₆alkyl or CF₃;

r is 0, 1, 2 or 3;

s is 0, 1, 2 or 3;

m is 0, 1 or 2;

R₅₇ is hydrogen, hydroxy, C₁-C₆alkoxy, C₁-C₆alkoxyalkoxy, C₁-C₆acyloxyalkoxy, trimethylsilylethoxy, C₁-C₆alkylsulfonylamino, C₁-C₆alkylthio, imidazolyl, benzyloxy, phenoxy or thiophenoxy, or benzyloxy, phenoxy or thiophenoxy;

R₅₈ is halogen, C₁-C₆haloalkyl, C₁-C₆alkyl, acylamino, C₃-C₆cycloalkyl, halosubstituted C₃-C₆cycloalkyl, C₂-C₆alkenyloxy, C₃-C₆alkynyloxy, C₁-C₆alkoxycarbonyl, C₁-C₆alkoxy, C₁-C₆alkylamino, di-C₁-C₆alkylamino, C₁-C₆alkoxyiminoalkyl, acyl, C₁-C₆alkylthio, phenyl, benzyl, phenylamino or benzylamino;

R₅₉ is halogen, C₁-C₆alkyl, C₁-C₆alkoxy, C₁-C₆alkylamino, di-C₁-C₆alkylamino,

C₁-C₆haloalkyl, C₁-C₆haloalkoxy, nitro, hydroxy, cyano, C₁-C₆alkoxyalkoxy, C₁-C₆alkoxycarbonylalkoxy, C₁-C₆alkylthioalkoxy, C₁-C₆alkylthio, C₁-C₆alkoxyalkyl, C₂-C₆alkenyl, C₃-C₆alkynyl, benzyloxy or phenoxy;

R₆₀ is halogen, C₁-C₆alkyl, C₁-C₆haloalkyl, C₃-C₆cycloalkyl, halo-substituted

C₃-C₆cycloalkyl, C₂-C₆alkenyloxy, C₃-C₆alkynyloxy, C₁-C₆alkoxycarbonyl, C₁-C₆alkoxy, C₁-C₆alkylamino, di- C₁-C₆alkylamino, phenyl, benzyl, C₁-C₆alkoxyiminoalkyl, acyl, C₁-C₆alkylthio, phenylamino or benzylamino;

R₆₁ is hydrogen, hydroxy, C₁-C₆alkoxy, C₁-C₆alkoxyalkoxy, C₁-C₆acyloxyalkoxy, trimethylsilylethoxy, C₁-C₆alkylsulfonylamino, C₁-C₆alkylthio, imidazolyl, benzyloxy, phenoxy or thiophenoxy, or benzyloxy, phenoxy or thiophenoxy;

R₆₂ is C₁-C₆alkyl or C₁-C₆alkoxy;

R₆₆ is C₁-C₆alkyl, or C₁-C₆alkyl which is substituted by up to 3 fluorine atoms, 1

chlorine atom, 1 C₁-C₄alkoxy group, 1 C₁-C₄alkoxycarbonyl group, 1

dimethylcarbamoyl group, 1 carbamoyl group, 1 cyano group, 1 vinyl group, 1 ethynyl group or 1 phenyl group which is unsubstituted by fluorine, chlorine, bromine, methyl, trifluoromethyl or methoxy, or is phenyl, or -phenyl which is up to trisubstituted by fluorine, chlorine, bromine, methyl, trifluoromethyl, methoxy or nitro; or NR₆₇R₆₈; or OR₆₉;

R₆₇ is hydrogen or C₁-C₄alkyl;

R₆₈ is hydrogen, C₁-C₆alkyl, phenyl, pyridyl, or phenyl which is monosubstituted to trisubstituted or pyridyl which is monosubstituted by C₁-C₄alkyl, fluorine, chlorine, bromine, trifluoromethyl, methoxy or nitro; or is C₁-C₆alkylcarbonyl, trifluoromethylcarbonyl, C₃-C₆cycloalkylcarbonyl, benzylcarbonyl, 2-, 3- or 4-pyridylcarbonyl, 2- or 3-furyl- or thiophenylcarbonyl, benzoyl, or benzoyl which is monosubstituted to disubstituted by fluorine, chlorine, bromine, methyl, trifluoromethyl, methoxy or nitro; or Q^alkoxycarbonyl, benzoyloxycarbonyl, aminocarbonyl, aminothiocarbonyl, or aminocarbonyl or aminothiocarbonyl each of which is monosubstituted to disubstituted by phenyl or Ci-C^alkyl, it being possible for the phenyl group to be substituted by fluorine, chlorine, methyl or methoxy; and

R₆₉ is hydrogen, C₁-C₆alkyl or C₂-C₆alkenyl, or C₂-C₆alkenyl which is substituted by halogen or phenyl, or C₁-C₄alkoxycarbonyl-C₁-C₄alkyl or C₁-C₄alkylthiocarbonylC₁-C₄alkyl; and b) as safener, a herbicide-antagonistically effective amount of a quinoline derivative of formula IIa

wherein

R₂₄ is hydrogen or C₁-C₈alkyl and

X₂ is hydrogen or chlorine;

or of an N-acylsulfamoylphenylurea of formula IIb

wherein

A₂ is a group

R₂₅ and R₂₆, independently of one another, are hydrogen, C₁-C₆alkyl, C₃-C₈cycloalkyl,

C₃-C₆alkenyl, C₃-C₆alkynyl, , or C₁-C₄alkyl substituted by

C₁-C₄alkoxy or by

or R₁ and R₂ together form a C₄-C₆alkylene bridge that can be interrupted by oxygen, sulfur, SO, SO₂, NH or by -N(C₁-C₄alkyl)-;

R₂₇ is hydrogen or C₁-C₄alkyl;

R_a is hydrogen, halogen, cyano, trifluoromethyl, nitro, C₁-C₄alkyl, C₁-C₄alkoxy,

C₁-C₄alkylthio, C₁-C₄alkylsulfmyl, 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-C₄alkylsulfmyl, C₁-C₄al-cylsulfonyl, -COOR_j, -CONR_kR_m, -COR_n, -SO₂NR_kR_m, -OSO₂-C₁-C₄alkyl, C₁-C₆alkoxy, or C₁-C₆alkoxy substituted by C₁-C₄alkoxy or by halogen; C₃-C₆alkenyloxy, or C₃-C₆alkenyloxy substituted by halogen; or C₃- C₆alkyny loxy ;

or R_a and R_b together form a C₃-C₄alkylene bridge that can be substituted by halogen or by C₁-C₄alkyl, or a C₃-C₄alkenylene bridge that can be substituted by halogen or by C₁-C₄alkyl, or a C₄alkadienylene bridge that can be substituted by halogen or by C₁-C₄alkyl;

R_b and R_h, independently of one another, are 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, independently of one another, are hydrogen, halogen, C₁-C₄alkyl,

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

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

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

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

R₂₈ is hydrogen, C₁-C₁₀alkyl, C₁-C₄alkoxy-C₁-C₄alkyl, C₁-C₄alkylthio-C₁-C₄alkyl, diC₁-C₄alkylamino-C₁-C₄alkyl, halo-C₁-C₆alkyl, C₂-C₈alkenyl, halo-C₂-C₈alkenyl, C₃-C₈alkynyl, C₃-C₇cycloalkyl, halo-C₃-C₇cycloalkyl, C₁-C₈alkylcarbonyl, allylcarbonyl, C₃-C₇cycloalkylcarbonyl, benzoyl that is unsubstituted or substituted at the phenyl ring by up to three identical or different substituents selected from halogen, C₁-C₄alkyl, halo-C₁-C₄alkyl, halo-C₁-C₄alkoxy and C₁-C₄alkoxy; or is furoyl or thienyl; or C₁-C₄alkyl 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-C₆alkylthiocarbonyl, C₃-C₈alkenylthiocarbonyl, C₃-C₈alkynylthiocarbonyl, carbamoyl, mono-Cι-C₄alkylaminocarbonyl or by di-C₁-C₄alkylaminocarbonyl; or phenylaminocarbonyl that is unsubstituted or substituted at the phenyl by up to three identical or different substituents selected from halogen, C₁-C₄alkyl, halo-C₁-C₄alkyl, halo-C₁-C₄alkoxy and C₁-C₄alkoxy or monosubstituted by cyano or by nitro; or dioxolan-2-yl that is unsubstituted or substituted by one or two C_1-C₄alkyl radicals; or dioxan-2-yl that is unsubstituted or substituted by one or two C₁-C₄alkyl radicals; or C₁-C₄alkyl substituted by cyano, nitro, carboxy or by C₁-C₆alkylthio-C₁-C₇alkoxycarbonyl;

or of a 1-phenylazole-3-carboxylic acid derivative of formula IIc

wherein

E₂ is nitrogen or methine;

R₂₉ is -CCl₃, phenyl or halo-substituted phenyl;

R₃₀ and R₃₁, independently of one another, are hydrogen or halogen; and

R₃₂ is C₁-C₄alkyl;

or of a chloroacetamide of formula IId

wherein

R₃₃ and R₃₄, independendy of one another, are C₁-C₆alkyl or C₂-C₆alkenyl;

or R₃₃ and R₃₄ together are ; wherein

R₃₅ and R₃₆, independently of one another, are hydrogen or C₁-C₆alkyl; or R₃₃ and R₃₄ together are ; ; w wherein

R₃₇ and R₃₈, independently of one another, are C₁-C₄alkyl;

or R₃₇ and R₃₈ together are -(CH₂)₅-;

R₃₉ is hydrogen, C₁-C₄alkyl or

;

or R₃₃ and R₃₄ together are

wherein

R₄₀, R_41, R₄₂, R₄₃, R₄₄, R₄₅, R₄₆, R₄₇, R₄₈, R₄₉, R₅₀, R₅₁, R₅₂, R₅₃, R₅₄ and R₅₅, independendy of one another, are hydrogen or C₁-C₄alkyl;

or of an oxime of formula IIh

wherein

R₆₃ is hydrogen or chlorine and

R₆₄ is cyano or trifluoromethyl;

or of a phenylpyrimidine of formula IIi

wherein

R₆₅ is hydrogen or methyl.

In the definitions used in this description, the generic terms given, as well as the individual definitions of the substituents obtainable by combining individual subsidiary terms, include, for example, the following individual substituents; this list does not represent a limitation of the invention.

In the diagrammatic representation of the substituents W₁, W₂ and W₃ the linkage point to the substituent Y is always at the upper free valency. For example, in the substituent W₁ the linkage point to substituent Y is in the ortho-position relative to substituent E.

In the above definitions, halogen is to be understood as being fluorine, chlorine, bromine and iodine, preferably fluorine, chlorine and bromine.

Alkyl is methyl, ethyl, isopropyl, n-propyl, n-butyl, isobutyl, sec-butyl, tert-butyl and the various isomeric pentyl, hexyl, heptyl, octyl, nonyl and decyl radicals.

Haloalkyl is, for example, 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, for example, methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy and tert-butoxy; preferably methoxy and ethoxy. Haloalkoxy is, for example, fiuoromethoxy, difluoromethoxy, trifluoromethoxy, 2,2,2- trifluoroethoxy, 1,1,2,2-tetrafluoroethoxy, 2-fluoroethoxy, 2-chloroethoxy and 2,2,2-trichloroethoxy; preferably difluoromemoxy, 2-chloroethoxy and trifluoromethoxy. Alkylthio is, for example, methylthio, ethylthio, propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio, tert-butylthio or isomeric pentylthio, preferably methylthio and ethylthio.

Alkenyl is to be understood as being straight-chain or branched alkenyl, such as vinyl, allyl, methallyl, 1-methylvinyl, but-2-en-1-yl, pentenyl, 2-hexenyl or 3-heptenyl.

Preference is given to alkenyl radicals having a chain length of 2 or 3 carbon atoms.

The alkynyl radicals occurring in the definitions of the substituents may be straight-chain or branched, such as, for example, ethynyl, propargyl, 3-butynyl, 1-methylpropargyl, 1-pentynyl or 2-hexynyl. Ethynyl and propargyl are preferred.

Cycloalkyl is, for example, cyclopropyl, dimethylcyclopropyl, cyclobutyl, cyclopentyl, methylcyclopentyl, cyclohexyl or cycloheptyl, but preferably cyclopropyl, cyclopentyl or cyclohexyl.

Alkoxycarbonyl is, for example: methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl and n-butoxycarbonyl, preferably methoxycarbonyl and ethoxycarbonyl.

Alkoxyalkyl is, for example: methoxymethyl, ethoxymethyl, propoxymethyl, methoxyethyl, ethoxyethyl, propoxyethyl, methoxypropyl, ethoxypropyl or propoxypropyl.

Alkylthioalkyl is, for example: methylthiomethyl, ethylthiomethyl, methylthioethyl, ethylthioethyl or isopropylthioethyl.

Alkylaminoalkyl is, for example: methylaminoethyl, dimethylaminoethyl, ethylaminoethyl or diethylaminoethyl.

Cyanoalkyl is, for example: cyanomethyl, cyanoethyl or cyanopropyl.

Halocycloalkyl is, for example: 2,2-dichlorocyclopropyl or pentachlorocyclohexyl.

Alkylsulfonyl is, for example: methylsulfonyl, ethylsulfonyl, propylsulfonyl or butylsulfonyl. Methyl- and ethyl-sulfonyl are preferred. Phenyl and thienyl, also as part of a substituent such as phenoxy', thiophenoxy, phenylthio, phenoxycarbonyl, phenylaminocarbonyl, benzyl or benzoyl, can generally be unsubstituted or substituted by further substituents. The substituents may be in the ortho-, metaand/or para-position(s) or in 2-, 3-, 4- or 5-position of the thienyl ring, respectively.

Preferred substituent positions are the ortho- and para-positions to the ring-linkage point. Preferred substituents are halogen atoms.

In the further substituents that are composed of several basic elements, the elements are as defined above by way of example. In those cases also, the lists do not represent a limitation of the invention: they are of an illustrative nature only.

Suitable salts of the free carboxylic acid are, especially, alkali metal salts such as lithium, sodium, potassium; alkaline earth metal salts such as magnesium or calcium; or salts of manganese, copper, zinc or iron; or salts of organic ammonium bases, such as ammonia, primary, secondary or tertiary alkylamines, such as methylammonium, diethylammonium, methylammonium, morpholinium, tetrabutylammonium, benzyltrimethylammonium, phosphonium, sulfonium, sulfoxonium or pyridinium.

The invention relates also to salts that the compounds of formula I are capable of forming with amines, alkali and alkaline earth metal bases or quaternary ammonium bases. Within the scope of the present invention, those salts also include hydrazonium salts that may be formed by compounds of formula I wherein R₂ is the group Q". Salt formation can also be effected by the addition of a strong acid to the pyrimidine moiety of the compounds of formula I. Suitable acids for that purpose are hydrochloric acid, hydrobromic acid, sulfuric acid or nitric acid.

Alkali metal and alkaline earth metal hydroxides that are especially suitable as salt formers are the hydroxides of lithium, sodium, potassium, magnesium or calcium, but especially those of sodium or potassium.

Examples of amines suitable for the formation of ammonium cations are both ammonia and primary, secondary and tertiary C₁-C₄alkylamines, C₁-C₄-hydroxyalkylamines and C₂-C₄alkoxyalkylamines, for example methylamine, ethylamine, n-propylamine, isopropylamine, the four isomeric butylamines, n-amylamine, isoamylamine, hexylamine, heptylamine, 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, hexyloctylamine, dimemylamine, diediylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, di-n-amylamine, diisoamylamine, dihexylamine, diheptylamine, dioctylamine, ethanolamine, n-propanolamine, isopropanolamine, N,N-diedιanolamine, 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, diemanolamine, 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, o,m,p-toluidines, phenylenediamines, benzidines, naphthylamines and o,m,p-chloroanilines; but especially triethylamine, isopropylamine and diisopropylamine.

Examples of quaternary ammonium bases are generally the cations of ammonium halides, for example the tetramethylammonium cation, the trimethylbεnzylammonium cation, the triethylbenzylammonium cation, the tetraethylammonium cation, the trimethylethylammonium cation, and also the ammonium cation.

When the substituents R_a and R_b together form a C₃-C₄alkylene, C₃-C₄alkenylene or C₄alkadienylene bridge, each of which may be substituted by halogen or by C₁-C₄alkyl, there are formed, together with the phenyl ring to which the bridge is bonded, binuclear systems, such as 1 ,2,3,4- tetrahydronaphthalene, l-chloro-2-methyl-3,4-dihydronaphthalene, indanes, 1,2-dihydronaphthalene, indene, naphthalene, 2-methylnaphthalene, 1-n-butylnaphdιalene, 2-ethylnaphthalene or 1-chloronaphthalene.

When the substituents R_d and R_e together form a C₃-C₄alkylene bridge, there are formed, together with the ring system to which they are bonded, polynuclear systems, such as 2,3-tetramethylenethiophene, 2,3-trimethylenedιiophene, 2,3-tetramethylenefuran,

3,4-tetramethylenepyridine or

Compounds of formula I, or salts uiereof, that are preferred for use in the composition according to the invention arc those wherein W is W₁, W₂, W₃ or W₄, but especially W₁,

-c— H and wherein Y is preferably -COOH, or an organic or inorganic salt of that acid,

o

or , but most especially -COOH, or an organic

or inorganic salt of that acid. Of that group, special preference is given to those compounds wherein R₁₂ is hydrogen, halogen, -OCH₃ or -COR₁₃, wherein R₁₃ is especially C₁-C₄alkyl. Preference is also given to those compounds wherein W is W₁ and

E is nitrogen.

Very especially preferred individual compounds of formula I are listed in the following Tables 1 to 4:

11.04 O

In especially preferred compositions according to the invention there are used, a herbicidally active pyrimidine of formula I, the above-mentioned preferences being given special mention, and as safener a herbicide-antagonistically effective amount of a quinoline derivative of formula IIg

Further safeners of formula Ila that may be given special mention are listed in Table 5:

Preference is also given to those compositions according to the invention that comprise a herbicide of formula I, special mention being made of the above-mentioned preferred substituents, and a herbicide-antagonistically effective amount of a safener of formula IIb wherein R₂₅ is C₁-C₄alkyl, especially methyl, R₂₆ is hydrogen or C₁-C₄alkyl, R₂₇ is

hydrogen and A₂ is a group or , wherein R_~ is

preferably hydrogen, R_g is hydrogen, methyl or methoxy, R_h is methyl or methoxy, and R_d, R_e and R_f are hydrogen.

Further safeners of formula lIb that may be given special mention are listed as compounds of formula IIe in Table 6:

Further preferred compositions according to the invention comprise a herbicide of formula I, special mention being made of the above-mentioned preferred substituents, and a herbicide-antagonistically effective amount of a safener of formula IIc wherein R₂₉ is preferably phenyl or halo-substituted phenyl, R₃₀ is 2-Cl, R₃₂ is methyl and E₂ is methine.

Further safeners of formula lie that may be given special mention are listed as compounds of formula IIf in Table 7:

Further preferred compositions according to the invention comprise a herbicide of formula I, the above-mentioned preferred substituents being given special mention, and a herbicide-antagonistically effective amount of a safener of formula IId wherein R_{33 and}

R₃₄ are allyl, or R₃₃ and R₃₄ together are ; or R₃₃ and R₃₄ together are

, wherein either R₃₇ and R₃₈ are each methyl and R₃₉ is ; or

R₃₇, R₃₈ and R₃₉ are each methyl; or R₃₉ is hydrogen; or R₃₇ and R₃₈ together are

-(CH₂)₅-; or R₃₃ and R₃₄ together are , wherein R₅₃, R₅₄ and R₅₅

are preferably methyl and R₄₉, R₅₀, R₅₁ and R₅₂ are preferably hydrogen.

Further safeners of formula IId that may be given special mention are listed in Table 8:

Outstanding selective herbicidal compositions according to the invention comprise as herbicide a compound of formula If

wherein

a) Y is -COOCH₃ and R₁₂ is hydrogen; or

b) Y is -COOCH₃ and R₁₂ is methylcarbonyl; or

c) Y is -COOCH₃ and R₁₂ is ethylcarbonyl; or

d) Y is -COOH and R₁₂ is hydrogen; or

e) Y is -COOH and R₁₂ is fluorine; or

f) Y is -COOH and R₁₂ is methoxy; or g) Y is 2-chlorophenylhydrazinoyl and R₁₂ is methoxy; or h) Y is 2-fluorophenylhydrazinoyl and R₁₂ is methoxy; or i) Y is o-tolylhydrazinoyl and R₁₂ is methoxy; or

j) Y is -NHNHC(CH₃)₃ and R₁₂ is hydrogen; or

k) Y is 2-phenylhydrazinoyl and R₁₂ is hydrogen; or

l) Y is 2-fluorophenylhydrazinoyl and R₁₂ is hydrogen;

m) Y is 2-trifluoromethylphenylhydrazinoyl and R₁₂ is hydrogen; or n) Y is o-tolylhydrazinoyl and R₁₂ is hydrogen; or

o) Y is 4-chlorophenylhydrazinoyl and R₁₂ is hydrogen;

p) Y is and R₁₂ is hydrogen; or

q) Y is and R₁₂ is hydrogen; or

r) Y and R₁₂ together are or

s) Y and R₁₂ together are or

t) Y and R₁₂ together are or

u) Y and R₁₂ together are ; or

v) Y and R₁₂ together are or

w) a compound of formula Ig

and as safener a herbicide-antagonistically effective amount of a compound of formula IIe

wherein A₂ is the group and R₂₆ is hydrogen;

or of a compound of formula IIe

wherein A₂ is the group and R₂₆ is hydrogen;

or of a compound of formula IIe

wherein A₂ is the group and R₂₆ is methyl;

or of a compound of formula IIe

wherein A₂ is the group and R₂₆ is methyl.

Of that group of compositions according to the invention, special preference is made of those that comprise as herbicide a compound of formula If wherein a) Y is -COOCH₃ and R₁₂ is hydrogen; or

b) Y is -COOCH₃ and R₁₂ is ethylcarbonyl; or

c) Y is -COOH and R₁₂ is hydrogen; or d) Y and R₁₂ together are or

e) Y and R₁₂ together are

or a compound of formula Ig

and as safener a herbicide-antagonistically effective amount of a compound of formula IIe

wherein A₂ is the group and R₂₆ is hydrogen;

or of a compound of formula IIe

wherein A₂ is the group and R₂₆ is hydrogen;

or of a compound of formula IIe

wherein A₂ is the group and R₂₆ is methyl;

or of a compound of formula IIe

wherein A₂ is the group and R₂₆ is methyl.

The herbicides of formula I can advantageously also be combined with the safeners mentioned in the following Tables 9 and 10 to form compositions according to the invention:

Especially outstanding compositions according to the invention comprise the following herbicide/safener combinations:

He bicide No. Safener No. Herbicide No. Safener No.

1.002 + 5.001 1.004 + 6.001

1.002 + 5.004 1.004 + 6.003

1.002 + 8.005 1.004 + 6.004

1.002 + 9.02 1.004 + 8.07

1.004 + 9.02

1.011 + 5.001 2.001 + 6.001

1.011 + 5.004 2.001 + 6.003

1.011 + 5.005 2.001 + 6.004

1.011 + 6.001

1.011 + 6.003

1.011 + 6.004

1.011 + 7.001

1.011 + 8.007

2.003 + 5.001 2.004 + 5.001

2.003 + 6.001 2.003 + 6.002

2.003 + 6.004

2.003 + 7.001

3.001 + 5.001 3.002 + 5.001

3.001 + 5.004 3.002 + 5.004

3.001 + 8.005 3.002 + 8.005

3.001 + 9.02 3.002 + 9.02

The compounds of formulae I, Ila, IIb, IIe, IId, IIh and IIi are known or they can be prepared analogously to known processes. Compounds of formula I are described, for example, in EP-A-0347 811, 0335 409, 0426476, 0315 889, 0435 170, 0402751, 0459 243, 0409369 and WO 91/05781 -A. Compounds of formula I wherein W is W₅ or W₆ are described in WO 92/17468.

The quinoline derivatives within the scope of formula IIa and their preparation are known or they can be prepared analogously to known processes which are described, for example, in patent specification EP-A-0094349. Compounds of formula IIb are described in EP-A-0365 484 and compounds of formula IIc are described in EP-A-0268 554 and 0 174562. Compounds of formula IId are known, for example, from USP 4971 618, USP 3 959304, USP 4256481, EP-A-0 149974, EP-A-0304409 and DE-OS-2948 535. Compounds of formula IIh are disclosed in EP-A-0089313 and compounds of formula IIi are disclosed in EP-A-0055 693.

The invention relates also to a method for the selective control of weeds in crops of useful plants, which method comprises treating the useful plants, the seeds or seedlings thereof or the cultivated area thereof with a herbicidally effective amount of the pyrimidine of formula I and a herbicide-antagonistically effective amount of a safener of formula IIa, lIb, IIe, IId, IIh or IIi, simultaneously or independendy of one another.

Crop plants that can be protected against the damaging effect of the above-mentioned herbicides by the safeners of formula IIa, lib, IIc, IId, IIh or IIi are especially those that are important in the food and textile sectors, for example sugar cane and, especially, sorghum, maize, rice and other species of cereal (wheat, rye, barley, oats), most especially wheat and maize. The weeds to be controlled may be both monocotyledonous and dicotyledonous weeds.

There come into consideration as crop plants or parts of those plants, for example, those mentioned above. Cultivated areas will be understood as meaning areas of land in which the crop plants are already growing or in which the seed of those crop plants has already been sown, and also ground intended for growing those crop plants.

A safener or antidote of formula IIa, IIb, IIe, IId, IIh or IIi can, depending on the intended use, be used to pre-treat the seed of the crop plant (dressing the seeds or seedlings) or can be introduced into the soil before or after sowing has taken place. It can, however, also be applied by itself or together with the herbicide before or after the emergence of the plants. The treatment of the plant or the seed with the safener can therefore in principle take place independendy of the time of application of the phytotoxic chemical. The plant can, however, also be treated by applying the phytotoxic chemical and the safener simultaneously (tank mixture). Preemergence treatment includes both treatment of the cultivated area before sowing and treatment of cultivated areas in which seed has been sown but in which the plants have not yet grown.

The rate of application of the safener relative to that of the herbicide depends largely on the mode of application. In the case of field treatment, which is effected either 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 is generally from 1:100 to 10:1, preferably from 1:20 to 1:1, and especially 1:1. In contrast, in the case of seed dressing, much lower amounts of safener are required relative to the rate of application of herbicide per hectare of cultivated area.

In the case of field treatment, 0.001 to 5.0 kg of safener/ha, preferably 0.01 to 0.5 kg of safener/ha, will usually be applied.

The rate of application of herbicide is generally from 0.001 to 2 kg/ha, but preferably from 0.05 to 1 kg/ha.

In the case of seed-dressing, 0.001 to 10 g of safener/kg of seed, preferably 0.05 to 2 g of safener/kg of seed, will generally be applied. If the safener is applied in liquid form by seed soaking shortly before sowing, then it is advantageous to use safener solutions that comprise the active ingredient in a concentration of 1 to 10000 ppm, preferably 100 to 1000 ppm.

For the purpose of application, the compounds of formula H or combinations of

compounds of formula IIa, IIb, IIc, IId, IIh or IIi with the herbicides of formula I to be antagonised are advantageously used together with the adjuvants conventionally employed in formulation technology, and are therefore formulated in known manner, e.g. into emulsifiable concentrates, coatable pastes, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granules, and also encapsulations in e.g. polymer substances. As with the nature of the compositions to be used, 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 comprising the compound (active ingredient) of formula E, or a combination of the compound of formula IIa, IIb, IIc, IId, IIh or IIi 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, e.g.

solvents, solid carriers and, where appropriate, surface-active compounds (surfactants).

Suitable solvents are: aromatic hydrocarbons, preferably the fractions containing 8 to 12 carbon atoms, e.g. xylene mixtures or substituted naphthalenes, phthalates such as dibutyl phthalate or dioctyl phthalate, aliphatic hydrocarbons such as cyclohexane or paraffins, alcohols and glycols and their ethers and esters, such as ethanol, ethylene glycol, ethylene glycol monomethyl or monoethyl ether, ketones such as cyclohexanone, strongly polar solvents such as N-methyl-2-pyrrolidone, dimethyl sulfoxide or dimethylformamide, as well as vegetable oils or epoxidised vegetable oils, such as epoxidised coconut oil or soybean oil; or water.

The solid carriers used e.g. for dusts and dispersible powders are normally natural mineral fillers such as calcite, talcum, kaolin, montmorillonite or attapulgite. In order 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, for example pumice, broken brick, sepiolite or bentonite; and suitable nonsorbent carriers are, for example, calcite or sand. In addition, a great number of pregranulated materials of inorganic or organic nature can be used, e.g. especially dolomite or pulverised plant residues. Depending on the nature of the compound of formula IIa, IIb, IIc, IId, IIh or IIi to be formulated and, where appropriate, also on the nature of the herbicide of formula I to be antagonised, suitable surface-active compounds are nonionic, cationic and/or anionic surfactants having good emulsifying, dispersing and wetting properties. The term

"surfactants" will also be understood as comprising mixtures of surfactants.

Both so-called water-soluble soaps and water-soluble synthetic surface-active compounds are suitable anionic surfactants.

Suitable soaps are the alkali metal salts, alkaline earth metal salts or unsubstituted 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 e.g. from coconut oil or tallow oil. Fatty acid methyltaurin salts may also be mentioned.

More frequently, however, so-called synthetic surfactants are used, especially fatty sulfonates, fatty sulfates, sulfonated benzunidazole derivatives or alkylarylsulfonates.

The fatty sulfonates or sulfates are usually in the form of alkali metal salts, alkaline earth metal salts or unsubstituted or substituted ammonium salts and contain a C₈-C₂₂alkyl radical which also includes the alkyl moiety of acyl radicals, e.g. the sodium or calcium salt of lignosulfonic 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 2 sulfonic acid groups and one fatty acid radical containing 8 to 22 carbon atoms. Examples of alkylarylsulfonates are the sodium, calcium or triethanolamine salts of dodecylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid, or of a condensate of naphthalenesulfonic acid and formaldehyde.

Also suitable are corresponding phosphates, e.g. salts of the phosphoric acid ester of an adduct of p-nonylphenol with 4 to 14 moles of ediylene oxide, or phospholipids.

Non-ionic surfactants are preferably polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, 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 non-ionic surfactants are the water-soluble adducts of polyethylene oxide with polypropylene glycol, ethylenediaminopolypropylene glycol and alkylpolypropylene glycol containing 1 to 10 carbon atoms in the alkyl chain, which adducts 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.

Representative examples of non-ionic surfactants are nonylphenolpoly ethoxy edianols, castor oil polyglycol ethers, polypropylene/polyethylene oxide adducts, tributylphenoxy-polyethoxyethanol, polyethylene glycol and octylphenoxy-polyethoxyethanol.

Fatty acid esters of polyoxyethylene sorbitan, e.g. polyoxyethylene sorbitan trioleate, are also suitable.

Cationic surfactants are preferably quaternary ammonium salts which contain, 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, e.g. stearyltrimethyl-ammonium chloride or benzyldi(2-chloroethyl)ethylammonium bromide.

The surfactants customarily employed in formulation technology are described inter alia in the following publications:

"Mc Cutcheon's Detergents and Emulsifiers Annual" MC Publishing Corp., Ridgewood,

New Jersey, 1981.

Stache, H., "Tensid-Taschenbuch", Carl Hanser Verlag, Munich/Vienna 1981.

The agrochemical compositions usually comprise 0.1 to 99 % by weight, preferably 0.1 to 95 % by weight, of a compound of formula IIa, IIb, IIe, IId, IIh or IIi or a mixture of antidote and herbicide, 1 to 99.9 % by weight, preferably 5 to 99.8 % by weight, of a solid or liquid adjuvant and 0 to 25 % by weight, preferably 0.1 to 25 % by weight, of a surfactant.

Whereas commercial products are preferably formulated as concentrates, the end user will normally employ dilute formulations. The compositions may also comprise further ingredients such as stabilisers, antifoams, viscosity regulators, binders and tackifiers, as well as fertilisers or other active ingredients for obtaining special effects.

Various methods and techniques are suitable for using compounds of formula IIa, IIb, IIc, lId, lIh or IIi or compositions comprising them for protecting crop plants against the damaging effects of herbicides of formula I. The following are examples thereof: i) Seed dressing

a) Dressing the seeds with a wettable powder formulation of a compound of formula IIa, lIb, lIe, IId, IIh or lIi by shaking in a vessel until the formulation is evenly distributed over the surface of the seeds (dry dressing). Approximately 1 to 500 g of a compound of formula lIa, lIb, IIc, IId, IIh or IIi (4 g to 2 kg of wettable powder) are used per 100 kg of seed. b) Dressing the seeds with an emulsifiable concentrate of a compound of formula IIa, IIb, lie, IId, Hh or IIi according to method a) (wet dressing). c) Dressing by immersing the seeds in a mixture comprising 100 to 1000 ppm of a compound of formula IIa, lIb, IIc, IId, lIh or lIi for 1 to 72 hours and, if desired, subsequendy drying the seeds (immersion dressing).

Dressing the seed or treating the germinated seedling are naturally the preferred mediods of application since the active ingredient treatment is directed wholly at the target crop. Normally 1 to 1000 g of antidote, preferably 5 to 250 g of antidote, are used per 100 kg of seed, aldiough, depending on the method employed, which also allows the addition of other active ingredients or micronutrients, amounts that exceed or fall short of specified concentration limits may be employed (repeat dressing). ii) Application from a tank mixture

A liquid formulation of a mixture of antidote and herbicide (ratio of the one to the other from 10:1 to 1:100) is used, the rate of application of herbicide being 0.01 to 5.0 kg per hectare. A tank mixture of this type is applied before or after sowing. iii) Application to the seed furrow

The antidote is introduced in the form of an emulsifiable concentrate, wettable powder or granules into the open, sown seed furrow and then, after covering the seed furrow, the herbicide is applied preemergence in the normal manner. iv) Controlled release of active ingredient

A solution of a compound of formula IIa, IIb, IIc, IId, lIh or lIi is applied to mineral granule carriers or polymerised granules (urea/formaldehyde) and allowed to dry. If desired, a coating may be applied (coated granules) that allows the active ingredient to be released in metered amounts over a specific period of time.

Formulation Examples for liquid active ingredients of formula lIa, lIb, lIc, lId, lIh or lIi or mixtures thereof with a herbicide of formula I (throughout, percentages are by weight)

1. Emulsifiable concentrates a) b) c) compound mixture 25 % 40 % 50 % calcium dodecylbenzenesulfonate 5 % 8 % 6 % castor oil polyethylene glycol

ether (36 moles of ethylene ojride)

tributylphenol polyethylene glycol

ether (30 moles of ethylene oxide) 12 % 4 % cyclohexanone 15 % 20 % xylene mixture 65 % 25 % 20 %

Emulsions of any desired concentration can be produced from such concentrates by dilution with water.

2. Solutions a) b) c) d) compound mixture 80 % 10 % 5 % 95 % ediylene glycol monomethyl

ether 20 %

polyethylene glycol

(mol. wt.400) 70 %

N-methyl-2-pyrrolidone 20 %

epoxidised coconut oil 1 % 5 % petroleum fraction (boiling

range 160-190°) 94 % These solutions are suitable for application in the form of micro-drops.

3. Granules a) b)

compound mixture 5 % 10 %

kaolin 94 % - highly dispersed silicic acid 1 % _

attapulgite - 90 %

The active ingredient is dissolved in methylene chloride, the solution is sprayed onto the carrier, and the solvent is subsequendy evaporated off in vacuo.

4. Dusts a) b)

compound mixture 2 % 5 %

highly dispersed silicic acid 1 % 5 %

talcum 97 % _

kaolin - 90 %

Ready-for-use dusts are obtained by intimately mixing the carriers with the active ingredient

Formulation Examples for solid active ingredients of formula lIa, lIb, lIc, lId, lIh or lIi or mixtures thereof with a herbicide of formula I (throughout, percentages are by weight)

5. Wettable powders a) b) c)

compound mixture 25 % 50 % 75 %

sodium lignosulfonate 5 % 5 % - sodium laurylsulfate 3 % _ 5 % sodium diisobutylnaphdialenesulfonate - 6 % 10 %

octylphenol polyethylene glycol

ether (7-8 moles of ethylene oxide) - 2 %

highly dispersed silicic acid 5 % 10 % 10 % kaolin 62 % 27 %

The active ingredient is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording wettable powders which can be diluted with water to give suspensions of the desired concentration.

6. Emulsifiable concentrates

compound mixture 10 %

octylphenol polyethylene glycol

ether (4-5 moles of ethylene oxide) 3 %

calcium dodecylbenzenesulfonate 3 %

castor oil polyglycol ether

(35 moles of ethylene oxide) 4 %

cyclohexanone 30 %

xylene mixture 50 %

Emulsions of any required concentration can be obtained from this concentrate by dilution with water.

7. Dusts a) b)

compound mixture 5 % 8 %

talcum 95 % - kaolin - 92 %

Ready-for-use dusts arc obtained by mixing the active ingredient with the carriers and grinding the mixture in a suitable mill.

8. Extruder granules

compound mixture 10 %

sodium lignosulfonate 2 %

carboxymethylcellulose 1 %

kaolin 87 %

The active ingredient is mixed and ground with the adjuvants, and the mixture is subsequently moistened with water. The mixture is extruded and then dried in a stream of air.

9. Coated granules

compound mixture 3 %

polyethylene glycol (mol. wt. 200) 3 % kaolin 94 %

The finely ground active ingredient is uniformly applied, in a mixer, to the kaolin moistened with polyethylene glycol. Non-dusty coated granules are obtained in this manner.

10. Suspension concentrates

compound mixture 40 %

ethylene glycol 10 %

nonylphenol polyethylene glycol

ether (15 moles of ethylene oxide) 6 %

sodium lignosulfonate 10 %

carboxymethylcellulose 1 %

37 % aqueous formaldehyde solution 0.2 %

silicone oil in the form of a 75 %

aqueous emulsion 0.8 %

water 32 %

The finely ground active ingredient is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired concentration can be obtained by dilution with water.

Biological Examples

Example B1: Safener action on maize:

Under greenhouse conditions maize is grown in plastics pots to the two-leaf stage. At that stage, herbicide No. 1.004 by itself and the mixtures of the herbicide with the safeners are applied to the test plants. The test compounds are applied in the form of an aqueous suspension in 5001 of water/ha. The rates of application for the herbicide are given in Table B 1 and the rate of application of the safener test compounds is 125 g/ha. 18 days after application the test is evaluated according to a scale of percentages. 100 % denotes that the test plant has died, 0 % denotes no phytotoxic action. The results in Table B1 show that the safener test compounds clearly reduce the damage to maize caused by the herbicide. Table B1:

Safener phytotoxicity to maize in %

concentration of herbicide in g/ha

500 250 125 60 30 - 85 75 50 30 10

6.001 20 10 5 0 0

6.003 25 15 5 0 0

6.004 30 15 10 5 0

Example B2: Safener action on maize:

Under greenhouse conditions maize is grown in plastics pots to the two-leaf stage. At that stage, herbicide No. 1.004 by itself and the mixtures of the herbicide with the safeners are applied to the test plants. The test compounds are applied in the form of an aqueous suspension in 5001 of water/ha. The rates of application for the herbicide are given in Table B2 and the rate of application of the safener test compounds is 125 g/ha. 11 days after application the test is evaluated according to a scale of percentages. 100 % denotes that the test plant has died, 0 % denotes no phytotoxic action. The results in Table B2 show that the safener test compounds clearly reduce the damage to maize caused by the herbicide.

Table B2:

Safener phytotoxicity to maize in %

concentration of herbicide in g/ha

250 125 - 75 60

8 . 007 35 25

9 . 02 45 30

Example B3: Safener action on maize and wheat:

Under greenhouse conditions, in plastics pots, maize is grown to the two-leaf stage and wheat to the three- leaf stage. At that stage, herbicide No. 1.002 by itself and the mixtures of the herbicide with the safeners are applied to the test plants. The test compounds are applied in the form of an aqueous suspension in 500 1 of water/ha. The rates of application for the herbicide are given in Table B3 and the rate of application of the safener test compounds is 125 g/ha. 22 days after application the test is evaluated according to a scale of percentages. 100 % denotes that the test plant has died, 0 % denotes no phytotoxic action. The results in Table B3 show that the safener test compounds clearly reduce the damage to maize and wheat caused by the herbicide.

Table B3:

phytotoxicity to:

Safener maize wheat in %

concentration of herbicide in g/ha

80 40 20 80 40 20 - 98 90 80 98 80 70

5 . 001 55 40 25 20 15 10

5 . 004 98 85 80 50 15 0

8 . 005 65 40 15 85 70 45

9. 02 80 75 55 85 65 40

Example B4: Safener action on maize:

Under greenhouse conditions maize is grown in plastics pots to the two-leaf stage. At that stage, herbicide No. 2.001 by itself and the mixtures of the herbicide with the safeners are applied to the test plants. The test compounds are applied in the form of an aqueous suspension in 5001 of water/ha. The rates of application for the herbicide are given in Table B4 and the rate of application of the safener test compounds is 125 g/ha. 18 days after application the test is evaluated according to a scale of percentages. 100 % denotes that the test plant has died, 0 % denotes no phytotoxic action. The results in Table B4 show that the safener test compounds clearly reduce the damage to maize caused by the herbicide. Table B4:

Safener phytotoxicity to maize in %

concentration of herbicide in g/ha

250 125 60 30 15 - 95 90 85 80 60

6.001 40 30 15 5 0

6.003 70 50 10 5 0

6.004 60 20 10 5 0

Example B5: Safener action on wheat, barley and rice:

Under greenhouse conditions, in plastics pots, wheat, barley and rice are grown to the two- to three-leaf stage. At that stage, herbicide No.2.003 by itself and the mixtures of the herbicide with the safeners are applied to the test plants. The test compounds are applied in the form of an aqueous suspension in 5001 of water/ha. The rates of application for the herbicide are 30 and 60 g/ha and the rate of application of the safener test compounds is 60 g/ha. Rice is evaluated according to a scale of percentages 15 days after application, wheat and barley 28 days after application. 100 % denotes that the test plant has died, 0 % denotes no phytotoxic action. The results in Table B5 show that the safener test compounds clearly reduce the damage to wheat, barley and rice caused by the herbicide.

Table B5:

Herbicide concentration 30 g/ha: phytotoxicity to:

Safener wheat barley rice in % - 85 50 20

5 .001 30 20 0

6.001 - - 0

6.002 - 0

6.004 - - 5

7.001 25 15 - Herbicide concentration 60 g/ha: phytotoxicity to:

Safener wheat barley rice in % - 98 70 35

5 . 001 70 45 10

6. 001 - - 10

6 . 002 - - 10

6 . 004 - - 5

7 . 001 85 25 -

Example B6: Safener action on maize and wheat:

Under greenhouse conditions, in plastics pots, maize is grown to the two-leaf stage and wheat to the three-leaf stage. At that stage, herbicides Nos. 3.001 and 3.002 by themselves and the mixtures of the herbicide with the safeners are applied to the test plants. The test compounds are applied in the form of an aqueous suspension in 5001 of water/ha. The rates of application for the herbicide are given in Table B6 and the rate of application of the safener test compounds is 125 g/ha. 22 days after application the test is evaluated according to a scale of percentages. 100 % denotes that the test plant has died, 0 % denotes no phytotoxic action. The results in Table B6 show that the safener test compounds clearly reduce the damage to maize and wheat caused by the herbicide.

Table B6:

Herbicide No. 3.001: phytotoxicity to

Safener wheat in %

concentration of herbicide in g/ha

1500 800 400 200 - 85 75 65 40

5.001 15 10 5 5

5.004 20 15 0 0

8.005 80 70 25 10

9.02 75 50 25 5 Herbicide No. 3.002: phytotoxicity to:

Safener maize wheat in %

concentration of herbicide in g/ha

1500 800 400 200 1500 800 400 200 - 98 85 65 30 85 70 55 25

5.001 75 40 20 10 20 5 0 0 5. 004 90 75 45 10 20 5 0 0 8 . 005 60 30 20 0 75 45 30 10 9. 02 70 55 35 20 75 55 25 15

Example B7: Safener action on maize and wheat:

Under greenhouse conditions, in plastics pots, maize is grown to the two-leaf stage and wheat to the dirce-leaf stage. At that stage, herbicide No. 1.011 by itself and the mixtures of the herbicide with the safeners arc applied to the test plants. The test compounds are applied in the form of an aqueous suspension in 5001 of water/ha. The rates of application for the herbicide arc 30 and 15 g/ha and the rates of application of the safener test compounds are 60 and 125 g/ha. Maize is evaluated according to a scale of percentages 20 days after application and wheat 21 days after application. 100 % denotes that the test plant has died, 0 % denotes no phytotoxic action. The results in Table B7 show that the safener test compounds clearly reduce the damage to maize and wheat caused by the herbicide.

Table B7:

Herbicide concentration 30 g/ha: phytotoxicity to:

Safener concentration in g/ha maize wheat in % - - 95 98

5.001 60 - 45

5.004 125 - 35

5.005 125 - 45

6.001 60 35 -

6.003 60 65 -

6.004 60 45 -

7.001 60 55 25

8.007 60 50 -

Herbicide concentration 15 g/ha: phytotoxicity to:

Safener concentration in g/ha maize wheat in % - - 80 90

5.001 60 - 30

5.004 125 - 15

5.005 125 - 15

6.001 60 30 -

6.003 60 40 -

6.004 60 40 -

7.001 60 40 20

8.007 60 25 -

Claims

What is claimed is:

1. A composition for the selective control of weeds in crops of useful plants, which, in addition to inert carriers and additives, comprises as active ingredient a mixture comprising a) a herbicidally effective amount of a pyrimidine of formula I

wherein

X is oxygen or sulfur or, when W is W₅, may also be NH, NC(O)H or NC(O)R_62; is -COOH, or an organic or inorganic salt of that acid,

or

, or the possible salts of these groups;

R is -OR_n;

R₁ is one of the groups (a), (b) and (c)

R₂ is hydrogen, methyl or the group Q"

wherein

Q₁ is hydrogen, methyl or, together with Q₄, is -(CH₂)₂-, -(CH₂)₃-, -CH₂CH(OH)CH₂- or -CH₂SCH₂-;

Q₂ is hydrogen or methyl;

Q₃ is hydrogen, trifluoromethyl, ethynyl, vinyl, phenyl, cyano or C_{1 -4}alkoxycarbonyl, C_{1 -4}alkyl, or C_{1 -4}alkyl substituted by hydroxy, C_{1 -4}alkoxy, mercapto, C_{1 -4}alkylmercapto, vinyl, phenyl, 4-hydroxyphenyl, 4-imidazolyl, 3-indolyl, hydroxycarbonyl, C_{1 -4}alkoxycarbonyl, 2-propenyloxycarbonyl, cyano or by carbamoyl; and Q₄ is hydrogen, methyl, hydroxymethyl, formyl or cyano;

or R₂ together with R₇ is -(CH₂)_p-, -CH₂SCH₂- or -CH₂CHOHCH₂-;

R₃ is hydrogen, C_{1 -4}alkyl, phenyl, or phenyl mono- or di- substituted by fluorine,

chlorine, bromine, methyl, trifluoromethyl, methoxy or by nitro;

R₄ is hydrogen or methyl;

R₅ is C_{1 -4}alkyl, C_{1 -6}haloalkyl, phenyl, benzyl, or phenyl substituted by fluorine,

chlorine, bromine, methyl, trifluoromethyl, methoxy, nitro, cyano, carboxy or by C_{1 -3}alkoxy carbonyl ;

R₆ is hydrogen, hydroxymethyl, formyl, cyano, hydroxyimino, C_{1 -4}alkoxyimino,

phosphono, phosphino, methylphosphino or a group COX₁;

R₇ is hydrogen; C_{1 -4}alkyl or C_{1 -4}alkyl substimted by hydroxy, C_{1 -4}alkoxy, mercapto, acylmercapto, C_{1 -4}alkylthio, vinyl, phenyl, 4-hydroxyphenyl, 4-imidazolyl,

3-indolyl, hydroxycarbonyl, C_{1 -4}alkoxycarbonyl, 2-propenyloxycarbonyl, cyano, carbamoyl, methylphosphino or by methylsulfoximino; trifluoromethyl; ethynyl; vinyl or vinyl substituted by chlorine or by methoxy; phenyl or phenyl substituted by fluorine, chlorine, methyl, trifluoromethyl or by methoxy; or cyano or C_{1 -4}alkoxycarbonyl;

R₈ is hydrogen or methyl;

A is oxygen, sulfur or -NH-;

m is 1, 2 or 3;

n is O, 1, 2 or 3;

p is 2 or 3;

X₁ is hydroxy, C_{1 -4}alkoxy, C_3-4alkenyloxy, mercapto, C_{1 -4}alkylthio, amino, C_{1 -4}alkyl amino, C_{1 -4}dialkylamino or C_{1 -4}alkoxyamino; or C_{1 -4}alkoxy, C_{3 -4}alkenyloxy, mercapto, C_{1 -4}alkylthio, amino, C_{1 -4}alkylamino, C_{2 -4}dialkylamino or C_{1 -4}alkoxyamino each substituted by phenyl, benzyloxy or by C_{1 -2}alkoxy, or is one of the groups (d), (e) and (f)

wherein

A₁ is oxygen, sulfur or -NH-;

R₉ is hydrogen, C_{1 -4}alkyl or benzyl;

R₁₀ is hydroxymethyl, cyano or a group COQ';

Q is hydroxy, C_{1 -4}alkoxy, 2-propenyloxy, benzyloxy, amino or the group (d); and

Q' is hydroxy, C_{1 -4}alkoxy, 2-propenyloxy, benzyloxy, amino or the group (d);

R_{1 1} is hydrogen, C₁-C₁₀alkyl, C₁-C₄alkoxy- C₁-C₄alkyl, C₁-C₄alkylthio-C₁-C₄alkyl, diC₁-C₄alkylamino-C₁-C₄alkyl, halo- C₁-C₈alkyl, C₂-C₈alkenyl, halo-C₂-C₈alkenyl, C₃-C₈alkynyl, C₃-C₇cycloalkyl, halo-C₃-C₇cycloalkyl, C₁-C₈alkylcarbonyl,

C₁-C₄alkylcarbonyloxy-C₁-C₂alkyl, allylcarbonyl, C₃-C₇cycloalkylcarbonyl, benzoyl that is unsubstituted or substituted at the phenyl ring by up to three identical or different substituents selected from halogen, C₁-C₄alkyl, halo-C₁-C₄alkyl, haloC₁-C₄alkoxy and C₁-C₆alkoxy; or is furoyl or thienyl; or C₁-C₄alkyl 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-C₆alkylthiocarbonyl, C₃-C₈alkenyldιiocarbonyl, C₃-C₈alkynylthiocarbonyl, carbamoyl, mono-C₁-C₄alkylaminocarbonyl, di-C₁-C₄alkylaminocarbonyl, tri-C₁-C₆alkylsilyl or by

di-C₁-C₆alkyl-phenylsilyl; or phenylaminocarbonyl that is unsubstituted or substituted at the phenyl by up to three identical or different substituents selected from halogen, C₁-C₄alkyl, halo-C₁-C₄alkyl, halo-C₁-C₄alkoxy and C₁-C₄alkoxy or is monosubstituted by cyano or by nitro; or dioxolan-2-yl that is unsubstituted or substituted by one or two C₁-C₄alkyl radicals; oxetan-3-yl or dioxan-2-yl that are unsubstituted or substituted by one or two C₁-C₄alkyl radicals; or C₁-C₄alkyl that is substituted by cyano, nitro, carboxy or by C₁-C₆alkylthio-C₁-C₆alkoxycarbonyl; or the groups -N=C(CH₃)₂ or -CH₂CH₂ON=C(CH₃)₂; W is

or W and Y together form a group W₄

or W and Y together form a group W₅

or W and Y together form a group W₆

E is nitrogen or -CR₁₂;

R₁₂ is hydrogen, halogen, hydroxy, C₁-C₄alkoxy, phenyl or benzyl; or phenyl substituted by C₁-C₄alkyl, C₁-C₄alkoxy, C₁-C₄haloalkyl or by halogen; benzyl substituted by C₁-C₄alkyl, C₁-C₄alkoxy, C₁-C₄haloalkyl or by halogen; -COR₁₃, -C-R₁₄ ,

N-R15

-S(O)_qR₁₆, (4,6-Dimethoxy-pyrimidin-2-yl)-oxy; C₁-C₄alkyl that is unsubstituted or substituted by halogen; ethenyl that is unsubstinited or substituted by C₁-C₄alkyl, phenyl, halogen, cyano or C₁-C₄alkoxycarbonyl; ethynyl that is unsubstituted or substituted by halogen, C₁-C₄alkyl or phenyl, phenoxy or phenylthio that arc unsubstituted or substimted by C₁-C₄alkyl, C₁-C₄alkoxy, C₁-C₄haloalkyl or halogen; R₁₃ is C₁-C₄alkyl, halo- C₁-_C4alkyl, C₁-C₄alkoxy-C₁-C₄alkyl; amino, C₁-C₄alkylamino, di-C₁-C₄alkylamino, C₂-C₄haloalkylamino, di-C₂-C₄haloalkylamino, C₁-C₄alkoxyalkylamino, di-C₁-C₄alkoxyalkylamino, C₃-C₄alkenylamino, diallylamino,

-N-pyrrolidino, -N-piperidino, -N-morpholino, -N-thiomorpholino, -N-piperidazino, -O-N=C(CH₃)-CH₃ or -O-CH₂-CH₂-O-N=C(CH₃)-CH₃;

R₁₄ is hydrogen, C₁-C₁₀alkyl that is unsubstituted or substimted by acyl or by cyano;

C₁-C₄alkoxy-C₁-C₄alkyl, C₁-C₄alkylthio-C₁-C₄alkyl, C₁-C₄alkylsulfonylC₁-C₄alkyl, C₁-C₄alkylsulfinyl-C₁-C₄alkyl, or phenyl that is unsubstituted or substimted at the phenyl ring by up to three identical or different substituents selected from halogen, C₁-C₄alkyl, halo-C₁-C₄alkyl, halo-C₁-C₄alkoxy and

C₁-C₄alkoxy;

R₁₅ is hydroxy, C₁-C₁₀alkyl that is unsubstimted or substimted by halogen; C₁-C₆alkoxy that is unsubstimted or substimted by halogen, benzyloxy, C₁-C₆alkoxycarbonyl, C₃-C₆Cycloalkyl, acyl, di-C₁-C₄alkylamino or by C₁-C₆alkoxy; phenyl, phenoxy or benzyloxy each of which is unsubstimted or substimted at the phenyl ring by up to three identical or different substituents selected from halogen, C₁-C₄alkyl, haloC₁-C₄alkyl, halo-C₁-C₄alkoxy and C₁-C₄alkoxy; C₂-C₈alkenyl, halo-C₂-C₈alkenyl, C₃-C₈alkynyl, C₃-C₇cycloalkyl, halo-C₃-C₇cycloalkyl, C₁-C₄alkoxyamino,

C₁-C₄alkylamino, phenylamino, -OSi(CH₃)₃, C₂-C₈alkenyloxy or C₃-C₈alkynyloxy; q is the number 0, 1 or 2;

R₁₆ is C₁-C₁₀alkyl that is unsubstituted or substimted by halogen; phenyl that is

unsubstituted or substimted by up to three identical or different substituents selected from halogen, C₁-C₄alkyl, halo-C₁-C₄alkyl, halo-C₁-C₄alkoxy and C₁-C₄alkoxy; C₂-C₈alkenyl, halo-C₂-C₈alkenyl, C₃-C₈alkynyl, C₃-C₇cycloalkyl or halo- C₃-C₇cycloalkyl;

R₁₇ is hydrogen, C_{1 -6}alkyl, C_3-6cycloalkyl, C_{1 -6}alkyl that is monosubstimted by chlorine or mono- to hexa-substituted by fluorine; phenyl or thienyl, or phenyl mono- or di- substituted by fluorine, chlorine, methyl.or by methoxy;

R₁₈ is hydrogen, methyl or, together with R₁₇, is -(CH₂)₂-, -(CH₂)₃-, -(CH₂)₄- or

-(CH₂)₅- ;

R₁₉ is hydrogen, methyl, fluorine, chlorine, bromine, C_{1 -4}alkoxy, C_3-6alkenyloxy,

C_3-6alkynyloxy, C_3-4cycloalkyl-C_1-2alkoxy, C_4-6cycloalkoxy, or C_{1 -4}alkoxy that is monosubstituted by cyano, C_{1 -4}alkoxy or by chlorine or is mono- to hexa-substituted by fluorine; C_{1 -6}alkylthio or cyano;

R₂₀ is hydrogen, C_{1 -4}alkyl, C_1-3alkylthio or, together with R₂₁, is -(CH₂)₄-, -(CH₂)₅-, -S(CH₂)₂S- or -S(CH₂)₃S- ;

R₂₁ is C_{1 -6}alkyl, C_2-6alkenyl, C_3-6cycloalkyl, C_{1 -6}haloalkyl, C_{1 -3}alkoxy, C_{1 -4}alkylthio, formyl, C_{1 -5}alkylcarbonyl, carboxy, C_{1 -4}alkoxycarbonyl, phenyl, or phenyl substituted by fluorine, chlorine, methyl, trifluoromethyl, methoxy or by nitro, or is 2-, 3- or 4-pyridyl, 2- or 3-furyl or 2- or 3-ttienyl; R₂₂ is hydrogen, C₁-C₆alkyl, C₃-C₆cycloalkyl, C₁-C₆haloalkyl, C₃-C₆alkenyl,

C₃-C₆alkynyl, C₃-C₆haloalkenyl, C₃-C₆haloalkynyl, phenyl or benzyl, or phenyl substituted by C₁-C₄alkyl, C₁-C₄alkoxy, C₁-C₄haloalkyl or by halogen; benzyl substimted by C₁-C₄alkyl, C₁-C₄alkoxy, C₁-C₄haloalkyl or by halogen; halogen, hydroxy, -CHO, -COOH, phenoxy, cyano, phenylthio, -CONH₂, -OCHO,

C₂-C₅alkanoyloxy, C₂-C₅alkoxycarbonyloxy, C₂-C₃alkylcarbamoyloxy,

di(C₁-C₂alkyl)carbamoyloxy or di(C₁-C₂alkoxy)phosphonyl;

R₂₃ is hydrogen, C₁-C₆alkyl or CF₃;

r is 0, 1, 2 or 3;

s is 0, 1, 2 or 3;

m is 0, 1 or 2;

R₅₇ is hydrogen, hydroxy, C₁-C₆alkoxy, C₁-C₆alkoxyalkoxy, C₁-C₆acyloxyalkoxy, trimethylsilyledioxy, C₁-C₆alkylsulfonylamino, C₁-C₆alkylthio, imidazolyl, benzyloxy, phenoxy or diiophenoxy, or benzyloxy, phenoxy or diiophenoxy;

R₅₈ is halogen, C₁-C₆haloalkyl, C₁-C₆alkyl, acylamino, C₃-C₆cycloalkyl, halosubstimted C₃-C₆cycloalkyl, C₂-C₆alkenyloxy, C₃-C₆alkynyloxy, C₁-C₆alkoxycarbonyl, C₁-C₆alkoxy, C_j-Qalkylamino, di-C₁-C₆alkylamino, C₁-C₆alkoxyiminoalkyl, acyl, C₁-C₆alkylthio, phenyl, benzyl, phenylamino or benzylamino;

R₅₉ is halogen, C₁-C₆alkyl, C₁-C₆alkoxy, C₁-C₆alkylamino, di-C₁-C₆alkylamino,

C₁-C₆haloalkyl, C₁-C₆haloalkoxy, nitro, hydroxy, cyano, C₁-C₆alkoxyalkoxy, C₁-C₆alkoxycaτbonylalkoxy, C₁-C₆alkylthioalkoxy, C₁-C₆alkylthio, C₁-C₆alkoxyalkyl, C₂-C₆alkenyl, C₃-C₆alkynyl, benzyloxy or phenoxy;

R₆₀ is halogen, C₁-C₆alkyl, C₁-C₆haloalkyl, C₃-C₆cycloalkyl, halo-substituted

C₃-C₆cycloalkyl, C₂-C₆alkenyloxy, C₃-C₆alkynyloxy, C₁-C₆alkoxycarbonyl, C₁-C₆alkoxy, C₁-C₆alkylamino, di-C₁-C₆alkylamino, phenyl, benzyl, C₁-C₆alkoxyiminoalkyl, acyl, C₁-C₆alkylthio, phenylamino or benzylamino;

R₆₁ is hydrogen, hydroxy, C₁-C₆alkoxy, C₁-C₆alkoxyalkoxy, C₁-C₆acyloxyalkoxy, trimethylsilyledioxy, C₁-C₆alkylsulfonylamino, C₁-C₆alkylthio, imidazolyl, benzyloxy, phenoxy or diiophenoxy, or benzyloxy, phenoxy or thiophenoxy;

R₆₂ is C₁-C₆alkyl or C₁-C₆alkoxy;

R₆₆ is C₁-C₆alkyl, or C₁-C₆alkyl which is substimted by up to 3 fluorine atoms, 1

chlorine atom, 1 C₁-C₄a&oxy group, 1 C₁-C₄alkoxycarbonyl group, 1

dimethylcarbamoyl group, 1 carbamoyl group, 1 cyano group, 1 vinyl group, 1 ediynyl group or 1 phenyl group which is unsubstituted by fluorine, chlorine, bromine, methyl, trifluoromethyl or methoxy, or is phenyl, or phenyl which is up to trisubstituted by fluorine, chlorine, bromine, methyl, trifluoromethyl, methoxy or nitro; or NR₆₇R₆₈; or OR₆₉;

R₆₇ is hydrogen or C₁-C₄alkyl;

R₆₈ is hydrogen, C₁-C₆alkyl, phenyl, pyridyl, or phenyl which is monosubstimted to trisubstituted or pyridyl which is monosubstituted by C₁-C₄alkyl, fluorine, chlorine, bromine, trifluoromethyl, methoxy or nitro; or is C₁-C₆alkylcarbonyl, trifluoromethylcarbonyl, C₃-C₆cycloalkylcarbonyl, benzylcarbonyl, 2-, 3- or 4-pyridylcarbonyl, 2- or 3-furyl- or diiophenylcarbonyl, benzoyl, or benzoyl which is monosubstituted to disubstituted by fluorine, chlorine, bromine, methyl, trifluoromethyl, medioxy or nitro; or C₁-C₄alkoxycarbonyl, benzoyloxycarbonyl, aminocarbonyl, aminodiiocarbonyl, or aminocarbonyl or aminodiiocarbonyl each of which is monosubstimted to disubstituted by phenyl or C₁-C₄alkyl, it being possible for the phenyl group to be substimted by fluorine, chlorine, methyl or methoxy; and

R₆₉ is hydrogen, C₁-C₆alkyl or C₂-C₆alkenyl, or C₂-C₆alkenyl which is substimted by halogen or phenyl, or C₁-C₄alkoxycarbonyl-C₁-C₄alkyl or C₁-C₄alkylthiocarbonyl- C₁-C₄alkyl; and b) as safener, a herbicide-antagonistically effective amount of a quinoline derivative of formula IIa

wherein

R₂₄ is hydrogen or C₁-C₆alkyl and

X₂ is hydrogen or chlorine;

or of an N-acylsulfamoylphenylurea of formula IIb

wherein

A₂ is a group

R₂₅ and R₂₆, independently of one another, are hydrogen, C₁-C₈alkyl, C₃-C₈cycloalkyl, C₃-C₆alkenyl, C₃-C₆alkynyl, , or C₁-C₄alkyl substituted by

C₁-C₄alkoxy or by

or R₁ and R₂ together form a C₄-C₆alkylene bridge that can be interrupted by oxygen, sulfur, SO, SO₂, NH or by -N(C₁-C₄alkyl)-;

R₂₇ is hydrogen or C₁-C₄alkyl;

R_a 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-C₆alkyl, 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 substimted by C₁-C₄alkoxy or by halogen; C₃-C₆alkenyloxy, or C₃-C₆alkenyloxy substimted by halogen; or

C₃-C₆alkynyloxy; or R_a and R_b together form a C₃-C₄alkylene bridge that can be substituted by halogen or by C₁-C₆alkyl, or a C₃-C₄alkenylene bridge that can be substimted by halogen or by C₁-C₄alkyl, or a C₄alkadienylene bridge that can be substimted by halogen or by C₁-C₆alkyl;

R_b and R_h, independendy of one another, are 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, independendy of one another, are hydrogen, halogen, C₁-C₄alkyl,

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

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

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

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

R₂₈ is hydrogen, C₁-C₁₀alkyl, C₁-C₄alkoxy-C₁-C₄alkyl, C₁-C₄alkylthio-C₁-C₄alkyl, diC₁-C₄alkylamino-C₁-C₄alkyl, halo-C₁-C₈alkyl, C₂-C₈alkenyl, halo-C₂-C₈alkenyl, C₃-C₈alkynyl, C₃-C₇cycloalkyl, halo-C₃-C₇cycloalkyl, C₁-C₈alkylcarbonyl, allylcarbonyl, C₃-C₇cycloalkylcarbonyl, benzoyl that is unsubstimted or substimted at the phenyl ring by up to three identical or different substituents selected from halogen, C₁-C₄alkyl, halo-C₁-C₄alkyl, halo-C₁-C₄alkoxy and C₁-C₄alkoxy; or is furoyl or thienyl; or C₁-C₄alkyl substimted by phenyl, halophenyl, C₁-C₄alkylphenyl, C₁-C₄alkoxyphenyl, halo-C₁-C₄alkylphenyl, halo-C₁-C₄alkoxyphenyl, C₁-C₆alkoxycarbonyl, C₁-C₄alkoxy-C₁-C₈alkoxycarbonyl, C₃-C₈alkenyloxycarbonyl, C₃-C₈alkynyloxycarbonyl, C₁-C₆alkylthiocarbonyl, C₃-C₈alkenylthiocarbonyl, C₃-C₈alkynyldιiocarbonyl, carbamoyl, mono-C₁-C₄alkylaminocarbonyl or by di-C₁-C₄alkylaminocarbonyl; or phenylaminocarbonyl that is unsubstituted or substimted at the phenyl by up to three identical or different substituents selected from halogen, C₁-C₄alkyl, halo-C₁-C₄alkyl, halo-C₁-C₄alkoxy and C₁-C₄alkoxy or monosubstituted by cyano or by nitro; or dioxolan-2-yl that is unsubstituted or substituted by one or two C₁-C₄alkyl radicals; or dioxan-2-yl that is unsubstituted or substituted by one or two C₁-C₄alkyl radicals; or C₁-C₄alkyl substituted by cyano, nitro, carboxy or by C₁-C₈alkylthio-C₁-C₈alkoxycarbonyl;

or of a 1-phenylazole-3-carboxylic acid derivative of formula IIc

wherein

E₂ is nitrogen or methine;

R₂₉ is -CCl₃, phenyl or halo-substituted phenyl;

R₃₀ and R₃₁, independendy of one another, are hydrogen or halogen; and

R₃₂ is C₁-C₄alkyl;

or of a chloroacetamide of formula IId

wherein

R₃₃ and R₃₄, independendy of one another, are C₁-C₆alkyl or C₁-C₆alkenyl;

or R₃₃ and R₃₄ together are ; wherein

R₃₅ and R₃₆, independently of one another, are hydrogen or C₁-C₆alkyl; or R₃₃ and R₃₄ together are ; wherein

R₃₇ and R₃₈, independendy of one another, are C₁-C₄alkyl;

or R₃₇ and R₃₈ together are -(CH₂)₅-;

R₃₉ is hydrogen, C₁-C₄alkyl or

^»

or R₃₃ and R₃₄ together are

wherein

R₄₀, R₄₁, R₄₂, R₄₃, R₄₄, R₄₅, R₄₆, R₄₇, R₄₈, R₄₉, R₅₀, R₅₁, R₅₂, R₅₃, R₅₄ and R₅₅, independendy of one another, are hydrogen or C₁-C₄alkyl;

or of an oxime of formula IIh

wherein

R₆₃ is hydrogen or chlorine and

R₆₆ is cyano or trifluoromethyl;

or of a phenylpyrimidine of formula IIi

wherein

R₆₅ is hydrogen or methyl.

2. A composition according to claim 1, wherein W is W₁, W₂, W₃ or W₄.

3. A composition according to claim 1, wherein W is W₁.

4. A composition according to claim 3, wherein Y is -COOH, or an organic or inorganic salt of that acid, , or

5. A composition according to claim 4, wherein R₁₂ is hydrogen, halogen -OCH₃ or -COR₁₃.

6. A composition according to claim 5, wherein R₁₃ is C₁-C₄alkyl.

7. A composition according to claim 3, wherein E is nitrogen.

8. A composition according to claim 3, wherein Y is -COOH, or an organic or inorganic salt of that acid.

9. A composition according to any one of claims 1 to 8, wherein there is used as safener a herbicide-antagonistically effective amount of a quinoline derivative of formula IIg

10. A composition according to any one of claims 1 to 8, wherein there is used a safener of formula IIb wherein R₂₅ is C₁-C₄alkyl, R₂₆ is hydrogen or C₁-C₄alkyl, R₂₇ is hydrogen

and A₂ is a group or

11. A composition according to claim 10, wherein R₂₅ is methyl, R_g is hydrogen, methyl or medioxy, R_h is methyl or methoxy and R_d, R_e and R_f are hydrogen.

12. A composition according to any one of claims 1 to 8, wherein there is used a safener of formula IIc wherein R₂₉ is phenyl or halo-substituted phenyl, R₃₀ is 2-Cl, R₃₂ is methyl and E₂ is methine.

13. A composition according to any one of claims 1 to 8, wherein there is used a safener of

formula IId wherein R₃₃ and R₃₄ are allyl, or R₃₃ and R₃₄ together are

or R₃₃ and R₃₄ together are ; wherein either R₃₇ and R₃₈ are each methyl

and R₃₉ is ; or R₃₇, R₃₈ and R₃₉ are each methyl; or R₃₉ is hydrogen; or R₃₇

and R₃₈ together arc -(CH₂)₅- ; or R₃₃ and R₃₄ together are ;

wherein R₅₃, R₅₄ and R₅₅ are preferably methyl and R₄₉, R₅₀, R₅₁ and R₅₂ are preferably hydrogen.

14. A composition according to claim 1, wherein there are used as herbicide a compound of formula If

wherein

Y is -COOCH₃ and R₁₂ is hydrogen; or

Y is -COOCH₃ and R₁₂ is methylcarbonyl; or

Y is -COOCH₃ and R₁₂ is ethylcarbonyl; or

Y is -COOH and R₁₂ is hydrogen; or

Y is -COOH and R₁₂ is fluorine; or

Y is -COOH and R₁₂ is methoxy; or

Y is 2-chlorophenylhydrazinoyl and R₁₂ is methoxy; or

Y is 2-fluorophenylhydrazinoyl and R₁₂ is methoxy; or

Y is o-tolylhydrazinoyl and R₁₂ is methoxy; or

Y is -NHNHC(CH₃)₃ and R₁₂ is hydrogen; or

Y is 2-phenylhydrazinoyl and R₁₂ is hydrogen; or Y is 2-fluorophenylhydrazinoyl and R₁₂ is hydrogen; or

Y is 2-trifluoromedιylphenylhydrazinoyl and R₁₂ is hydrogen; or

Y is o-tolylhydrazinoyl and R₁₂ is hydrogen; or

Y is 4-chlorophenylhydrazinoyl and R₁₂ is hydrogen;

Y is and R₁₂ is hydrogen; or

Y is and R₁₂ is hydrogen; or

Y and R₁₂ together are ; or

Y and R₁₂ together are ; or

Y and R₁₂ together are ^{; or}

Y and R₁₂ together are ; or

Y and R₁₂ together are ; or

a compound of formula Ig

and as safener a herbicide-antagonistically effective amount of a compound of formula IIe

wherein A₂ is the group and R₂₆ is hydrogen;

or of a compound of formula IIe

wherein A₂ is the group and R₂₆ is hydrogen;

or of a compound of formula IIe

wherein A₂ is the group and R₂₆ is methyl;

or of a compound of formula IIe

wherein A₂ is the group and R₂₆ is methyl.

15. A composition according to claim 1, wherein there are used as herbicide a compound of formula If according to claim 14, wherein

Y is -COOCH₃ and R₁₂ is hydrogen; or

Y is -COOCH₃ and R₁₂ is ethylcarbonyl; or

Y is -COOH and R₁₂ is hydrogen; or

Y and R₁₂ together are ; or

Y and R₁₂ together are

or a compound of formula Ig

and as safener a herbicide-antagonistically effective amount of a compound of formula IIe

wherein A₂ is the group and R₂₆ is hydrogen;

or of a compound of formula IIe

wherein A₂ is the group and R₂₆ is hydrogen;

or of a compound of formula IIe

wherein A₂ is the group and R₂₆ is methyl;

or of a compound of formula IIe

wherein A₂ is the group and R₂₆ is methyl.

16. A method for the selective control of weeds and grasses in crops of useful plants, which comprises treating the crops, the seeds thereof or the cultivated area thereof with an effective amount of a herbicide of formula I according to claim 1 and a herbicide-antagonistically effective amount of a safener of formula IIa, IIb, IIc, IId, IIh or IIi according to claim 1, simultaneously or independently of one another.

17. A method according to claim 16, which comprises treating crop plants or cultivated areas intended for crop plants with 0.05 to 2 kg/ha of a compound of formula I according to claim 1 and an amount of 0.01 to 0.5 kg/ha of a compound of formula IIa, IIb, IIc, IId, IIh or IIi according to claim 1.

18. A method according to claim 16 for the selective control of weeds and grasses in maize and cereal crops.