SI9200191A - Safening herbicidal pyrazolylsulphonylureas - Google Patents

Description

PROTECTION AGAINST HERBICIDAL PYRAZOLYLSULFONYLUREUS

SUBJECT MATTER OF THE INVENTION

It is an object of the present invention to protect against herbicidal pyrazolylsulfonyl arrangements, alone or in the presence of various co-herbicidal compounds, in particular (X.-chloroacetamides.

HISTORY OF THE INVENTION

Many herbicides damage crops at the doses of herbicides needed to suppress weed growth. Therefore, many herbicides cannot be used to control weeds if certain crops are present. Uncontrolled weed growth, of course, results in a reduced hectare crop yield and poorer crop quality since weeds compete with crops for light, water and nutrients in the soil. Reducing damage to crops due to herbicides without unacceptably reducing the effect of herbicides on weeds can be achieved by using crop protection agents known as herbicide counterparts, antidotes or protective agents.

Weed control among crops, especially cereals, is one of the oldest and most developed areas of weed science. In order for a herbicide to be commercially accepted for cereals, it must provide a relatively high degree of control of both grass and broadleaf weeds during cereals, in addition to meeting several other criteria. The herbicide must have e.g. relatively high activity per unit, so that lower doses of herbicide can be used. Lower doses are desirable in order to minimize the exposure of the environment to herbicides. At the same time, such an herbicide must be selective in its effect so that it does not damage the crops. The selectivity of the herbicides can be increased by the use of an appropriate antidote in combination with the herbicide. But identifying a ptotistrup that protects crops from a herbicide or herbicide mixture is a very complicated task.

Whether a compound or class of compounds provides effective antidote or protective activity is not a matter of theoretical decision, but must be determined empirically. Protective activity is determined empirically by observing the complex interplay of several biological and chemical factors, namely the type of herbicide compound, the type of weed to be suppressed, the type of crop to be protected from weed competition and herbicide damage, and from the antidote itself. . In addition, the herbicide and antidote must have chemical and physical properties that allow the preparation of a permanent formulation that is environmentally safe and easy to use in the field.

Among the various classes of compounds that have been found suitable for various herbicidal applications are " C-halogenated acetanilides and sulfonylureas. The first of these in commercial embodiments include, for example: alachlor, acetoclor, metolachlor, etc., are excellent herbicides for pre-emergence and shortly after emergence for the control of annual grasses and many broad-leaved weeds between cereals, peanuts, soybeans and other crops; while some of the other herbicides, e.g. chlorosulfuron, tifensulfuron methyl, chlorimuron ethyl, triasulfuron, metsulfuron methyl, bensulfuron methyl and the like, used as leaf herbicides or herbicides used on the earth, suitable for the control of perennial or permanent deciduous species among asparagus, cereals, maize, maize, maize, maize, maize, maize, maize soybeans and other crops, forest shrubs and vines, for pasture control, pastureland and fields. Other sulfonylureas can be used for pre-sowing or pre-emergence applications.

It is common agricultural practice to use different antidote compounds to reduce the phytotoxicity of certain herbicides for different crops. Flurazole e.g. (active ingredient in SCREEb ^ protective agent is used as a seed disinfectant to protect cultivated grass seeds from alaclor (active ingredient of LASSC ^ herbicide. Ciomethrin is active (active ingredient of COCEI ^ protective agent used as a protective agent for cultivated grass seeds for use with metolachlor, oxabetrinil (the active ingredient of the CONCEP protective agent is also used to protect seed of cultivated grass from damage by metolachlor. Ciomethrin is also described in U.S. Pat. No. 4,070,389 as an antidote to chloroacetanilide and thiocarbamate herbicide between millet and rice, N-dialacetate. Compound (commonly called * 'dichloromide; code R-25 788) is used to protect cereals from damage by thiocarbamate 5-ethyl-N, N-dipropylthiocarbamate (the active ingredient of the herbicide ERADICANl ^ and acetoclorine (the active ingredient of the herbicides WENNEI ^^. The antidote compound AD -67 is used to protect cereals from damage by acetoclor in commercial h herbicides GUARDIAii ^ and ACENIT ^ R

The literature also describes the use of the preservative fenchlorim to protect against tffc-chloroacetanilide herbicide pretilachlor, alone or in the presence of sulfonylurea, commonly called cinosulfuron (the active ingredient of the SOFIT ^ SUPER herbicide). Fenchlorin and cinosulfuron are identified by the chemical name that follows. Cinosulfuron is characterized by substituted phenylsulfonyl- and substituted triazinyl radicals on individual nitrogen atoms in urea. It is also known that a variety of sulphonyl urea protective agents commonly known as primisulfuron (the active ingredient of the herbicide BEACObr. Is used. Primisulfuron is labeled with substituted phenylsulfonyl and substituted pyrimidinyl radicals on individual urea nitrogen atoms; its chemical structure is listed below).

The use of 1,8-naphthalic anhydride, R-25788 and ciomethrin for the protection of cereals, e.g. maize, wheat, rice, and cultivated grasses before certain sulphonyl ureas, which are characterized by substituted phenylsulfonyl radicals and substituted pyrimidinyl or tri-zynyl radicals on individual urea nitrogen atoms (U.S. Patent 4, 343, 649). Other literature (EP Patent File No. 147365, published 3/7/1985) also describes protection against a class of sulfonylureas similar to those in U.S. Patent No. 649, with the same protective agents and two additional, i.e. R-28725 and flurazole; the chemical identity of the protective agents in these two literatures is described below.

The Applicant's Attorney published patent applications relating to the use of various 5-heterocyclic substituted oxazolidine dichloroacetamide protecting agents for use in a variety of herbicides including och-chloroacetanilide and sulfonylureas and mixtures thereof.

- 4 Prior to my present disclosure, I was not aware of the protection against pyrazolylsulfonylurea herbicides, although such herbicides were already known to themselves, e.g. of U.S. Pat. No. 4,668,277 and 4,931,081 and EP Patent Nos. 282,613 (9/21/1988), 087, 780 (8/18/1982) and South African patent file 83/03850 (11/28/1983).

It is an object of the present invention to provide compositions of pyrazolylsulfonylureas, optionally containing a co-herbicide, in combination with antidotes, the compositions of which are suitable for reducing crop damage due to the phytotoxicity of said herbicides.

SUMMARY OF THE INVENTION

The subject of the present invention are herbicide compositions containing pyrazolylsulfonylurea derivatives and antidote compounds to reduce damage to various crops, especially cereals, due to the phytotoxic effects of said herbicide when used alone or in combination with other compounds, in particular <-halogenated acetamides and ct-halogenated acetamides like soherbicides. Unless mentioned herein, the term tfHhalogenated acetanilides generally includes <X-halogenated acetanilides as a subgroup (requiring phenyl or substituted phenyl bound to the nitrogen atom in acetamide) and acetamides having substituents other than (un) substituted phenyl.

Specifically, from the main point of view, the object of the present invention is a composition comprising:

a) a herbicide compound of the formula:

R,

R,

-CO ₂ nhc-nN in which: R 1 = H, alkyl or phenyl;

R4 = H, alkyl or halogen;

R 3 = R _2> NO ₂ or COOR ^;

R 2 = alkyl, C ₂₂ alkenyl;

N (R ₅ ) (R ₆ ), SO ₂ N (R _? ) (Θ) or SO ₂ R ₉ ;

- R 8 = C 1-6 alkyl;

R ₁₀ = H or C 1-3 alkyl;

= independently alkyl or alkoxy, nalogen or ^{N (R} 13 ^{) (R} 14 ^); = alkyl and

N in

b) an anti-toxic effect amount (s) of the compound of the formula:

? / ^R 16 ^R 13 ^{and R} 14 A = CH or

wherein R1 can be selected from the group consisting of halogenated alkyl; halogenated alkenyl; alkyl; alkenyl; cycloalkyl; cycloalkyl-alkyl halogen; hydrogen; carboalkoxy; N-alkenylcarbamylalkyl; N-alkenylcarbamyl; N-alkyl-N-alkynylcarbamylalkyl; N-alkenylcarbamylalkoxyalkyl; N-alkyl-Nalkynylcarbamylalkoxyalkyl; alkynyloxy; halogenated alkoxy; ' N-alkylNalkynylcarbamyl; thiocyanatoalkyl; alkenylaminoalkyl; alkylcarboalkyl; cyanoalkyl; cyanatoalkyl; alkenylaminosulfonylalkyl; alkylthioalkyl; halogenated alkylcarbonyloxyalkyl; alkoxycarboalkyl; halogenated alkenylcarbonyloxyalkyl; hydroxy haloalkyloxyalkyl; hydroxyalkylcarboalkyloxyalkyl, hydroxyalkyl; alkoxysulfonoalkyl; furil; thienyl; alkyldithiolenyl; thienalkyl; phenyl and substituted phenyl, said substituents being selected from halogen, alkyl, halogenated alkyl, alkoxy, carbamyl, nitro carboxylic acids and their salts, halogenated alkylcarbamyl, phenylalkyl, phenylhaloalkyl, phenylalkenyl, substituted phenylalkenyl, where said substituents can be selected of the following: halogen, alkyl, halogenated alkyl, alkoxy, carbamyl, nitro, carboxylic acids and their salts, halogenated alkylcarbamyl, phenylalkyl, phenylhaloalkyl, phenylalkenyl, substituted phenylalkenyl, wherein said substituents can be selected from halogen, alkyl, alkoxy, halogenated phenyl , phenylalkoxy, phenylalkylcarboxyalkyl, phenylcycloalkyl, halogenated phenoxyalkyl, bicycloalkyl, alkenylcarbamylpyridinyl, alkynylcarbamylpyridinyl, dialkenylcarbamylbicycloalkenyl; alkynylcarbamylbicycloalkenyl; halogenated phenylalkenoxy; halogenated thiophenylalkyl;

R ^ · and may be the same or different and can be selected from the group consisting of: alkenyl; halogenated alkenyl; hydrogen; alkyl; halogenated alkyl; alkynyl; cyanoalkyl; hydroxyalkyl; hydroxyhaloalkyl; halogenated alkylcarboxyalkyl; alkylcarboxyalkyl; alkoxycarboxyalkyl; thioalkylcarboxyalkyl; alkoxycarboalkyl; alkylcarbonyloxyalkyl; amino; formyl *, halogenated alkyl-N-alkylamido; halogenated alkylamido; halogenated alkylamidoalkyl; halogenated alkyl-N-alkylamidoalkyl; halogenated alkylamidoalkenyl; alkylimino; cycloalkyl; alkylcycloalkyl; alkoxyalkyl; alkylsulfonyloxyalkyl; mercaptoalkyl; alkylaminoalkyl; alkoxycarboalkenyl; halogenated alkylcarbonyl; alkylcarbonyl; alkenylcarbamyloxyalkyl; cycloalkylcarbamyloxyalkyl; alkoxycarbonyl; halogenated alkoxycarbonyl; halogenated phenylcarbamyloxyalkyl; cycloalkenyl; phenyl; substituted phenyl, wherein said substituents may be selected from alkyl, halogen, halogenated alkyl, alkoxy, halogenated alkylamido, phthalamido, hydroxy, alkylcarbamyloxy, alkenylcarbamyloxy, alkylamido, halogenated alkylamido or alkylcarboalkenyl; phenylsulfonyl ', substituted phenylalkyl, wherein said substituents may be selected from the following: halogen or alkyl; dioxyalkylene, halogenatedphenoxy dialkylaminoalkyl; alkylthiodes azolyl; piperidyl; piperidylalkyl; dioxolanylalkyl, thiazolyl; alkylthiazolyl; benzothiazolyl; halogenated benzothiazolyl; alkyl substituted with furyl; furylalkyl; pyridyl; alkylpyridyl; alkyloxazolyl; tetrahydrofurylalkyl; 3-cyano, thienyl; alkyl substituted thienyl; 4,5-polyalkylene-thienyl; cX-halogenated alkylacetamidophenylalkyl; R-halogenated alkylacetamidonitrophenylalkyl-cyanoalkenyl; cG-halogenated alkylacetamidoohalophenylalkyl,

R ^ and when taken together may form a structure consisting of: piperidinyl; alkylpiperidinyl; pyridyl; di- or tetrahydropyridinyl; alkyltetrahydropyridyl; morpholyl; alkylmorpholyl; azabicyclononyl; diazacycloalkanyl; benzoalkylpyrrolidinyl; oxazolidinyl; perhydrooxazolidinyl; alkyloxazolidinyl; furyloxazolidinyl; thienyloxazolidinyl; pyridyloxazolidinyl; pyrimidinyloxazolidinyl; benzooxazolidinyl; spirocycloalkyloxazolidinyl; alkylaminoalkenyl; alkylidenimino; pyrrolidinyl; piperidonyl; perhydroazepinyl; perhydroazocinyl; pyrozo2.il; dihydropyrazolyl; piperazinyl; perhydro 1,4,4-diazepinyl; quinolinyl; isoquinolinyl; dihydro-, tetrahydroin perhydroquinolyl · or -isoquinolyl; indolyl and di- and perhydroindolyl and the aforementioned combinations of members and R R .substituted by those independent radicals R ^ and R ^ listed above; or (ii) one of the following compounds:

ot- / (cyanomethoxy) imino7 benzenoacetonitrile (commonly called ciomethrinyl), dr 1,3-dioxolan-2-yl-methoxy) imino / benzercacetonitrile (commonly called oxybetrinyl),

0- [1,3-dioxalan-2-ylmethyl] -2,2,2-trifluoromethyl-4 ¹

-chloroacetophenone oxime (code CGA-133205),

Benzene-methylamine, N- / 4- (dichloro-methylene-1,3-dithiolan-2-ylidene-methylmethyl, hydrochloride,

1,8-naphthalic anhydride,

4,6-dichloro-2-phenyl-pyrimides) t (commonly called fenchlorim),

2-chloro-N- [1- (2,4,6-trimethylphenyl) ethenyl / acetamide,

Ethylene glycol acetal 1,1-dichloroacetone,

1,3-dioxolane, 2- (dichloromethyl) -2-methyl-,

5-Thiazolecarboxylic acid, 2-chloro-4 (trifluoromethyl) -, (phenylmethyl) -ester (commonly called flurazole)

Phosphorothioic acid, 0,0-diethyl (- (3-methylphenyl) ester,

4-pentenenitrile, 2-methyl-2- (4-methylphenyl) thio7 ~,

5- chloro-8 · - (cyanomethoxy) quinoline, 1-methylhexyl-2- (5-chloro-8-quinolinoxy) acetate,

O- (methoxycarbonyl) -2- (8-quinolinoxy) acetamide oxime,

5-Oxazolecarboxylic acid, 2 - [(2,2-dimethylethyl) amino] -4- (trifluoro-methyl) -, ethyl ester,

Acetic acid, (diphenylmethoxy) -, methyl ester (code ΜΟΝ-7400),

Allyl-N-methylditl, carbanilate,

4-isoxazolecarboxylic acid, 5- (2,4-dichlorophenyl) -, ethyl ester,

Pyrimidine, 4,6-dichloro-2-phenyl-,

4-pentenitrile, 2-methyl-2 - / (A-methylphenyl) thio7-> acetonitrile, N (5-chloro-8-quinolinyl) oxy / -,

Acetamide 2- (diphenylmethoxy) -N-methyl-,

Glycine, N- / bis (4-methoxyphenyl) - methyl7-, ethyl ester,

Glycine, N-fbis (4-chlorophenyl) - methyl-, ethyl ester,

Acetic acid, N, 10-l-dihydro-5H-dibenzoyl-1-cyclohepten-5-yl) oxy7,

1,1-dimethylethyl ester,

Ethantioamide, 2- (diphenylmethoxy) -,

Acetic acid, (diphenylmethoxy) -, propyl ester,

Acetic acid, (diphenylmethoxy) -, 2,2,2 trifluoro-ethyl ester,

Acetic acid, N-phenyl ^ 3- (trifluoro-methyl) phenyl / methoxy · -, 2-methyl-2-proponamine salt,

Acetic acid, (diphenylmethoxy) -, phenyl ester,

Ethanethioic acid, 2- (diphenylmethoxy) -,

5-ethyl ester,

Acetic acid, (diphenylmethoxy) -, 2-cyanoethyl ester, Acetic acid, {phenyl / 3- (trifluoromethyl) phenyl / methoxy} -, 2,2,2-trifluoroethyl ester,

Acetic acid, (diphenylmethoxy) -, 2-propynyl ester, Acetic acid, (diphenylmethoxy) -, 3-furanylmethyl ester, Acetic acid, / bis (2,6-dimethylphenyl) - methoxy7 ^_ , Acetic acid, (diphenylmethoxy) -,

3-nitrophenyl ester,

Acetic acid, f / bis (2,6-dimethylphenyl) 7- methoxy-, ethyl ester,

Acetic acid, (diphenylmethoxy) -, 1-cyano1-methylethyl ester,

5- Thiazolecarboxylic acid, 2-chloro-4- (trifluoromethyl) -, ethyl ester,

5-thiazolecarboxylic acid, butyl ester,

2- chloro-, 4- (trifluoromethyl) -,

5-Thiazolecarboxylic acid, 2-chloro-, hexyl ester, 4- (trifluoromethyl) -,

5-Thiazolecarboxylic acid, 2-chloro-4 (trifluoromethyl) -, octyl ester,

5-Thiazolecarboxylic acid, 2-chloro-4 (trifluoromethyl) -, phenyl ester,

5-Thiazolecarboxylic acid, 2-chloro-4 (trifluoromethyl) -,

5-Thiazolecarboxylic acid, 2- [bromo-4 (trifluoromethyl) 7-, ethyl ester

5-Thiazolecarboxylic acid, 2-iodo-4 (trifluoromethyl) -, ethyl ester,

5-Thiazolecarboxylic acid, 2-chloro-4 (trifluoromethyl1) -, 1-methylethanamine salt

Benzylamine-, (alpha-methyl-, N-4- (methyl) 1,3-dithiol-2-ylidene) hydrochloride,

Pyridine, N-oxide, 2- (3,4,5,6-tetrachloro2-pyridylthio) -,

Acetic acid, / 3,5-bis (trifluoromethyl) phenoxy _ / »

Propanamide, 2-chloro-N- [5-iodo-4- (trifluoromethyl) -2-thiazolyl] -,

Cyclopropanecarbonitrile, 1 - [(3,4-dimethylphenyl) thio] -,

Propannitrile, 3 - // 2- (1,1-dimethyl-ethyl) phenyl7-thio-,

4-pentenenitrile, 2-methyl-2 - // 4- (1-methylethyl) phenyl7thio_7-,

Ethanimidamide, N '- [(methoxycarbonyl) - oxo7 -2- (8-quinolinyloxy) -, (3H) -isobenzofuranone, 3- [2- (2,5-dimethoxyphenyl) -2-oxoethyl] -,

Acetic acid, 2- (diphenylmethoxy) -Natrium salt, hemihydrate,

Acetic acid, 2- (diphenylmethoxy) - or

Acetic acid, (diphenylmethoxy) -, 2-propanamine salt.

Preferred pyrazolylsulfonylurea compounds for tonamous use are those of formula IA below, a subset of formula I:

Oh

II

wherein: R 1 and R 1 are C 1-6 alkyl;

3-3 is H, 2 alkyl, bromo or chloro; and and are independently alkyl or alkoxy.

Even more advantageous are the species of Formula IA, in which:

R ^ and methyl or ethyl,

R4 is H, methyl bromo or chloro and

R ^ and are independently methyl or methoxy.

Among the types of pyrazolylsulfonylurea of particular interest are the following species:

N - [(4-methoxy-6-methylpyrimidin-2-yl) amino-carbonyl] -3-chloro-4-methoxy-carbonyl-1-methylpyrazole5-sulfonamide;

N - / ”(4,6-dimethoxypyrimidin-2-yl) aminocarbonyl7 *

3-chloro-4-methoxycarbonyl-1-methylpyrazole5-sulfonamide;

N - [4-methoxy-6-methylpyrimidin-2-yl) amino-carbonyl73-chloro-4-ethoxycarbonyl-1- methyl-pyrazole5-sulfonamide;

N - [(4,6-dimethoxypyrimidin-2-yl) amino-carbonyl73-chloro-4-ethoxycarbonyl-1-methylpyrazole5-sulfonamide;

N-Z \ 4-Methoxy-6-methylpyrimidin-2-yl) amino-carbonyl73-bromo-4-ethoxycarbonyl-1-methylpyrazole

5-sulfonamide,

N- [(4,6-dimethoxypyrimidin-2-yl) aminocarbonyl] -3-bromo-4-ethoxy-carbonyl-1-methylpyrazole5-sulfonamide and

N - [(4,6-dimethoxy-pyrimidin-2-yl) -amino-carbonyl] -4-ethoxycarbonyl-1-methyl-pyrazole 5-sulfonamide.

The types of pyrazolylsulfonylurea compounds having the highest priority according to the present invention are:

N - / (4,6-dimethoxypyrimidin-2yl) aminocarbonyl73-chloro-4-methoxycarbonyl-1-methylpyrazole5-sulfonamide (code NC-319) and

N-Z7 +, 6-dimethoxypyrimidin-2-yl) aminocarbonyl-4-ethoxycarbonyl-1-methylpyrazole-5-sulfonamide (code NC-311).

One group of preferred antidote compounds includes those of formula II wherein halogenated alkyl, R 5 and R 5 are independently alkenyl or halogenated alkenyl or 2,3-dioxolan-2yl-methyl and R and R 4 when the combined form a heterocyclic ring, saturated or unsaturated, with and containing 0, S and / or N atoms which may be substituted by alkyl, halogenated alkyl, alkoxy or alkoxyalkyl or halogenated acyl groups. A preferred moiety of halogenated alkyl R 5 in formula II is dichloromethyl. Preferred species in this group of antidote compounds are N, N-diallyl-dichloroacetamide and N- (2-propenyl) -N- (1,3-dioxolanylmethyl) dichloroacetamide.

The antidote compounds of formula II, of even greater advantage, are the group of substituted 1,3-oxazolidinyl dichloroacetamides having the following formula:

O in which: R ^ g is hydrogen, alkyl, alkylol, halogenated alkyl or alkoxy, C ', alkoxyalkyl, bicyclic, carbon Zo radical having up to 10 carbon atoms, phenyl or saturated or unsaturated heterocyclic or heterocyclic methyl radical which has C, ring atoms and contains 0, S and / or N atoms _; or known phenyl and heterocyclic (methyl) radicals substituted by one or more of alkyl, halogenated alkyl, alkoxy, alkoxyalkyl, halogen or nitro radical ^, and and _{R? o} are independently hydrogen, alkyl or halogenated alkyl, phenyl or heterocyclic (methyl) R The ^ g term or together with the carbon atom to which they are attached may form a C1-C, spiro-cycloalkyl group.

Preferred formula III members are those wherein R 1 and 2 are one of said heterocyclic members and R 1 and R 2 are independently methyl, trifluoromethyl or, when combined with the carbon atom to which they are attached, form or cycloalkyl radical.

Preferred Formula III antidote compounds are the following compounds:

Oxazolidine, 3- (dichloroacetyl) -2,2,5-tri-methyl-, (code R-29148),

Oxazolidine, 3- (dichloroacetyl) -2,2-di-methyl (code R-28725 and AD-2)

Oxazolidine, 3- (dichloroacetyl) -2,2-dimethyl5-phenyl-,

Oxazolidine, 3- (dichloroacetyl) -2,2-dimethyl5 (2-furanyl) -,

Oxazolidine, 3- (dichloroacetyl) -2,2-dimethyl5- (2-thienyl) -,

PyridoO, 3- / 3- (dichloroacetyl) -2,2-dimethyl '

-5-Oxazolidinyl7 ^- ,

4- (dichloroacetyl) -1-oxa-4-azaspiro- (4,5) decane (code AD-67).

Another group of dichloroacetamide antidote compounds of formula II are the following compounds:

4- (dichloroacetyl) -3,4-dihydro-3-methyl-2H2,4-benzoxazine (commonly called benoxychlor; code CGA-154281),

Ethanone, 2,2-dichloro-1- (1,2,3,4-tetrahydro-methyl-2-isoquinolinyl) -,

N- (dichloroacetyl) -1,2,3,4-tetrahydroquinaldin,

1- (dichloroacetyl) -1,2,3,4-tetrahydroquinoline, Cis / trans-piperazine, 1,4-bis / dichloro 1,4-acetyl) 2,5-dimethyl-,

Ν, Ν-dipropenyl dichloroacetamide,

N- (2-propylene) -N- (1,3-dioxolan-2-ylmethyl) dichloroacetamide (code PPG-1291),

1,5-diazacyclononane, 1,5-bis- (dichloroacetyl, 1-azaspiro / 4.47 nonane, Ι-dichloroacetyl), Pyrrolo [1,2-a7-pyrimidin-1 '(6H) 7-one, 1 - (dichloroacetyl) hexahydro-3, 3,?-trimethyl,

2.2-dimethyl-3- (dichloroacetyl) -1,3-oxazole and

2.2-dimethyl-5-methoxy-3- (dichloroacetyl) 1,3-oxazole.

Another group of antioxidant compounds which are preferred are those listed in paragraph (b) (ii) in the Summary of the Invention.

The particular utility of these compounds of the present invention has been found e.g. in cereals, rice, wheat, cereals (eg barley and rye), soybeans, sugar beet, cotton, etc.

Another aspect of the present invention is the combination of various Soherbicides in mixtures containing pyrazolylsulfonylurea herbicide (s) and to broaden the spectrum of control of undesirable plants associated with beneficial crops.

'Herbicide compounds that can be used as co-herbicides with the pyrazolyl sulfonylurea compounds of formula I come from a wide variety of known chemical classes, e.g. ot-chloroacetamides, thiocarbamates, imidazolinones, pyridines, triazines, heterophenyl ethers, diphenyl ethers, ureas, sulfonylureas, azolopyrimidine sulfonamides, thiazoles, pyrazoles, isoxazoles, nitroanilines, pyrrolidinones, aromatic and heterocyclic cyclocyclics Individual members of the preceding classes may be derivatives having one or more substituents selected from a wide variety of radicals, commonly and appropriately used in herbicide molecules.

The class of compounds that has the highest priority and is the same ···! herein, as a component of co-herbicides, includes <X-chloroacetamides of formula IV,

IV

C1CH _Z C - N

where R_, and R_ are independently hydrogen; C, _o alkyl, alkoxy, alkoxyalkyl, j 21 22 1-8 acylaminomethyl, acyl-lower alkyl substituted amino-methyl cycloalkyl, cycloalkylmethyl, mono- or polyunsaturated alkenyl, alkynyl, cycloalkenyl, cycloalkenylmethyl having up to 8 carbon atoms; phenyl; or heterocyclyl or heterocyclylmethyl containing 1-4 -hetero atoms in the ring selected independently from N, S or 0; and wherein said members R10 and R22 may be substituted by alkyl, alkenyl, alkynyl, alkenyloxy, alkynyloxy, alkoxy, alkoxyalkyl, alkoxycarbomethyl or ethyl having up to 8 carbon atoms; nitro; halogen; cyano; amino or amino substituted with alkyl, and wherein R21 and R22 may be combined with an N atom to form one of said heterocyclyl or substituted heterocyclyl members.

Preferred Formula IV herbicide compounds are those in which R21 is an alkoxyalkyl radical of structure -BO-R23 in which B and R23 are alkyl radicals in a straight or branched chain having a combined sum of up to 8 carbon atoms; or a substituted or unsubstituted heterocyclyl or heterocyclylmethyl radical containing from 1 to 4 hetero.atoms in the ring selected independently from the N, S or O atoms, member ^ 22 'P ^a * - either one of said heterocyclyl or heterocyclylmethyl radicals or optionally substituted phenyl radical.

Preferably, the phenyl radical is substituted with alkyl groups, especially in the ortho positions. Similarly, some preferred heterocyclyl members are substituted with alkyl or alkoxy radicals.

Among the more important heterocyclyl members and / or formulas IV are independently mentioned: furanyl, thienyl, pyrazonyl, pyrrolyl, isoxazolyl, isothiazolyl, triazolyl, imidazolyl and pyrimidinyl radicals and their analogs having a methylene (-CH ^ -) linking heterocyclyl radical a nitrogen atom of acetamide, e.g. pyrazol-1-ylmethyl. When the heterocyclyl radical is attached directly to the nitrogen in the amide (without a methylene intermediate, the bonding via the carbon atom in the ring or the heteroatom in the ring may be appropriate. , alkoxyiminoalkyl, benzyl, hydroxyalkyl, halogenated alkoxy and -alkoxyalkyl, cyanoalkoxy and -alkoxyalkyl, methyl, ethyl, propyl, butyl and their isomers and the like.

Preferred types of Formula IV include N- (2,4-dimethylthienyl-3-yl) -N- (1-methoxy-prop-2-yl) -2-chloroacetamide; N- (1H-pyrazol-1-ylmethyl) N- (2,4-dimethylthien-3-yl) -2-chloroacetamide; N- (1-pyrazol-1-ylmethyl) N- (4,6-dimethoxypyrimidin-5-yl) -2-chloroacetamide and 2-chloro-N-isopropyl-1- (3,5,5-trimethylcyclohexene-1- il) acetamide.

Another important subtype of <RTI ID = 0.0> X-halogenated </RTI> acetamide compounds which are advantageous and useful here as a component of co-herbicides are e ('chloroacetanilides of formula V:

in which:

(^ $ 2) 1

R24 is hydrogen, alkyl, halogenated alkyl, alkoxy or alkoxyalkyl, alkenyl, halogenated akenyl, alkynyl or halogenated alkynyl having up to 6 carbon atoms, C, heterocyclyl or heterocyclylmethyl having atoms 0, S and / or N and which may be substituted by halogen, alkyl, carbonalkyl or carbonylalkoxyalkyl, nitro, amino and cyano groups, ^ 25 ⁱⁿ dichloromethane, nitro, amino, alkyl, alkoxy or alkoxyalkyl and n is 0 - 5.

Examples of important acetamide herbicides of formulas IV and V are as follows:

2-chloro-N-isopropylacetanilide (commonly called propachlor);

2-chloro-2 ', 6'-diethyl-N- (methoxymethyl) -, acetanilide (commonly called alachlor)

2-chloro-2 ', 6'-diethyl-N- (butoxymethyl-acetamide) (commonly called butachlor)

2-chloro-N- (ethoxymethyl) -6 * -ethyl-o-acetoluidide (commonly called acetochlor);

N-Chloroacetyl-N- (2,6-diethylphenyl) glycine ethyl ester (commonly called diethyl ethyl);

2-chloro-N- (2,6-dimethylphenyl) -N- (2-methoxyethyl) acetamide (commonly called dimethachlor);

2-chloro-N- (2-n-propoxyethyl) -2 ', 6'-diethylethanethilide (commonly called pretilachlor);

2-chloro-N- (2-methoxy-1-methylethyl) -6'ethyl-o-acetotoluidide (commonly called metolachlor);

2-chloro-2 ', 6'-dimethyl-N- (1-pyrazol-1-yl-methyl) acetanilide (commonly called metazachlor);

2-chloro-N- (2,6-dimethyl-1-cyclohexan-1-yl) -N (1H-pyrazol-1-ylmethyl) acetamide;

2-chloro-N-isopropyl-1- (3,5,5-trimethylcyclohexen-1-yl) acetamide (commonly known as trimexachlor);

2-chloro-2 ¹ -methyl-6 ¹ -methoxy-N- (isopropoxymethyl) acetanilidine;

2-chloro-2'-methyl-6 ¹ -trifluoromethyl-N- (ethoxymethyl) acetanilidine;

N- (2,4-dimethylthien-3-yl) -N- (1-methoxyprop-2-yl) 2-chloroacetamide;

N- (1H-pyrazol-2-ylmethyl) -N- (2,4-dimethylthien-3-yl) 2-chloroacetamide;

N- (1-pyrazol-1-ylmethyl) -N- (4,6-dimethoxypyrimidin5-yl) -2-chloroacetamide.

The types of compounds of formula V that have the highest priority are 2-chloro-2 '~ ethyl-6'-methyl-N- (ethoxymethyl) acetamylide (commonly called acetochlor), 2-chloro-2', 6'-diethyl- N- (methoxymethyl) acetanilide (commonly called alachlor), 2-chloro-2'6'-diethyl-N- (butoxymethyl) acetanilide (commonly called butachlor), 2-chloro-2'-ethyl-6'-methyl-N- (1-methyl-2-methoxyethyl) -acetanilide (commonly called metolachlor), 2-chloro-2 ', 6'-diethyl-N- (2-n-propoxyethyl) -acetanilide (commonly called pretachlor) and 2-chloro- 2 ', 6'-dimethyl-N- (pyrazolylmethyl) acetanilide (commonly called metazachlor).

A broader group of preferred o-chloroacetamide and o (-halogenated acetanilide herbicides include the particularly preferred types of formulas IV and V identified below.

Another class of preferred compounds useful as a component of the co-herbicides in the composition / method of the present invention are thiocarbamates.

Examples of important thiocarbamate herbicides are as follows:

cis / trans -2,3-dichloroallyl-diisopropyl-thiolcarbamate (commonly called dialate);

2,3,3-trichloroallyl diisopropylthiocarbamate (commonly called trialate).

Ethyl dipropylthiocarbamate (commonly called EPTC); S-Ethyldiisobutylthiocarbamate (commonly called butylate);

S-propyl dipropylthiocarbamate (commonly called vernolate);

Examples of important sulfonylureas of co-herbicides include:

Benzene sulfonamide, 2-chloro-N- ^[ z (4-methoxy-6-methyl-1,3,5-triazin-2-yl) amino] -carbonyl (commonly called chlorosulfuron);

Benzoic acid, 2- (Y7) (4-chloro-6-methoxy-2-pyrimidin-2-yl) aminocarbonyl7amino] -sulfonyl-ethyl ester (commonly called chlorimuronetyl);

2-Thiophenecarboxylic acid, 3 - //// (4,6-dimethoxy-1,3,5-triazin-2-yl) amino-carbonyl-7-amino / sulfonyl7-, methyl ester (commonly called tifensulfuron methyl; code DPX M6316) ;

Benzoic acid, 2 - [((4,6-dirnetyl-2-pyrimidinyl) -amino] carbonyl7amino7-sulfonyl) -methyl ester (commonly called sulfuron methyl);

Benzenesulfonamide, 2- (2-chloroethoxy) -N - // ”(4-methoxy-6-methyl · *

1.3.5-triazin-2-yl) amino N-carbonyl7 (commonly called triasulfuron);

Benzoic acid, 2-.////(( 4-methoxy-6-methyl- 1,3,3- triazin2- yl) amino7carbonyl7 ^- amino7sulfonyl / -methyl ester (commonly called metstifuron methyl);

Benzoic acid, 2 - ///// 4,6-di (difluoromethoxy) -2pyrimidin-2-yl7amino7-carbonyl7aminq7 sulfonyl / methyl ester (commonly called primisulfuron);

Pyridine, 3 - //// 4,6-dimethyl-2-pyrimidin-2-yl) amino / carbonyl / amine sulfone 1 / -N, N-d has ylcarbamoyl 1 (commonly called nicosulfuron);

Pridin, 3 - [((4,6-dimethoxy-2-pyrimidin-2-yl) amino] carbonyl / aminosulfonyl) ethylsulfonyl (DPX code E9636);

Benzenesulfonamide, 2- (methoxyethoxy) -N - [(4,6-dimethoxy-1,3,5-1r and azin-2-yl) amino / carbonyl] (commonly called cinosulfuron)

Met Ϊ1-2 - //// Π 4,6 - d imethoxy i - 2 - p i r imidine - 2 - i 1) amino / carbon and l7amino sulf onyl7-methyl / benzoate (common name (bensulfuron methyl);

N - [(4,6-dimethylpyrimidin-2-yl) amino-carbonyl] -1- (1-methylethyl) -1H-imidazole-2-sulfonamide;

N - [(4-methoxy-6-methylpyrimidin-2-yl) -aminocarlyl] onyl] -1- (1-methylethyl) -1H-imidazole-2-sulfonamide;

N - [(4,6-dimethoxypyrimidin-2-yl) amino-carbonyl] -1- (1-methylethyl) -1H-imidazole-2-sulfonamide;

N- [4,6-dimethylpyrimidin-2-yl) aminocarbonyl] -1-ethyl-1H-imidazole-2-sulfonamide;

N - ((4-methoxy-6-methylpyrimidin-2-yl) -aminocarbonyl7-1-ethylH-imidazole-2-sulfonamide;

N- (4,6-dimethoxypyrimidin-2-yl) aminocarbonyl7-1-ethylH-imidazole-2-sulfonamide;

N-A (4,6-dimethoxypyrimidin-2-yl) aminocarbonyl / -5-bromo-1-methyl-1H-imidazole-4-sulfonamide.

Important soherbicides control include the following compounds:

N- (4-chlorophenoxy) phenyl1-N, N-d has a ylurea;

Ν, Ν-dimethyl-N ′ - (3-chloro-4- (e) ylphenyl) urea;

3- (3,4-dichlorophenyl) -1,1-dimethylurea;

1,3-dimethyl-3- (2-benzothiazolyl) urea;

3- (p-chlorophenyl) -1,1-dimeth ylurea a and

1- Butyl-3- (3,4-dichlorophenyl) -1-methylurea a.

Another class of preferred compounds useful here as a component of co-herbicides is imidazolinones.

Examples of important imidazolinone herbicides include:

3-quinolinecarboxylic acid, 2- [4,5-dihydro-4-methyl-4 (1-methylethyl) -5-oxo-1H-imidazol-2-yl];

3-Pyridinecarboxylic acid, 2- [4,5-dihydro-4-methyl-4 (1-methylethyl) -5-oxo-1H-imidazol-2-yl];

Benzoic acid, 2- / 4,5-dihydro-4-methyl-4- (1-methylethyl) -5-oxo-1H-imidazol-2-yl) -4 (or 5) -methyl;

3-Pyridinecarboxylic acid, 5-ethyl-2- [4-methyl-4- (1-methylethyl) ~ 5-oxo-1H-imidazol-2-yl] -;

3-Pyridinecarboxylic acid, 2- [4 > 5-dihydro-4-methyl-4- (1methyl-ethyl) -5-oxo-1H-imidazol-2-yl7-5methyl-, ammonium salt;

2- (5-methyl-5-trifluoromethyl-1-H-imidazol-4-one-2-yl) -pyridine-3-carboxylic acid;

2- (5-methyl-5-trifluoromethyl-1-H-imidazol-4-one-2-yl) - (m) ethyl isonicotinic acid;

2- [5- (1-Fluoroethyl) -5- (m) ethyl-H-imidazol-4-one-2-yl] isonicotinic acid;

2- [5- (difluoromethyl-1 (m) ethyl-1-H-imidazol-4-one-2-yl) -5 (m) ethyl-isonicotinic acid;

2- (5- (1-Fluoroethyl) -5- (m) ethyl) -imidazol-4-one-2-yl7-isonicotinic (m) ethyl ester.

Examples of important pyri din co-herbicides include:

3- pyridinecarboxylic acid, -2 (difluoromethyl) -5-4,5-dihydro2-thiazolyl-4- (2-methyl-propyl) -6- (trifluoromethyl) -, methyl ester;

3-Pridinecarboxylic acid, 2- (difluoromethyl) -4- (2-methylpropyl) -5- (1H-pyrazol-1-ylcarbonyl) -6- (trifluoromethyl) -, methyl ester;

3,5-pyridinedicarboxylic acid, 2- (difluoro-methyl) -4 (2-methylpropyl) -6-trifluoromethyl, dimethyl ester;

3,5-pyridine dicarbothioic acid, 2- (difluoromethyl) -4- (2methylpropyl) -6- (trifluoromethyl) -, S, S-dimethyl ester;

5- (trifluoromethyl) -4-chloro-3- (3 '- / 1-ethoxy-carbonyl7-ethoxy-4-nitrophenoxy) -1-methylpyrazole;

5- (Trifluoromethyl) -4-chloro-3- (3 ¹ -methoxy-4 ¹ -nitrophenoxy)

-1-methylpyrazole;

5- (trifluoromethyl) -4-chloro-3- (3 '- (1-butoxycarbonyl) -ethoxy-4'-nitrophenoxy) -4-methylpyrazole;

5- (trifluoromethyl) -4-chloro-3- (3'-methyl-sulfamoylcarbonyl propoxy-4'-nitrophenoxy) -4-methylpyrazole;

5- (Trifluoromethyl) -4-chloro-3- (3'-propoxy-carbonylmethyloxy-4'-nitrophenoxy) -1-methylpyrazole;

(+) - 2- [4 - [[5- (trifluoromethyl) -2-pyridinyl] -oxy] phenoxy] propanoic acid (9CI);

5.5-dimethyl-2- (difluoromethyl) -4-isobutyl-6-trifluoromethyl-3,5-pyridinedicarbothioate;

3- (pyridinecarboxylic acid, 2- (difluoromethyl) -5- (4,5-dihydro-2-thiazolyl) -4- (2-methyl-propyl) -6- (trifluoromethyl) -, methyl ester;

3,5-pyridinecarboxylic acid, 2- (difluoromethyl) -4- (2-methylpropyl) -6- (trifluoro-methyl) -, dimethyl ester;

3.5- Pyridindicarbothioic acid; 4- (cyclopropylmethyl) -2 (difluoromethyl) -6- (trifluoromethyl) -, S, S-dimethyl ester;

Sulfoximine, N- (diethoxyphosphinyl) -S-methyl-S-phenyl-.

Examples of important heterocyclyl phenyl ethers of co-herbicides include:

5- (trifluoromethyl) -4-chloro-3- (3 '- (1-ethoxycarbonyl) -ethoxy- * and nitrophenoxy) -1-methylpyrazole;

5- (Trifluoromethyl) -4-chloro-3- (3'methoxy4'-nitrophenoxy) 1-methylpyrazole;

5- (trifluoromethyl) -4-chloro-3- (3 '- / 1-butoxycarbonyl-ethoxy 4'-nitrophenoxy) -4-methylpyrazole;

5- (Trifluoromethyl) -4-chloro-3- (3 * -methylsulfamoylcarbonyl proxy -4 ^1- nitrophenoxy) -4-methylpyrazole;

5- (Trifluoromethyl) -4-chloro-3- (3'-propoxy-carbonylmethyloxime 4 ^1- nitrophenoxy) -1-methylpyrazole;

(+) - 2- [4- (R) 5- (trifluoromethyl) -2-pyridinyl ^- oxy / phenoxy] propanoic acid.

Examples of important herbicides - benzoic acid derivatives include

3,6-Dichloro-2-methoxybenzoic acid (commonly called dicamba) »

2.5-dichloro-3-aminobenzoic acid (commonly called amiben and chloramiben),

5- (2'-Chloro-4'-trifluoromethylphenoxy) -2-nitrobenzoic acid (commonly called acifluorfen)

2.6- Dichlorobenzonitrile (commonly called diclobenil),

3.5.6- Trichloro-2-methoxybenzoic acid (commonly called tricamba),

2.3.6- Trichlorobenzoic acid, and

2.3.5.6- Tetrachlorobenzoic acid and the salts, esters and amides of the above acids.

Another class of compounds useful as co-herbicides in the compositions of the present invention are azolopyrimidine sulfonamides, which illustrate the following preferred species:

5,7-dimethyl-N- (2,6-dichlorophenyl) -2,2,4-triazolo / 1,5-pyrimidine-2-sulfonamide;

5-methyl-N- (2-bromo-6-chlorophenyl) -1,2,4-triazolo / 1,5-a] pyrimidine-2-sulfonamide;

5-methyl-N- (2,6-difluoro-3-methylphenyl) -1,2,4-triazoloN, 5-αptrimidine-2-sulfonamide;

5-methyl-N- (2,6-difluorophenyl) -1,2,4-triazolo-1,5,5-pyridine midin-2-sulfonamide;

5.7-dimethoxy-N- (2,6-dichloro-3-methylphenyl) -1,2,4-triazoloA, 5-aptrimidine-2-sulfonamide;

5.7-dimethoxy-N- (2-methoxy-6-trifluoromethylphenyl) -1,2,4triazolo-1H! , 5-α-phtimidine-2-sulfonamide;

5.7-dimethyl-2- (N- / 2-chloro, 6-proparglyloxyphenyl7-sulfamoyl)

-1,2,4-tr iazolo / Ί, 5- ^ 7 ~ prrimidine;

5.7- dimethyl-2- (N-Z 2-chloro-6- (2-ethoxyethoxy) -phenyl / ^-su lf ^a MOIL) -l, 2,4-triazolo, 5-a7-pyrimidine;

5.7-dimethyl-2- (N- [2-allyloxy-6-fluorophenyl-sulfamoyl) 2,2,4-triazoloA, 5-a] -ptrimidine;

5-methoxymethyl-N- (2-chloro-6-methylphenyl) -1,2,4-triazoloA, 5-7-pyrimidin-2-sulfonamide;

N- (2,6-difluorophenyl) -4,6-dimethylimidazolo / 1,2-7-pyrimidine2-sulfonamide;

N- (2,6-dichlorophenyl) -4,6-dimethylimidazolo Z, 1,2-pyrimidine 2-sulfonamide;

N- (2,6-difluorophenyl) -3-cyano-4,6-dimethylimidazolo / 1,2-7-pyrimidine-2-sulfonamide;

5.7-dimethyl-N- (2-chloro-6-methylphenyl) -1,2,4-triazolo-A, 5-a (4H, 7H) -dihydropyrimidine-2-sulfonamide;

7-methyl-N- (2-chloro-6-methylphenyl) -1,2,4-triazolo-N, 5-a7 / 4H, 7H-dihydropyrimidine-2-sulfonamide;

5.7-dimethyl-N- (2-chloro-6-ethoxyphenyl) -1,2,4-triazolo-1,5-7- [4H, 7H7-dihydropyrimidine-2-sulfonamide;

5-fluoro-7-methoxy-N- (2,6-difluorophenyl) -1,2,4-triazolo A, 5-cis-pyridine-2-sulfonamide;

N- (2,6-dichlorophenyl) -6,7-dihydro-5,6-dimethyl-7-oxo, 2,4 (triazole), 5-a7 Z,1,3,57-triazine-2 -sulfonamide;

N- (2,6-dichlorophenyl) -6,7-dihydro-5,6-dimethyl-7-thioxoA, 2,47triazoloA, 5-7-A, 3,5'-triazine-2-sulfonamide;

6 _with 7-dihydro-5,6-dimethyl-N- (2-methyl-6-nitrophenyl) -7-thioxoA, 2,47triazolo-5,5-a7- 1,8,57-triazine-2-sulfonamide ;

N, (2,6-dichlorophenyl) -6,7-dihydro-5,6-dimethyl-3-methoxycarbonyl-7-oxopyrazolo-A, 5-a7 ~ A, 3,57-triazine-2-sulfonamide;

N- (2,6-difluorophenyl) -6,7-dihydro-5,6-dimethyl-3-methoxycarbonyl-7-thioxo-pyrazolo / 1,5-7-Zl 3,57-triazine-2-sulfonamide;

N- (2-chloro-6-fluorophenyl) -6,7-dihydro-5,6-dimethyl-3-methoxycarbonyl-7-oxopyrazolo-1,5,5-trifluoro, 3,5-triazine-2-sulfonamide;

N- (2-chloro-6-fluorophenyl) -6,7-dihydro-5,6-dimethyl-3-methoxycarbonyl-7-thioxopyrazolo-1,5,5-zi, 3,57 ^- triazine-2-sulfonamide;

N- (2,6-difluorophenyl) -thiazole / N, 3,2-b7 / N, 2,47-triazole-2-sulfonamide;

N-5-methyl-4,5,6,7-tetrahydro-1,2,4-triazolo [1,5-7-pyrimidin-2-yl-2- (1,6-difluorophenyl) sulfonamide;

N- (5,7-dimethyl-1,2,4-triazolo) 1,5-7-pyrimidin-2-yl-thiophene sulfonamide;

N-acetyl-2,6-dichloro-N- (5,7-dimethyl-1,2,4-triazolo / 1,5-7 'pyrimidin-2-61) -benzenesulfonamide;

N- (5,7-dimethyl-1,2,4-triazolo / T, 5-7-pyrimidin-2-yl) -2-nitrobenzenesulfonamide;

N- (5-amino-1,2,4-triazol-3-yl) -2,5-dichlorobenzenesulfonamide; 2-chloro-N- (5-methyl-7-trifluoromethyl-1,2,4-triazoloZi> 5-a7 pyrimidin-2-yl) -benzenesulfonamide;

2-chloro-N- (6-chloro-1,2,4-triazolo / 1,5-7-primidin-2-yl) benzenesulfonamide;

N- (5,7-dimethyl) -6,7-dihydro- [2,47-triazole-5,5-a] 3,5?

-triazine-2- (2,6-difluorophenyl) -sulfonamide;

N- (7-methoxy-6,7-dihydro- / 1,2,47-triazole triazine-2- (2,6-dichlorophenyl) -sulfonamide;

N- (5-chloro) -6,7-dihydro- [2,4]-triazoleZl, 5-a7- [3,57-triazine 2- (2-acetyl-6-methylphenyl) sulfonamide;

N- (5-methoxy-ethyl) -6,7-dihydroZ1,4,47-triazole-5,5-a-trifluoro-3,5-triazine-2- (2,6-difluyl-phenyl) -sulfonamide.

Examples of other important compounds useful as co-herbicides include:

2-chloro-4- (ethylamino) -6- (isopropylamino) -s-triazine;

4-amino-6-tetrabutyl-3- (methylthio) as-triazin-5 (4H) one;

Trifluoro-2,6-dinitro-N, N-dipropyl-p-toluidine;

Benzenamine, N- (1-ethylpropyl) -3,4-dimethyl-2,6-dinitro-y

2- J (rolidinone, 3-chloro-4- (chloromethyl) -1- (3- (trifluoromethyl) phenyl), trans-;

3- isoxazolidinone, 2 - [(~ chlorophenyl) -methyl] -4,4-dimethyl-; 2-imidazolidinone, 3- / 5- (1,1-dimethylethyl) -3-isoxazolyl7 '

4-hydroxy-1-methyl-;

2-chloro-4- (1-cyano-1-methylethylamino) -6-ethylamino-1,3,5triazine;

Methyl 5- (2,4-dichlorophenoxy) -2-nitro-benzoate;

1 ^1- (carboethoxy) ethyl-5- / 2-chloro-4- (trifluoromethyl) phenoxy7

-2-nitrobenzoate;

Ammonium-DL-homoalanin-4-yl (methyl) -phosphinate;

1- [(2-fluoro-4-chloro-5- (2,3-dimethylbutoxyphenyl)} tetrahydrophthalimide)

2- (3,4-dichlorophenyl) -4-methyl-1,2,4-oxadiazolidine-2,5-dione;

2,6-dichlorobenzonitrile;

Monosodium acid methanarsonate;

Disodium methanarsonate;

2- (2-chlorophenyl) methyl-4, 4-dimethyl-3-isoxazolidinone; 7-Oxabicyclo (2,2 _> 1) heptane, 1-methyl-4- (1-methylethyl) -2- (2-methyl phenylmethoxy) -, exo-;

Glyphosate and its salts;

(2,4-dichlorophenoxy) acetic acid (commonly called 2,4-D) and its salts and esters and ·

2- (4-Chloro-2-methylphenoxy) propionic acid (commonly called mecoprop), its salts and esters.

In various embodiments within the scope of the present invention, the component (e) of the co-herbicide in admixture with the compounds of the pyrazolylsulfonylureas of formula I and the protective agent may comprise mixtures of different herbicides. Commercial composition of TRIMEci® e.g. is a mixture of dimethylamine salt 2,4-D mecoprop and dicamba. Many other such mixtures of 2,4-D and other herbicidal compounds are commercially available under many trade names; many of these mixtures are listed in the 9th edition of the Pesticides Manual (1991), page 220.

- 25 Herbicides of particular and particular interest with respect to co-herbicides with pyrzolsulfonyl urea compositions containing the antidotes of the present invention include each of the aforementioned species from different chemical classes of compounds illustrated as important herbicides, especially those which are common commercially interesting, and those that may be designated as commercially useful.

Preferably co-herbicide compounds include the following: alachlor, acetochlor, butachlor, metolachlor, pretilachlor, metazachlor, dimethachlor,

EPTC, butylate and vernolate.

The aforementioned and other co-herbicides may previously be mixed with the optional protective agents before being mixed or in any way combined with the pyrazolylsulfonylurea herbicides of formula I. The compounds listed above may be mixed in a container or in a wrap with AD-67, R -25788, R-29148, PPG-1292 or oxazolidine, 3- (dichloroacetyl) 2,2-dimethyl-5- (2-furanyl) - or other suitable protective agent described herein ₍ and optionally with other additives such as e.g., developers, e.g., dietolate, etc., used simultaneously or sequentially at the site of plant growth together with compounds of formula I.

Particularly preferred herbicidal compositions are those containing pyrazolylsulfonylureas of formula IA and safeners of formula III, formula II (b) (ii), and selected safeners of formula II (b) (i).

The herbicide and antidote compounds of formulas I - V are known in the art.

- 26 The compositions of particular interest here include combinations of Formula I, herbicide components NC-311 or NC-319 and antidote components: R-29148, PPG-1292, AD-67 and oxazolidine,

3- (dichloroacetyl) -2,2-dimethyl-5- (2-furanyl) - and other compounds of formula III, said composition optionally containing as a component of a soherbicide (X-chloroacetamide of formula IV or V, in particular acetoclor, alachlor, butachlor, metolachlor, pretachlor or trimexachlor.

Furthermore, compositions of NC-311 or NC-319 as a component are of particular interest. herbicides; and R-25788, AD-67 or oxazolidine, 3- (dichloroacetyl) -2,2-dimethyl-5- (2-furanyl) - as antidote components and acetoclor as any component of the herbicide.

The composition components may contain individual members of each class, i.e. components of herbicides, co-herbicides and antidotes, or a combination of members of each class, specifically classes of herbicides and antidotes. Illustrative other herbicide compounds that may be particularly suitable as co-herbicides of the Formula I preferred class for herbicides include types of thiocarbamates.pyridines, heterophenyl esters, sulfonylureas, imidazolinones and azolopyrimidine sulfonamides, which are illustrated above.

As described in more detail below, the above compositions may be formed in various ways, including mixing in a container of said separate components or for bulk dispensing or pre-packaging for storage, transport, sale and use. Said compositions are also formed when the individual components are used at the site of use separately and there combined in contact with one another simultaneously or sequentially in any order. Components of antidotes and / or herbicides of formula I e.g. we can first apply the soil separately or together, then apply the component of the soherbicide _; or the component of the antidote is applied to the seeds of the crop prior to sowing into the soil, previously or subsequently treated with the components of the formula I and / or co-herbicides. The only caveat in the formation of said composition is that the antidote component must always be present, ie in contact with the herbicide components at the seed site of the plant or plant at the time of contact of both components.

The term halogenated alkyl as used herein includes radicals in which one or more carbon atoms, preferably 1 to 4 in number, is substituted by one or more halogen groups, preferably selected from bromo, chloro and fluoro. Particularly covered by the term halogenated alkyl are monohalogenated, dihalogenated and polyhalogenated alkyl groups. A monohalogenated alkyl group e.g. may have in the group either a bromo or chloro or fluoro atom. The halogenated and polyhalogenated alkyl groups may be substituted by two or more identical halogen groups or may have a combination of different halogen groups. The dihalogenated alkyl group e.g. can have two bromo atoms, such as e.g. a dibromomethyl group, or two chloro atoms, such as e.g. a dichloromethyl group, or one bromo and one chloro atom, such as a bromochloromethyl group. Examples of polyhalogenated alkyl are perhalogenated alkyl groups such as e.g. trifluoromethyl and perfluoromethyl groups.

Where, in formulas II, V and III, the halogen attached to the acetyl radical is a chlorine ion, it is expected that other halogens, such as bromo, iodine or fluoro, may be substituted by chloro.

Preferred halogenated alkyl members in the antidotes of formula II are dihalogenated methyl, especially dichloromethyl, while the preferred halogenated alkyl member R1 or R1g in the antidotes of formula III is a trihalogenated methyl radical, preferably trifluoromethyl.

Where the term alkyl is used alone or in the form of a compound (as in halogenated alkyl), it comprises straight and branched radicals having up to four carbon atoms, methyl and ethyl being preferred.

By agriculturally acceptable salts of the compounds defined by any of the foregoing formulas, we mean a salt or salts which like to ionize in an aqueous medium to form a cation or anion of said salts, and a corresponding cation or anion of salts whose salts have no adverse effect on the antidote the properties of said compounds or the herbicidal properties of a given herbicide, which enable the formulation of the herbicide - antidote composition without undue problems with mixing, suspension, stability, use of spray equipment, packaging, etc.

a The term antidote is intended to mean the amount of antidote required to reduce the phytotoxic effect of the herbicide, preferably by at least 10 Z or 15 Z; of course, the greater the reduction in herbicide damage, the better.

The term herbicidally effective means the amount of herbicide component (individual or more) needed to cause significant damage or destruction to a large portion of an unwanted plant or weed. Although there is no firm rule, it is desirable from a commercial point of view to destroy 80 - 85 With more or less weeds, although commercially important weed growth suppression can be achieved at much lower rates, especially in some harmful herbicide-resistant plants.

The terms antidote, protective agent, etc. are commonly used terms to denote a compound capable of reducing the phytotoxicity of a herbicide for a plant or seed of a field. The term protective agent is sometimes used to refer to a composition containing as active ingredients a combination of a herbicide and an antidote that protects against the growth of competing weeds by reducing the damage to the valuable crop by the herbicide while simultaneously suppressing or suppressing the growth of weeds growing in the presence of the crop. Antidotes protect crops by hindering the herbicidal effect of the herbicide on crops by making the herbicides selective against weeds that occur or grow in the presence of crops.

As detailed below, while not necessary, a composition containing a combination of herbicide and antidote may also contain other additives, e.g. various biocides, e.g. insecticides, fungicides, nematicides, etc. fertilizers, inactive formulation additives, e.g. surfactants, emulsifier j <2, antifoams, dyes _/ developers.

All those skilled in the art will recognize that herbicides have varying degrees of phytotoxicity with respect to different plants, due to their different sensitivity / to ^S ^ e ^ icides. Although they have certain crops, e.g. cereals and soybeans, with a high degree of tolerance (ie low sensitivity) to the phytotoxic effect of alclor, while other crops have a low degree of tolerance (ie, a high sensitivity) to the phytotoxic effect of alclor. Weeds are the same kind of susceptibility to herbicides as the crops, some very sensitive, others very resistant to the phytotoxic effect of the herbicide.

When the crop is slightly susceptible to the herbicide and the weeds are strong against the same herbicide, the selectivity factor of the herbicide, which in particular damages the weeds but not the crop®, is high.

In an analogous but more complex way, the antidote compound also typically has a different degree of protective effect against different herbicides in different crops. As those skilled in the art will appreciate, therefore, different antidotes of the present invention, like all classes of antidote compounds, will have greater or lesser protective effect against different herbicides and combinations of herbicides in one. crops than in others. It may happen that a particular antidote compound cannot protect the crop

- 29 against a particular herbicide in a particular crop, and the same antidote compound may very well protect another crop against the same herbicide or the same crop against another herbicide at the same or different dosage or different route of administration, i.e. introduced before sowing, before emergence, seed testing, etc. This is an expected occurrence.

DETAILED DESCRIPTION OF THE INVENTION

Antidote compounds

As mentioned above, the antidote compounds used in the practice of the present invention are known compounds. Preferred compounds used herein are 1,3-oxazolidine dichloroacetamides of formula III, wherein the R _1Q moiety is a heterocyclic radical.

Biological assessment

Effective weed control combined with low crop damage results from treatment of the plant site with a combination of herbicide and antidote compounds. By application to the site of a plant, we mean an application to a substance where the plant grows, e.g. soil, as well as seeds, shoots, roots, stems, leaves or other plant parts.

The phrase combination of herbicide and / or antidote compounds encompasses different treatment methods. The soil at the plant site may be e.g. treated with a composition mixed in a container containing a herbicide and an antidote to be combined. Or we treat the soil with herbicide compounds and antidote compounds separately so that the combination only occurs in the soil or on the ground. After such treatment of the soil with a mixture of herbicide and antidote or with a separate sequential application of the herbicide and antidote into the soil, the herbicide or antidote can be brought to the soil by mechanical mixing with the tool or washed into the soil by irrigation, or rain.

The soil at the plant site can also be treated with antidote by the application of antidote in the form of a dispersing concentrate, e.g. granules.

The granulate can be sprayed into the grooves prepared for crop seeds, and the herbicide can be applied to the plant site before or after the granulation containing the antidote, so that the herbicide and the antidote form a combination. Crop seeds can be treated with an antidote compound when it is already sown in the furrows or, more typically, before sowing in the furrows. The herbicide can be applied to the site of the plant before or after sowing, and a combination of the herbicide and the antidote occurs when both are in the soil. A commercially prepared mixture of herbicide and antidote is also considered as a combination. For example, the herbicide and antidote components in concentrated form may be stored in separate containers, but such containers may be marketed together as a combination (composition) Or the herbicide and antidote components in concentrated form may be present in one container as a combination. Such combination may be diluted or mixed with devices suitable for application to the floor.

Another example is the commercially available combination of an antidote-treated seed-filled container that is sold with a herbicide-filled container. These may or may not be physically linked to one another, but may still be a combination of a herbicide and an antidote when intended for final consumption at the same plant site.

In the foregoing description of the various uses of combinations of herbicides and antidotes, it is proper for each form of use to require that the herbicide and antidote be combined in some way to form a combination of these agents.

The amount of antidote used according to the methods and compositions of the present invention varies with the individual herbicide with which the antidote is used, the dose of the herbicide, the crop to be protected and the method of application to the site of the plant. In each case, the amount of antidote used is the amount that has a protective effect, i.e. an amount that reduces or protects the plant from damage that would otherwise result from the presence of the herbicide. The amount of antidote used will be less than the amount that severely damages the crop.

The antidote can be applied to the crop site in admixture with the selected herbicide. Where we first sow the seeds of a crop, e.g. the appropriate antidote and herbicide mixture, either in the form of a homogeneous liquid, emulsion, suspension or solid form, may be applied to the surface or ground into the soil where the seed has been sown.

Or the mixture of herbicide and antidote is applied to the ground and the seed is then ground into a soil layer containing a mixture of herbicide and antidote. The herbicide will suppress or reduce the presence of unwanted weeds.

However, where the herbicide itself would damage the seedlings, the presence of the antidote reduces or prevents damage to the seeds of the crop, otherwise caused by the herbicide, often exacerbated by the insecticide. It is not essential that the herbicide and antidote be applied to the plant site in the form of a mixture. The herbicide and antidote can be applied to the plant site sequentially. First of all, e.g. an antidote is applied to the plant site, followed by a herbicide. Or, first, apply a herbicide to the plant site and then an antidote.

The ratio of herbicide to antidote may vary depending on the crop to be protected, the weeds to be suppressed, the herbicide used, etc., but usually the ratio between the herbicide and the antidote is from 1: 25 to 60: 1 (preferably 1: 5 to 30: 1) by weight, although much larger doses of antidote may be used, e.g. 1: 100 - 1: 300 parts by weight of herbicide and antidote. As mentioned above, the antidote can be applied to the site of the plant in the mixture, i.e. a mixture of a herbicidal herbicide and an antidote effectant, or sequentially, i.e. the site of the plant is treated with an effective amount of herbicide, followed by an antidote or vice versa. In general, effective doses of herbicide are moving

0.03 to about 12 kg / ha, but even doses as low as 0.004 kg / ha can be effective. Preferably, the dose range is from about 0.1 to about 10 kg / ha. Preferably, antidote doses range from 8-10 kg / ha to 0.05 kg / ha. We will keep in mind that sometimes quantities will be required above or below these limits for best results. The choice of herbicide to impede the emergence and growth of weeds depends on the type of weed to be suppressed and the grain to be protected.

Any biocide used is used in doses recommended by the supplier / manufacturer.

The antidote can be applied directly to the seed before sowing. In this case, a certain amount of seed is first treated with an antidote, then the treated seed is sown. The herbicide can be applied to the soil ₍ before the treated seed is sown or after.

When used in the field, the herbicide, antidote or mixture thereof can be applied to the site of the plant with no additives other than solvent. Typically, the herbicide, antidote or mixture thereof is administered with one or more additives in solid or liquid form. Compositions or formulations containing a mixture of a suitable herbicide and antidote are typically prepared by mixing one or more additives, e.g. biocide (s), thinners, solvents, developers, carriers, conditioners, water, wetting agents, dispersing agents or emulsifiers, or any suitable combination thereof. These mixtures may be in the form of individual solids, granules, pills, wettable powders, powders, solutions, aqueous dispersions or emulsions.

The herbicide, antidote or mixture thereof can be applied by a variety of techniques using hand spreaders or spreaders on the tractor, motor dusters, spray rods and hand sprayers, spray dusters and granulators. if desired, the compositions of the present invention may be applied to plants by introducing the compositions into the soil or other means.

The sequence of adding chemicals is optional, but in normal use the antidote can be applied to the seed or soil, followed by the application of the herbicide only according to Formula I or in admixture with the soherbicide.

Various modifications to the sequence of application of chemicals common in the art are being studied.

The evaluation of the protective effect of representative herbicide and antidote compounds of the present invention was carried out in the greenhouse and field testing using the specific procedures described below.

Biological response measurements, as given in the tables, were performed visually, and the rate of plant injury was recorded as a percentage of injury.

The names of the various antidote compounds tested here and the representative compounds for which the data are given in the tables are given below.

Nomenclature

Acetamide, N, N-bis (2-propenyl) -at, & - dichloro, (commonly called dichloromide, code No. R-25788),

1H, 3H-naphtho / N, 8-cd / pyran-1,3-dione, cis / trans-piperazine, 1,4-bis (dichloroacetyl) -2,5-dimethyl-, 5-thiazolecarboxylic acid, 2-chloro -4- (Trifluoromethyl) -, (commonly called flurazole),

Oxazolidine, 3- (dichloroacetyl) -2,2,5-trimethyl-, (code

(commonly called oxabetrinyl), l-oxa-4-azaspiro / 4,5 / decane, 4- (dichloroacetyl) -, (code No AD-67),

1,5-diazacyclononane, 1,5-bis (dichloroacetyl) -,

1-azaspiro / 4,4 / nonam, 1- (dichloroacetyl) -,

Acetamide, 2,2-dichloro-N- (1,3-dioxolan-2-ylmethyl) -N-2propenyl (code no. PPG-1292),

Oxazolidine, 3- (dichloroacetyl) -2,2-dimethyl-5- (2-thienyl) -, ethanone, 2,2-dichloro-1- (1,2,3,4-tetrahydro-1-methyl / -2-isoquinolinyl) ) -,

1,3-dioxolane, 2- (dichloromethyl) -2-methyl-, (code No MG-191),

5-dichloroacetyl-3,3,6-trimethyl-9-oxo-1,5-diazabicyclo / 4.3.0 / nonone (code no. BAS-145138),

Oxazolidine, 3- (dichloroacetyl) -5- (2-furonyl) -2,2-dimethyl, pyridine, 3- / 3- (dichloroacetyl) -2,2-dimethyl-5-oxazolidinyl7 4- (dichloroacetyl) -3, 4-dihydro-3-methyl-2H-1,4-benzoxazine (commonly known as benoxychlor; Code No. CGA-154281),

Acetic acid (diphenylmethoxy) sodium salt, hemihydrate, Acetic acid (diphenylmethoxy) -,

Acetic acid, (diphenylmethoxy) -, methyl ester, (code No MON-7400),

Ethanethioic acid, 2- (diphenylmethoxy) -5-ethyl ester.

The names of the various herbicide compounds tested here are listed below! , and representative compounds for which data are given in the tables.

Herbicide No.Nomenclature

N - [(4,6-dimethoxypyridin-2-yl) aminocarbonyl] -3-chloro-4methoxycarbonyl (code No. A-84110; also NC-319),

N- / 4,6-dimethoxypyrimidin-2-yl) aminokarbonil7 ^- 3-chloro-4etoksikarbonil (code no. A-841 065; also NC-319-Εχ)

N - [(4,6-dimethoxypyridin-2-yl) aminocarbonyl7-4-ethoxycarbonyl (code NC-311),

Ethyl dipropylthiocarbamate (commonly called EPTC),

2-chloro-N-isopropylacethanilide (commonly called propachlor),

2-chloro-N- (ethoxymethyl) -6 ^{1 11} -ethyl-o-acetoluidid (usually the name of acetochlor)

2-chloro-2 ', 6'-diethyl-N- (methoxymethyl) -acetanilide (commonly called alachlor),

3,6-dikk> ro-2-methoxybenzoic acid (commonly called dicamba),

2-chloro-2 ', 6'-diethyl-N- (butoxymethyl) -acetanilide (commonly called butachlor),

S-ethyl diisobutylthiocarbamate (commonly called butylate),

S-propyl dipropylthiocarbamate (commonly called vernolate)

2-chloro-N- (2-methoxy-1-methylethyl) -6 '-ethyl-o-aceto [uido] (commonly called metolachlor),

2-chloro-N- (2-n-propoxyethyl) -2 ', 6'-diethylethanethilide (commonly called pretilachlor),

2-chloro-2 ', 6'-dimethyl-N- (1-pyrazol-1-yl-methyl) acetanilide (commonly called metazachlor).

Experiments in the greenhouse with the above-mentioned compounds were carried out in accordance with the general procedures I-II described below with the modifications indicated in the individual examples.

Procedure I

The following procedure shows the interaction of the herbicide and the antidote when both are coupled to the surface layer of soil before the crop and weeds emerge. The containers were filled and pressed with a disinfected clay loamy topsoil to a depth of about 1.3 cm from the edge of the container. The first container was intended as a control with untreated soil, the second container was intended for the control of the herbicide and the third was for the test of the herbicide and antidote. We sowed each of the vessels with one type of crop. A measured amount of herbicide sprayed or dissolved in acetone was applied to a measured amount of soil. To this same amount of herbicide-treated soil was added a measured amount of antidote, sprayed or dissolved in acetone. The amount of soil treated with the herbicide and antidote was thoroughly mixed so that the herbicide and antidote were evenly distributed across the earth.

The seed beds in the third soil container were covered with soil treated with herbicide and antidote, and then leveled. For each test series, seed beds in the first and second vessels were similarly covered with a layer of soil. The cover layer in the first container was not treated with a herbicide or antidote. The cover layer in the second container contained a measured amount of herbicide.

The vessels were then placed on the greenhouse bench and irrigated below ground, as required, for the duration of the test.

Plant response was monitored at different times, but usually three weeks after initial treatment; changes will be seen in the examples. Plant response is measured by the percentage of damage. Antidote efficacy is expressed as the difference between an antidote-free herbicide (s) and an antidote

Procedure II

This procedure is the same as procedure I, but it is modified in such a way that after the introduction of chemicals (herbicide and antidote), the containers with seed beds covered with seed were first treated with above-ground irrigation corresponding to 0.6 cm of rainfall, and then irrigated underground surface, as required, in the greenhouse.

In a series of greenhouse trials, a number of antidote compounds were tested for their effectiveness against various herbicides. In one series of tests (Examples 1-4), the antidote compounds were tested against a representative and preferred herbicide compound of Formula I in the absence of soherbicide. In the second series of tests (Examples 5 22), the compound of formula I was combined with different co-fertilizers from different types of chemical compounds to determine if the antidote effect was retained in such a combination of herbicides.

In the series of greenhouse tests described below, for routine selection, we tested herbicide and antidote compositions in combinations of crops and weeds that included cereals as a crop and one or both weeds, "i.e. common grebe (Echinochloa crusgalli), monocotyledonous weeds, and spleen (Abutilontheophrasti), dicotyledonous weeds, like weeds. In the tables below, weeds are marked with the EC symbol (Echinochloa crusgalli) or. AT (Abutilontheophrasti).

Example 1

This case was intended to investigate the antidote effect of a whole range of antidotes with respect to herbicide no. Iv cereals in the presence of common grebe and spleen. The antidotes used in this case _y were antidotes no. 1 - 10, 12, 13 and 15.

The test in this case was performed according to procedure II. The antidotes were applied to the top layer of the earth with a pipette after we sprayed and hit the herbicide and simulated the rain.

in the table, the abbreviations are as follows: EC - Echinochloa crusgalli = fly AT - Abutilontheophrasti = spleen SF - Setaria fabergi = fly

Table 1

Herbicide no. 1 kg / ha Antidote no. Dose kg / ha With the injury wheat EC AT 0.56 - - 40 75 95 0.14 - - 5 50 85 0.56 15 8.96 10 55 70 0.14 II 15 40 65 0.56 II 2.24 5 55 80 0.14 II II 5 45 65 0.56 7 8.96 15 55 90 0.14 II II 5 35 75 0.56 II 2.24 30 75 90 0.14 II II 0 55 60 0.56 1 8.96 0 85 90 0.14 II II 20 50 85 0.56 tl 2.24 15 75 95 0.14 II II 10 60 75 0.56 5 8.96 10 65 80 0.14 II II 5 40 70 0.56 tl 2.24 15 80 90 0.14 II II 10 50 70 0.56 10 8.96 10 '50 65 0.14 II II 20 40 80 0.56 II 2.24 5 65 80 0.14 II II 20 50 65 0.56 3 8.96 20 65 85 0.14 II II 5 40 80 0.56 -II ' 2.24 5 65 95 0.14 II II 5 45 75 0.56 12 8.96 25 50 85 0.14 II II 15 50 65 0.56 II 2.24 10 60 95 0.14 II II 5 30 80 0.56 9 8.96 0 65 75 0.14 II n 5 40 55 0.56 II 2.24 10 60 65 0.14 II II 5 35 60 0.56 8 8.96 10 60 85

Table 1 (continued)

Herbicide no. 1 kg / ha Antidote no. Dose kg / ba With the injury wheat EC AT 0.14 8 8.96 5 20 65 0.56 1 » 2.24 20 70 85 0.14 It IV 5 40 70 0.56 2 8.96 10 35 85 0.14 II II 10 15 65 0.56 II 2.24 10 35 85 0.14 II II 5 40 55 0.56 13 8.96 20 85 95 0.14 II II 5 35 75 0.56 II 2.24 25 60 65 0.14 VI II 15 25 55 0.56 4 8.96 10 60 70 0.14 n IV 10 45 60 0.56 II 2.24 5 50 80 0.14 II It 0 20 65 0.56 6 8.96 20 30 85 0.14 M II 10 15 70 0.56 II 2.24 10 30 65 0.14 II II 15 15 55 control 0 0 0 control 0 0 0

With regard to the data in Table 1, we notice that all antidotes tested for herbicide no. 1 of 0.56 kg / ha applied before sowing reduces cereal damage from 40% (no antidote) to levels from 0% to a maximum of 30% damage. In this test, the best protective effect after four treatments was obtained with antidote no. 9.

For herbicide to antidote ratios of 1: 16, all antidotes other than four (Nos. 3, 6, 12 and 13) gave commercially acceptable protection (i.e., no more than 15% of the damage) of the grain. However, reducing the herbicide-antidote ratio to 1:57 gave a commercial degree of protection for all antidotes, except antidotes 1 and 10, which were only slightly more harmful to the grain in 20% of the damage.

Example 2

In this case, a whole range of dichloroacetamide antidotes was tested for their protective effect against herbicide no. Iv cereals using procedure II. In this test, weed was spleen (AT), and no common bone (EC) was present. The test results are shown in Table 2.

Table 2

Herbicide no. 1 kg / ha Antidote no. Dose kg / ha With the injury wheat AT 0.14 10 95 0.56 - - 55 85 2.24 - - 80 95 0.14 1 0.56 10 100 0.56 1 tl 10 95 2.24 1 It 30 100 0.14 1 2.24 10 90 0.56 1 11 25 85 2.24 1 II 40 100 0.14 3 0.56 15 90 0.56 3 II 10 90 2.24 3 II 40 90 0.14 3 2.24 10 90 0.56 3 II 10 90 2.24 3 tl 50 100 0.14 5 0.56 10 95 0.56 5 11 8 95 2.24 5 II 30 100 0.14 5 2.24 25 90 0.56 5 tl 15 95 2.24 5 II 20 100 0.14 7 0.56 5 95 0.56 7 II 15 85 2.24 7 II 40 95 0.14 7 2.24 10 75 0.56 7 II 5 90 2.24 7 II 50 95 0.14 10 0.56 5 95 0.56 10 II 10 65 2.24 10 II 40 90

Herbicide no. 1 Antidote Table 2 (continued) Dose With the injury kg / ha no. kg / ha wheat AT 0.14 10 2.24 10 95 0.56 10 H 15 95 2.24 10 II 20 95 0.14 12 0.56 5 100 0.56 12 II 20 95 2.24 12 H 35 95 0.14 12 2.24 10 80 0.56 12 II 5 85 2.24 12 II 15 95 0.14 14 0.56 5 95 0.56 14 II 5 80 2.24 14 II 20 95 0.14 14 2.24 0 60 0.56 14 It 5 90 2.24 14 II 20 95 0.14 15 0.56 5 75 0.56 15 tl 10 90 2.24 15 II 10 95 0.14 15 2.24 10 65 0.56 15 II 15 95 2.24 15 It 10 90

According to the data in Table 2, it is observed that antidote no. 15 fully gave the best commercial-grade protection and protection for cereals at all test ratios, temqpa followed in the order of antidote no. 14, 12, 7 and 10.

In general, the dose effect at higher antidote and herbicide ratios gave the highest protective effect.

Example 3

This example details the results of antidote tests no. 12, and 16 for protection against herbicide no. Iv doses from 4.48 kg / ha k 'down to 0.56 kg / ha in the cereals, in the presence of ordinary hedge. The above procedure was used for these tests. The results of the tests are shown in Table 3.

Herbicide no. 1 kg / ha Antidote no. Table 3 Dose kg / ha With the injury wheat EC- 4.48 - - 60 75 2.24 - - 38 70 1.12 - - 13 70 0.56 - - 7 50 4.48 11 0.56 50 80 2.24 11 n 30 75 1.12 11 It 5 80 0.56 11 n 15 70 4.48 11 2.24 30 80 2.24 11 n 0 30 1.12 11 II 0 15 0.56 11 II 0 20 4.48 11 8.96 5 50 2.24 11 II 0 0 1.12 11 II 0 0 0.56 11 II 0 0 - 11 II 15 0 4.48 15 0.56 0 75 2.24 15 II 15 60 1.12 15 II 0 75 0.56 15 II 0 50 4.48 15 2.24 5 70 2.24 15 11 0 70 1.12 15 II 0 60 0.56 15 tl 0 35 4.48 15 8.96 0 80 2.24 15 II 0 50 1.12 15 tl 0 60 0.56 15 II 0 10 - 15 II 0 0

Herbicide no. 1 kg / ha Antidote no. Table 3 (continued) Dose kg / ha With the injury wheat EC 4.48 16 0.56 5 75 2.24 16 H 5 85 1.12 16 II 0 70 0.56 16 II 0 65 4.48 16 2.24 5 80 2.24 16 It 0 ⁹⁰ 1.12 16 II 0 80 0.56 16 VI 0 60 4.48 16 8.96 5 95 2.24 16 II 0 80 1.12 16 II 0 85 0.56 16 II 0 50 - 16 II 0 0

- 45 Table 3 shows that each of the antidotes tested, in particular no. 15 and 16, gives the grain excellent protection over a range of antidote and herbicide ratios. Moreover, at the selected herbicide to antidote ratios, the protection of the observed cereal was accompanied by comparable to increased weed control relative to that of the unprotected herbicide. Unexpected synergistic effect.

Example 4

This example describes antidote tests no. 15 and 16 for protection against herbicide no. 1 according to Procedure I, and the test plants are cereals and weeds: common grebe and spleen.

Test results (averages of two replicates) are shown in Table 4.

Table 4

Herbicide no. 1 kg / ha Antidote no. Dose kg / ha wheat % injuries EC AT 6.72 - - 90 90 90 4,48 - - 85 80 90 6.72 15 0.56 35 90 95 4,48 15 II 10 95 95 6.72 15 2.24 50 90 95 4,48 15 It 13 90 95 6.72 16 0.56 35 95 95 4,48 16 tl 70 95 95 6.72 16 2, -24 30 95 95 4,48 16 n 15 95 95

The data in Table 4 show that they give both antidotes, i.e. no. 15 and 16, significant protection against herbicide no. 1, which in itself significantly damages the grain. Increased herbicide protection was achieved by a combination of reduced herbicide doses and / or increased antidote doses. For both antidotes, the commercial protection of cereals against herbicide 1 was achieved with a herbicide of 4.48 kg / ha and an antidote of 2.24 kg / ha, while the weeds were actually completely suppressed.

As mentioned above, the tests performed in Examples 1 - 4 _; found an antidote effect of a whole range of antidotes with respect to a typical, representative herbicide of formula I. In the following cases, tests were conducted to determine the efficacy of different antidotes with respect to the combination of said herbicide together with different soherbicide compounds.

Example 5

In the tests described in this case, the same procedure as in Example 4 was performed at the same time and under the same conditions, except that it was a soherbicide, i.e. Alcohol included in the same composition with herbicide no. 1 and antidotes no. 15 and 16. Alachlor (here herbicide No. 7) is the active substance in the commercial LASSO herbicide product. The test results are listed in Table 5

Table 5

Herbicide Antidote kg / ha 7. injuries kg / ha no. 1 6.72 4.48 no. 7 no. dose wheat 90 85 EC 90 80 AT 90 90 6.72 2.24 - - 95 100 98 4.48 n - - 95 100 98 6.72 0.56 - - 93 99 98 4.48 n - - 95 99 98 6.72 - 15 0.56 35 90 95 4.48 - 15 It 10 95 95 6.72 - 15 2.24 50 90 95 4.48 - 15 II 13 90 95 6.72 2.24 15 0.56 45 100 99 4.48 tl 15 II 30 100 98 6.72 0.56 15 II 25 99 95 4.48 tl 15 II 23 99 95 6.72 2.24 15 2.24 50 100 95 4.48 II 15 II 23 100 95 6.72 0.56 15 II 25 99 99 4.48 II 15 II 40 95 95 6.72 - 16 0.56 35 95 95 4.48 - 16 II 70 95 95 6.72 - 16 2.24 30 95 95 4.48 - 16 II 15 95 95

Table 5 (continued)

Herbicide Antidote kg / ha kg / ha_ With damage

no. 1 no. 7 no. dose wheat EC AT 6.72 2.24 16 0.56 80 100 98 4.48 II 16 II 53 100 98 6.72 0.56 16 II 43 95 98 4.48 It 16 II 48 100 95 6.72 2.25 16 2.24 55 100 99 4.48 II 16 n 40 100 98 6.72 0.56 16 II 55 100 95 4.48 tl 16 II 18 100 95

- 49 As can be seen from the data in Table 5, both antidotes, i.e. no. 15 and 16, a strong protection against the herbicidal effects of both herbicides, i.e. no. 1 and 7, which almost completely suppressed both weeds. Cereal damage at a dose of 4.48 kg / ha of herbicide no. 1 decreased from 85% to 10% respectively. 13 Z with an antidote effect of 0.56 and 2.24 kg / ha of antidote no. 15, without the presence of alaclor. However, at all doses of herbicide, no. 7 Minimum damage reduction 45 Z (ie from 95 Z at a dose of 2.24 kg / ha of herbicide No. 7, at doses 6.72 and 4.48 kg / ha of herbicide No. 1 when no antidote was present at 50 Z injuries when the antidote No.1 at a dose of 2.24 kg / ha was present).

Similarly, but to a lesser extent, antidote no. 16 is effective in reducing the combined damage caused by two herbicides, especially at increased antidote and herbicide concentration ratios.

Example 6

This case was intended to investigate the antidote efficacy of a whole range of antidote compounds against a herbicide composition no. Iv in combination with herbicide no. 7 (alachlor). The antidote compounds used here were those of Nos. 1, 2, 7, 13 and 15.

In this case, the previously described procedure II was used.

The data from the tests in this case are shown in Table 6 and are represented by averages of two replicates.

Table 6

Herbicide Antidote kg / ha_ kg / ha_% damage

no. 1 No.7 no. dose wheat EC AT 0.56 4.48 - - 30 100 85 0.14 1 « - - 20 100 70 0.56 11 15 8.96 15 100 95 0.14 II 15 10 100 65 0.56 It 15 2.24 15 100 90 0.14 II 15 II 20 100 80 0.56 II 7 8.96 5 100 90 0.14 II 7 II 10 100 75 0.56 II 7 2.24 10 100 90 0.14 II 7 II 0 100 75 0.56 II 1 8.96 5 100 85 0.14 II 1 II 0 100 80 0.56 II 1 2.24 15 100 80 0.14 II 1 II 10 100 75 0.56 II 2 8.96 15 100 90 0.14 II 2 II 15 100 75 0.56 II 2 2.24 10 100 90 0.14 II 2 II 0 100 70 0.56 ' II 13 8.96 15 100 90 0.14 II 13 II 0 100 65 0.56 II 13 2.24 5 100 90 0.14 II 13 0 100 75 0.56 - - - 25 70 60 0.14 - - - 5 20 40 - 4.48 - - 10 100 25 control 0 0 0

The data in Table 6 show that all protostrops during the test protected the grain against the combination of herbicides 1 and 7 applied against sowing. Antidote no. 13 had the best protective effect in four treatments. The best grain protection in this test was given by antidotes no. 7 and 1, administered at the highest test dose of herbicide and antidote The common grebe was well suppressed and the spleen was well suppressed while providing reduced cereal damage due to herbicides.

Example 7

The tests in this case were performed by the same procedure and with the same antidotes as in Example 6. However, the herbicide no. 12 (metolachlor) used as a co-herbicide with herbicide no. 1.

The test results are shown in Table 7.

Herbicide

kg / ha no. 1 No.12 0.56 3.36 0.14 n 0.56 II 0.14 II 0.56 II 0.14 II 0.56 II 0.14 II 0.56 II 0.14 II 0.56 II 0.14 II 0.56 II 0.14 II 0.56 II 0.14 tl 0.56 n 0.14 II 0.56 VI 0.14 II 0.56 II 0.14 II 0.56 II 0.14 II - 3.36

control

Table 7

Antidote kg / ha % injuries no. dose wheat EC AT - - 30 100 85 - - 20 100 70 15 8.96 15 100 70 15 II 10 100 65 15 2.24 15 100 75 15 II 0 100 70 7 8.96 15 100 85 7 II 10 100 65 7 2.24 20 100 85 7 II 10 100 70 1 8.96 10 100 80 1 II 0 100 75 1 2.24 0 100 85 1 II 0 100 70 2 8.96 15 100 85 2 II 0 100 75 2 2.24 10 100 80 2 II 0 100 75 13 8.96 10 100 85 13 II 0 100 80 13 2.24 10 100 85 13 II 0 100 75 - - 10 75 75 - - 0 35 60 - - 0 100 20 - - 0 0 0

As can be seen in Table 7, all antidotes gave the crop protection, while the compositions containing both test herbicides provided strong weed control or suppression. All antidote treatments gave commercially acceptable protection at all test doses except antidote no. 7. At a dose of 0.56 kg / ha herbicide no. 1 plus dose of 3.36 kg / ha of herbicide no. 12 and a dose of 2.24 kg / ha of antidote no. 7, the grain injury was slightly greater than commercially desirable. Antidote no. 1 had the best protective effect in four treatments. The common bonfire was completely suppressed and the spleen was well to excellent.

Example 8

In this test, the efficacy of the same five antidotes as in cases 6 and 7 was investigated in compositions containing herbicide no. 1 and as a co-herbicide, butachlor (herbicide No. 9), the active substance in the MACHET ^ herbicide, a leading commercial rice herbicide.

The test procedure used in this case was the same as in Examples 6 and 7. The test results are shown in Table 8.

Table 8

Herbicide Antidote kg / ha_ kg / ha_ With damage

no. 1 no. 9 no. dose wheat EC AT 0.56 2.24 - - 65 100 85 0.14 II - - 25 100 70 0.56 H 15 8.96 10 97 75 0.14 n 15 II 15 98 70 0.56 II 15 2.24 10 95 80 0.14 It 15 II 20 99 85 0.56 II 7 8.96 20 99 65 0.14 II 7 II 10 99 65 0.56 II 7 2.24 25 99 75 0.14 II 7 II 5 97 70 0.56 II 1 8.96 15 99 80 0.14 II 1 II 10 99 70 0.56 II 1 2.24 20 98 85 0.14 II 1 II 20 99 70 0.56 II 2 8.96 20 98 80 0.14 II 2 II 15 99 75 0.56 tl 2 2.24 25 99 90 0.14 II 2 II 15 99 70 0.56 II 13 8.96 30 100 85 0.14 II 13 II 10 99 80 0.56 II 13 2.24 45 99 85 0.14 II 13 II 25 99 75 0.56 - - - 60 93 85 0.14 - - - 10 55 70 - 2.24 - - 5 99 25 control 0 0 0

According to the above information, herbicide no. 1 at a dose of 0.56 kg / ha plus herbicide no. 9 at a dose of 2.24 kg / ha caused 65% damage to the grain without antidote.

Antidote supplementation significantly reduced cereal damage in all cases; many combinations and doses of the composition tested reduced cereal damage to commercially acceptable rates while maintaining or increasing weed control or suppression. The best protective effect in all four treatments was achieved by antidote no. 15.

Example 9

In this case, we investigated the protective effect on herbicide no. 1 and another leading rice herbicide, i.e. herbicide no. 13, using the same antidotes and the same test procedure as described in the previous example. Herbicide no. 13 is pretilachlor, an active substance used in the commercial herbicides for rye RITO®, SOFIT® and SOFI ·] ® SUPER.

The test results are shown in Table 9.

Table 9 poison

Prot herbicide Prot kg / ha_ kg / h,

no No.13 no. 0.56 2.24 - 0.14 tl - 0.56 II 15 0.14 tl 15 0.56 II 15 0.14 tl 15 0.56 tl 7 0.14 II 7 0.56 II 7 0.14 tl 7 0.56 tl 1 0.14 tt 1 0.56 It 1 0.14 It 1 0.56 tl 2 0.14 It 2 0.56 tt 2 0.14 tl 2 0.56 tt 13 0.14 tl 13 0.56 tt 13 0.14 tl 13 0.56 tt 0.14 tl - - 2.24 -

control

With the injury

dose wheat EC AT - 65 100 90 - 10 100 70 8.96 5 100 75 tl 0 100 90 2.24 15 99 85 It 5 100 60 8.96 25 100 85 It 0 100 75 2.24 30 100 85 tl 10 100 80 8.96 10 100 85 It 0 100 75 2.24 5 100 85 It 0 100 75 8.96 20 100 80 tl 5 100 75 2.24 20 100 85 It 5 100 80 8.96 20 100 90 II 0 100 75 2.24 25 100 90 tt 10 100 70 - 20 75 80 - 5 60 70 - 0 100 5 0 0 0

Herbicide no. 1 at a dose of 0.56 kg / ha and no. 13 at a dose of 2.24 kg / ha, in combination, caused 65% damage to the grain; however, cereal damage was greatly reduced by each of the five antidotes used in the test. The best protective effect in all four treatments was achieved by antidote no. 1, which together with antidote no. 15 at the commercial level provided protection of the grain against two herbicides in all herbicide and antidote combinations. All treatments resulted in complete crushing of the common bone and previous crushing or suffocation

Example 10

In this test we investigated the protective effect of various antidotes against combinations of herbicide no. 1 and the other on (-chloroacetanilide soherbicide (herbicide no. 5). Propaklor is the active substance in the commercial herbicide RAMROD®.

As in the previous example, we also used procedure II here. The test results are shown in Table 10.

Table 10

Herbicide Antidote kg / ha kg / ha_ 7, damage

no no. 5 no. dose wheat EC AT 0.56 4.48 - - 70 100 80 0.14 > 1 - - 5 100 70 0.56 II 15 8.96 10 85 75 0.14 II 15 II 0 90 80 0.56 It 15 2.24 10 93 80 0.14 II 15 II 0 98 70 0.56 II 7 8.96 25 96 80 0.14 II 7 II 10 98 75 0.56 tl 7 2.24 40 98 95 0.14 II 7 II 10 99 70 0.56 II 1 8.96 0 99 80 0.14 II 1 II 0 99 70 0.56 tt 1 2.24 15 98 70 0.14 II 1 II 10 99 75 0.56 II 2 8.96 25 99 80 0.14 II 2 VI 10 99 80 0.56 11 2 2.24 15 99 75 0.14 tt 2 II 15 100 60 0.56 II 13 8.96 10 98 75 0.14 II 13 II 15 97 70 0.56 II 13 2.24 45 99 80 0.14 II 13 0 98 70 0.56 - - - 30 80 75 0.14 - - - 20 75 70 - 4.48 - - 0 100 15 control 0 0 0

Significant harm reduction in terms of herbicide composition was achieved with all antidotes tested. Antidote no. 15 has the best protective effect, closely followed by antidote no. 1; these two antidotes, together with antidote no. 13 (except for 0.56 kg / ha of herbicide No 1, 4.48 kg / ha of herbicide No 13 and 2.24 kg / ha of antidote) have reached a commercial level of grain protection ₍ as they provide excellent suppression of common grebe and excellent suppression or even its suffocation.

Example 11

In this case, the (- kloroacetanilid soherbicid, metazachlor (herbicide-No. _14)? Combined with the herbicide no. 1 to investigate the effects of different protective agents to the composition.

Metazachlor is a gestational substance in the commercial BUTISAi ^ S herbicide used as a 500 g / L formulation here. Again, procedure II was followed in performing the test; the results are shown in Table 11.

- 60 Table 11

Herbicide Antidote kg / ha_ kg / ha_ With damage

no. 1 no. 14 no. cereal dose EC AT 1.12 3.36 - - 97 99 95 0.56 »1 - 93 99 85

1.12 15 8.96 40 100 85 0.56 15 II 65 100 90 1.12 15 2.24 25 100 85 0.56 15 II 65 100 90

1.12 7 8.96 45 99 90 0.56 ” 7 II 45 100 85 1.12 ... 7 2.24 70 99 90 0.56 7 II 10 99 80

1.12 1 8.96 50 100 80 0.56 1 II 50 100 90 1.12 1 2.24 45 99 85 0.56 1 It 25 99 80

1.12 2 8.96 75 100 85 0.56 '· 2 II 75 99 90 1.12 '' 2 2.24 75 100 97 0.56 » 2 II 75 99 85

1.12 13 8.96 70 100 95 0.56 ” 13 II 40 100 85 1.12 13 2.24 60 100 90 0.56 13 II 75 100 85

1.12 - - - 65 80 80 0.56 - - - 65 75 75 - 3.36 - - 85 100 65

0 0 control

As shown in Table 11, the damage to the cereals with herbicides 1 and 14, both alone and in combination, was too great. Although different antidotes reduced cereal damage by varying degrees (markedly in some cases), this particular combination of herbicides at the test doses did not give overall dramatic protection to other herbicide combinations. In these tests, dichloroacetamide antidotes (Nos. 1, 7 and 15) outperformed antidotes (2 and 13) of other chemicals.

Example 12

This case was intended to investigate the efficacy of thirteen different antidotes from different chemical classes as protective agents against herbicide no. 1 and acetoclorine (herbicide No. 6) as a co-herbicide. Acetochlor is the active substance in the commercial herbicides GUARDIAI ^ and WENNElf ^.

The test procedure used in this case is Procedure II described above.

The test results are shown in Table 12.

Table 12

Herbicide Antidote kg / ha % injuries kg / ha no no. 6 no. dose wheat EC AT 0.56 2.24 - - 45 100 95 0.14 M - - 25 100 75 0.56 H 15 8.96 5 100 80 0.14 II 15 II 10 100 75 0.56 H 15 2.24 20 100 90 0.14 II 15 II 15 100 70 0.56 II 7 8.96 5 100 75 0.14 n 7 It 5 100 65 0.56 II 7 2.24 20 100 85 0.14 It 7 II 15 100 80 0.56 It 1 8.96 15 100 80 0.14 It 1 II 10 100 80 0.56 II 1 2.24 15 100 80 0.14 II 1 II 10 100 65 0.56 II 5 8.96 5 100 90 0.14 II 5 II 10 100 85 0.56 II 5 2.24 10 100 85 0.14 II 5 II 5 100 75 0.56 II 10 8.96 10 100 90 0.14 II 10 II 10 100 80 0.56 II 10 2.24 30 100 80 0.14 II 10 II 10 100 75 0.56 II 3 8.96 20 100 90 0.14 II 3 II 15 100 70 0.56 II 3 2.24 15 100 80 0.14 II 3 II 10 100 75

Table 12 (continued)

Herbicide Antidote kg / ha With the injury kg / ha no. 1 no. 6 no. dose žitc > EC AT 0.56 2.24 12 8.96 15 100 85 0.14 II 12 II 10 100 85 0.56 II 12 2.24 25 100 95 0.14 II 12 It 15 100 75 0.56 9 8.96 25 100 75 0.14 tl 9 II 15 100 75 0.56 II 9 2.24 20 100 90 0.14 II 9 II 15 100 65 0.56 II 8 8.96 10 100 80 0.14 II 8 II 10 100 70 0.56 1 « 8 2.24 20 100 90 0.14 II 8 II 15 100 85 0.56 II 2 8.96 25 100 90 0.14 II 2 II 20 100 70 0.56 II 2 2.24 10 100 85 0.14 II 2 II 20 100 75 0.56 1 « 13 8.96 40 100 90 0.14 II 13 IV 30 100 85 0.56 II 13 2.24 35 100 95 0.14 II 13 II 10 100 80 0.56 II 4 8.96 25 100 95 0.14 II 4 II 35 100 80 0.56 II 4 2.24 40 100 90 0.14 It 4 II 25 100 65

- 64 Table 12 (continued)

Herbicide Antidote kg / ha_ kg / ha_% damage

no no. 6 no. dose wheat EC AT 0.56 2.24 6 8.96 20 100 80 0.14 • 1 6 II 15 100 80 0.56 II 6 2.24 20 100 75 0.14 II 6 II 15 100 90 0.56 - - - 20 75 85 0.14 - - - 15 55 50 - 2.24 - - 25 100 10 control 0 0 0

According to the data in Table 12, we can see that without antidote, the herbicide no. 1 at a dose of 0.56 kg / ha and herbicide no. 6 at a dose of 2.24 kg / ha (maximum test doses) results in 20 Z / oz. 25 Grain damage to the grain and thus total damage to the grain at the same doses of 45 Z. However, with the addition of the antidote at a dose of 8.96 kg / ha, the grain damage was dramatically reduced in all cases, except for the use of herbicide no. 13, but was most dramatically reduced in the case of dichloroacetamide antidotes (Nos. 15, 7, 1, 5, 10, 3,

12, 9 and 8). At the maximum test doses, all dichloroacetamide antidotes except no. 3 and 9, reduced the grain damage to a commercially acceptable level, but when the herbicide dose was no. 1 reduced to 0.14 kg / ha, even antidotes 3 and 9 reduced the herbicidal grain damage to the commercial level.

In a similar but less spectacular way, non-dichloroacetamide antidotes were commercially available at certain levels and in certain combinations of herbicide (s) and antidotes: antidote no. 6 containing herbicide no. 1: herbicide no. 6 and antidotes in ratios 0.14: 2.24: 8.96 kg / ha; antidote no. 2 and said herbicides: antidotes in the ratios of 0.56: 2.24: 2.24 kg / ha, and antidotes 6 and 13 and said herbicides: antidotes in the ratios of 0.14: 2.24: 2.24 kg / ha.

In all the tests above, the common gill was completely suppressed, and the suppression of the spleen was generally comparable to that of a combination of herbicides without a protective agent.

Example 13

In this case, several dichloroacetamide antidotes were tested in terms of protection against the herbicide composition containing herbicide no. 1 and a co-herbicide, acetoclor (herbicide No. 6), in cereals in the presence of spleen. The procedure used in this case was the process described above II. The test results are shown in Table 13.

Table 13

Herbicide Antidote kg / ha no. 1 No.6 kg / ha With the injury no. dose wheat AT 0.14 - - - 10 95 0.56 - - - 55 85 2.24 - - - 80 95 - 4.48 - - 50 10 0.56 1 » - - 65 100 - II 1 0.56 20 100 0.5o II 1 t » 5 5 - II 1 2.24 10 60 0.56 II 1 II 10 85 - II 3 0.56 10 80 0.56 VI 3 II 40 100 - II 3 2.24 5 0 0.56 II 3 II 10 95 - II 5 0.56 5 0 0.56 II 5 II 10 90 - II 5 2.24 15 30 0.56 VI 5 II 10 100 - II 7 0.56 0 0 0.56 II 7 tl 25 95 - II 7 2.24 5 40 0.56 II 7 II - - - II 10 0.56 15 30 0.56 II 10 II 40 100 - II 10 2.24 5 0 0.56 II 10 II 40 9

Table 13 (continued)

Herbicide kg / ha Antidote kg / ha With the injury no No.6 no. dose wheat AT - II 12 0.56 25 60 0.56 II 12 H 10 100 - It 12 2.24 10 25 0.56 II 12 II 10 100 - II 14 0.56 5 0 0.56 II 14 II 15 100 - II 14 2.24 5 60 0.56 II 14 n 15 95 - II 15 0.56 5 20 0.56 II 15 II 5 100 - n 15 2.24 15 95 0.56 II 15 II 15 90

It is observed that all the antidotes in the trial of Case 13 reduced the damage to the cereals caused by the herbicides used alone or in combination when used at higher doses. The importance of spleen suppression with herbicide no. 1 is evident in view of the low weed control values in cases where this herbicide was omitted from the composition.

Antidote no. The 15 was very effective everywhere, followed by the No. 14, 1, 12, 7 and 10. Protection at the commercial level was performed in all doses and combinations of antidotes no. 5, 14 and 15.

Example 14

In this case, the antidote no. 17 to determine its effectiveness against the herbicide combination of herbicide no. 1 and metolachlor (herbicide No. 12) as a co-herbicide, (metolachlor is the active substance in the DUAL® herbicide). This test was performed under the same test conditions as described and performed in Example 13. The test results are shown in Table 14; the dose of chemicals is in kg / ha.

Table 14

Herbicide Herbicide Antidote With the injury no. 1 no. 12 no. 17 wheat AT 0.14 4,48 0.15 15 90 0.56 It tt 25 95 2.24 tl tt 80 100

The above test results indicate that antidote no. 17, even at a low dose of 0.15 kg / ha, able to protect the grain against the combination of herbicides (No 1: No 12 at a ratio of 0.14: 4.48) at a commercially acceptable level. This protection was reduced and significantly lost at higher doses of herbicide no. 1. But this reduced protection can no doubt be replaced by an increased concentration of the antidote to an appropriate and appropriate level.

In the preceding examples, which described the protective compositions of the herbicides of the present invention, the compounds were scherbicides o (-chloroacetamides. Examples 15-22 described the protective compositions of the herbicides containing combinations of sulfonylurea compounds of formula I (and IA) and as a compound of co-herbicides of significant commercial herbicides of the chemical class of thiocarbamates.

Example 15

This example describes tests investigating the antidote effect of multiple antidotes against the herbicidal effect of a combination of herbicide no. 1 and butylate in cereals and widespread weeds, common hams and spleen.

The antidotes used in these tests were no. 1 - 10, 12, 13 and 15.

The test procedure used in these tests was Procedure II described above. Antidotes were introduced into the upper layer of the earth by pipette after the herbicides were sprayed over the soil, harvested and watered over the earth.

The test results are shown in Table 15.

Table 15

Herbicide Antidote kg / ha_ kg / ha_% damage

no. 1 no. 10 no. dose .wheat . EC AT 1.12 6.72 - - 25 98 85 0.56 II - - 20 97 80 1.12 II 15 8.96 15 97 85 0.56 II 15 11 10 99 80 1.12 II 15 2.24 15 97 85 0.56 II 15 II 20 98 75 1.12 II 7 8.96 10 98 85 0.56 11 7 It 0 98 70 1.12 11 7 2.24 20 90 85 0.56 II 7 II 15 95 80 1.12 II 1 8.96 30 90 65 0.56 11 1 II 10 90 70 1.12 11 1 2.24 20 93 70 0.56 II 1 It 15 97 80 1.12 11 5 8.96 15 98 85 0.56 II 5 It 20 95 70 1.12 II 5 2.24 10 90 85 0.56 II 5 II 5 97 85 1.12 11 10 8.96 10 98 85 0.56 11 10 II 5 96 70 1.12 It 10 2.24 20 96 80 0.56 II 10 11 5 97 70 1.12 11 3 8.96 15 97 80 0.56 II 3 11 10 97 80 1.12 II 3 2.24 5 93 80 0.56 11 3 11 15 95 75

Table 15 (continued)

Herbicide Antidote kg / ha With the injury kg / ha no. 1 no. 10 no. dose wheat EC AT 1.12 6.72 12 8.96 20 98 80 0.56 H 12 II 0 96 80 1.12 tl 12 2.24 35 97 85 0.56 VI 12 II 10 90 75 1.12 II 9 8.96 15 97 80 0.56 II 9 IV 15 95 70 1.12 II 9 2.24 5 97 80 0.56 It 9 It 15 97 65 1.12 «T 8 8.96 20 85 85 0.56 II 8 It 10 90 70 1.12 II 8 2.24 5 95 80 0.56 II 8 tt 0 93 75 1.12 II 2 8.96 20 98 85 0.56 II 2 II 15 90 75 1.12 II 2 2.24 10 96 85 0.56 tl 2 II 25 96 75 1.12 II 13 8.96 0 95 85 0.56 II 13 II 15 95 70 1.12 tl 13 2.24 20 97 90 0.56 II 13 II 10 97 85 1.12 II 4 8.96 25 90 85 0.56 II 4 II 5 85 85 1.12 II 4 2.24 15 95 85 0.56 II 4 II 15 93 85

Table 15 (continued)

Herbicide Antidote kg / ha_ kg / ha_ With damage

no. 1 No.10 no. dose wheat EC AT 1.12 6.72 6 8.96 20 99 95 0.56 > 1 6 II 20 97 85 1.12 in 6 2.24 10 98 90 0.56 «1 6 II 5 95 80 1.12 - - - 20 55 70 0.56 - - - 20 35 50 - 6.72 - - _5 97 55 control 0 0 0

According to the data in Table 15, it is observed that all herbicide no. 1 at doses of 1.12 and 0.56 kg / ha, together with herbicide no. 10 at a dose of 6.72 kg / ha introduced before sowing reduced cereal damage at one or both doses to a commercially acceptable level. In this test, antidote no. 13, followed closely by antidotes no. 7 and 10. With different dosage combinations of the two herbicides and antidotes, the four prot / poisons (Nos. 7, 8, 12 and 13) allowed complete protection of the grain from damage, with the ordinary bones being perfectly suppressed and the spleen well suppressed. or suffocated.

Example 16

In this case, the same antidotes and procedures were used as in the previous case, except that the co-herbicide in the tests of this case was EPTC, the active substance in the commercial herbicide EPTAl ^ EPTC was identified as herbicide no. 4.

The test results are shown in Table 16.

Table 16

Herbicide Antidote kg / ha _ kg / ha_% damage

no EPTAM no. dose wheat EC AT 1.12 6.72 - - 25 90 85 0.56 II - - 25 93 80 1.12 II 15 8.96 15 85 75 0.56 II 15 II 10 85 75 1.12 II 15 2.24 5 80 70 0.56 II 15 II 10 85 75 1.12 II 7 8.96 * 20 75 80 0.56 II 7 II 5 80 75 1.12 II 7 2.24 5 75 80 0.56 II 7 II 0 80 80 1.12 II 1 8.96 15 85 75 0.56 II 1 II 0 95 70 1.12 II 1 2.24 0 85 80 0.56 II 1 II 0 80 80 1.12 II 5 8.96 10 75 85 0.56 II 5 II 15 80 80 1.12 11 5 2.24 10 80 85 0.56 II 5 II 0 80 80 1.12 II 10 8.96 5 95 85 0.56 II 10 II 5 98 80 1.12 II 10 2.24 20 85 85 0.56 II 10 II 0 85 85 1.12 II 3 8.96 15 85 80 0.56 II 3 II 15 85 80 1.12 II 3 2.24 0 85 80 0.56 II 3 II 15 85 85

Table 16 (continued)

Herb: kg / ha Lcid Antidote injuries kg / ha z no EPTAM no. dose wheat EC AT 1.12 6.72 12 8.96 10 90 85 0.56 M 12 II 15 85 75 1.12 VI 12 2.24 0 90 85 0.56 11 12 11 5 90 85 1.12 1 « 9 8.96 15 75 75 0.56 II 9 II 10 80 75 1.12 II 9 2.24 0 80 80 0.56 11 9 11 5 85 85 1.12 II 8 8.96 25 75 80 0.56 II 8 11 10 85 80 1.12 H 8 2.24 25 80 80 0.56 11 8 11 5 80 80 1.12 11 2 8.96 5 85 85 0.56 II 2 II 0 80 80 1.12 11 2 2.24 15 90 80 0.56 tl 2 11 5 85 75 1.12 II 13 8.96 10 75 80 0.56 II 13 II 0 80 75 1.12 II 13 2.24 15 85 85 0.56 II 13 11 10 85 85 1.12 II 4 8.96 5 85 80 0.56 II 4 II 0 90 80 1.12 11 4 2.24 30 80 80 0.56 11 4 11 10 80 80 1.12 II 6 8.96 10 90 90 0.56 11 6 II 0 90 85 1.12 II 6 2.24 5 85 85 0.56 11 6 n 15 85 80

Table 16 (continued)

Herbicide Antidote

kg / ha kg / ha % injuries No. l EPTAM no. dose wheat EC AT 0.56 10 70 60 1.12 - 15 55 40 6.72 - 5 95 55

0 0 control

The data in Table 16 show that when combining the maximum test doses of herbicide no. 1 at 1.12 kg / ha and EPTAM at 6.72 kg / ha, all antidotes except nos. 8, protect the grain.

In addition, the herbicidal damage to the grain with all other combinations of herbicides no. 1 and EPTAM reduced except for antidote no. 4 for herbicide combination no. 1 at a dose of 1.12 kg / ha, EPTAM at a dose of 6.72 kg / ha and antidote at a dose of 2.24 kg / ha. Seven dichloroacetamide antidotes and herbicides 1, 4, 6 and 13 from other chemistries have shown commercial suppression of common gill and suppression or suppression of the spleen.

Example 17

In this case, the co-herbicide compound tested with the herbicide no. 1, vernolate (herbicide No. 11); this compound is the active substance of the herbicide VERNAl · ^? The antidotes and procedures used in these tests were the same as in Examples 15 and 16. The test results are shown in Table 17.

Table 17

Herbicide Antidote kg / ha_ kg / ha__With injury

no. 1 VERNAM no. dose wheat EC AT 1.12 6.72 - - 70 99 85 0.56 II - - 75 99 85 1.12 II 15 8.96 0 99 95 0.56 It 15 15 99 80 1.12 II 15 2.24 15 99 80 0.56 II 15 II 0 99 85 1.12 II 7 8.96 5 99 98 0.56 II 7 II 10 99 95 1.12 II 7 2.24 15 99 85 0.56 II 7 II 0 99 90 1.12 II 1 8.96 10 99 85 0.56 II i II 0 98 80 1.12 II 1 2.24 10 100 85 0.56 tl 1 II 5 98 85 1.12 II 5 8.96 5 98 97 0.56 H 5 II 10 99 90 1.12 tl 5 2.24 10 99 85 0.56 II 5 It 15 99 85 1.12 II 10 8.96 15 99 95 0.56 II 10 It 10 99 90 1.12 1 « 10 2.24 10 99 90 0.56 II 10 11 5 99 95 1.12 II 3 8.96 0 99 85 0.56 II 3 II 15 99 90 1.12 II 3 2.24 10 99 90 0.56 II 3 II 15 99 85

Table 17 (continued)

Herbicide

Antidote

kg / ha kg / ha % injuries no. 1 VERNAM no. dose wheat EC AT 1.12 6.72 12 8.96 5 99 85 0.56 n 12 10 99 85 1.12 M 12 2.24 15 99 90 0.56 II 12 5 99 85

1.12 II 9 8.96 0 99 95 0.56 It 9 II 5 99 85 1.12 tl 9 2.24 10 99 85 0.56 II 9 II 5 99 90

1.12 II 8 8.96 10 99 85 0.56 II 8 II 0 99 90 1.12 II 8 2.24 15 99 95 0.56 II 8 II 15 99 95

1.12 II 2 8.96 15 99 80 0.56 II 2 II 25 99 80 1.12 II 2 2.24 25 98 85 0.56 II 2 II 35 98 85

1.12 tl 13 8.96 10 99 85 0.56 II 13 II 25 99 85 1.12 II 13 2.24 15 99 85 0.56 II 13 II 15 99 85

1.12 II 4 8.96 20 99 85 0.56 tl 4 II 15 99 90 1.12 II 4 2.24 25 99 85 0.56 II 4 II 15 99 80

1.12 It 6 8.96 15 100 95 0.56 II 6 II 20 99 90 1.12 II 6 2.24 35 99 95 0.56 II 6 tt 25 99 80

- ao Table 17 (continued)

Herbicide Antidote

kg / ha kg / ha % injuries No. VERNAM no. cereal dose EC AT 1.12 “5 45 65 0.56 - - 0 25 10 6.72 - - 80 100 75

0 0 control

The data in Table 17 show that for one or more combination doses of herbicides and antidotes, all antidotes have reached a commercial level of protection against the combination of sulfonylurea herbicide herbicide no. 1 and thiocarbamate, vernolate, without reducing the excellent suppression of common grebe and good to excellent suppression of weed spleen.

In fact, all antidotes, except no. 2, 4, 6 and 13 were effective against all combinations of the two herbicides at the commercial level of protection. Again, dichloroacetamide antidotes were more effective in reducing cereal damage (mainly caused by vernolate) than other types of antidotes. In this test, the best protective effect was achieved by antidote no. 9.

Example 18

In the test in this case, the composition of the herbicide was similar to that of Example 16, in that the herbicide no. 1 combined with EPTC (herbicide No. 4) as a co-herbicide, and the antidotes used were no. 1, 2, 7, 13 and 15. However, in this test, EPTC was introduced as a formulation of ERADICANE (EPTC + antidote R-25788, i.e. antidote # 1) at a dose of 8.96 kg / ha. Thus, two antidotes were present in this trial, i.e. R-25788 and one of the ancillary antidotes, no. 2, 13 and 15.

The test procedures have already been described in Procedure II.

The test results are shown in Table 18.

Table 18

Herbicide Antidote kg / ha__ kg / ha __% damage

no. 1 ERADICANE no. dose wheat EC AT 1.12 8.96 - - 20 85 75 0.56 1 * - - 25 90 80 0.56 VI 15 8.96 25 90 85 1.12 v * 15 II 30 85 65 0.56 II 15 2.24 25 90 80 1.12 II 15 n 15 93 80 0.56 II 7 8.96 20 85 80 1.12 II 7 II 10 85 75 0.56 II 7 2.24 15 90 75 1.12 tt 7 11 15 85 70 0.56 II 1 8.96 25 90 85 1.12 II 1 II 25 85 75 0.56 II 1 2.24 30 90 85 1.12 II 1 H 35 90 75 0.56 II 2 8.96 25 85 93 1.12 If 2 11 20 95 75 0.56 n 2 2.24 15 93 80 1.12 II 2 IV 20 85 70 0.56 II 13 8.96 20 85 80 1.12 II 13 II 40 90 75 0.56 II 13 2.24 10 85 80 1.12 II 13 It 10 85 75 1.12 - - - 25 55 55 0.56 - - - 30 30 45 - 8.96 - - 10 95 35 control 0 0 0

In the test given in Table 18, the chemicals were used before sowing.

Barnyardgrass was repressed, p slezenec _a choke, but it was the worst grain protection.

Although the grain damage was slightly less with the four treatments using antidote no. 7, other protective agents did not reduce this minimum level of grain damage at the highest test doses of herbicides and safeners.

Example 19

The test described in this case was performed in the same manner and with the same antidotes as in Example 18, the only difference being the replacement of the commercial herbicide ERADICAN ^ EXTRA with ERADICAN ^.

ERADICAN1 ^ EXTRA is a formulation containing such an antidote, i.e.

R-29148 (Antidote No. 5) as Developer Dietolate.

The test results are shown in Table 19.

Table 19

Herbicide Antidote kg / ha ERADICANE kg / ha_ _% damage

no. 1 EXTRA no. dose wheat EC AT 1.12 8.96 - - 20 95 85 0.56 II - - 30 95 80 1.12 II 15 8.96 25 90 75 0.56 II 15 II 30 85 75 1.12 II 15 2.24 25 85 85 0.56 It 15 1 » 20 90 70 1.12 II 7 8.96 25 85 85 0.56 II 7 II 20 85 80 1.12 II 7 2.24 25 90 75 0.56 II 7 II 15 85 75 1.12 tl 1 8.96 25 95 85 0.56 tl 1 II 15 90 75 1.12 tl 1 2.24 35 90 70 0.56 II 1 tt 35 90 70 1.12 tl 2 8.96 20 85 75 0.56 It 2 It 25 90 75 1.12 It 2 2.24 25 85 85 0.56 It 2 tl 20 90 75 1.12 tl 13 8.96 15 95 85 0.56 It 13 It 15 90 70 1.12 It 13 2.24 20 90 80 0.56 It 13 tt 25 90 65 1.12 - - - 25 70 65 0.56 - - - 20 30 50 - 8.96 - - 5 98 55 control 0 0 0

The addition of other antidotes to the EPTC formulation, which already contains the R-29148 antidote, has reduced the grain damage in certain cases. Antidote no. 13 was the most effective antidote in all four treatments. On the other hand, for some combinations of herbicide and antidote doses in this test, some antidotes appear to be exacerbating cereal damage: e.g. at the highest doses of antidotes and herbicides, antidotes are no. 1, 7 and 15 slightly increased cereal damage by. 20 Z to 25 Z. In this test, the common grebe was well suppressed and the spleen was suffocated to well suppressed.

Example 20

This example describes tests designed to test two generally effective antidote compounds, i.e. antidotes no. 5 and 15, in comparison with the herbicidal effect of the compounds of ^ feulfonylurea, herbicide no. 1 and commercial EPTC herbicides (herbicide No. 4) and ERADICAN ^ EXTRA (EPTC + R29148, antidote No. 5). Procedure II was used to perform these experiments. EPTC and ERADICAN ^ EXTRA formulations were applied to the cover layers of the soil (applied to seed beds), followed by sequential application of herbicide no. 1 and antidote no. 15 using a pipette. The soil was evenly mixed and spread over seed beds, followed by an above-ground irrigation to a depth of 0.6 cm. Particular attention was paid to the suppression of the spleen, and the common bonfire was not included in this test.

The test results are shown in Table 20.

Herbicides ERADICANE EXTRA .Table 20 Antidote no. 15 With the injury kg / ha no. 1 no. 4 wheat AT - - 2.24 - 0 0 - - 4.48 - 0 15 - - 6.72 - 0 85 - - - - 0 0 - 2.24 - - 0 0 - 4.48 - - 0 0 - 6.72 - - 10 18 0.56 - - - 70 95 2.24 - 2.24 - 90 100 0.56 - II - 55 95 2.24 - 4.48 - 85 100 0.56 - n - 65 90 2.24 - 6.72 - 95 95 0.56 - II - 75 100 2.24 - - - 85 100 0.56 2.24 - - 75 95 2.24 II - - 90 95 0.56 4.48 - - 35 90 2.24 II - - 70 95 0.56 6.72 - - 85 100 2.24 tl - - 90 100 0.56 2.24 - 0.18 5 90 2.24 II - n 35 95 0.56 4.48 - 0.35 15 95 2.24 II - II 15 95 0.56 6.78 - 0.56 0 95 2.24 II - II 15 100

The data in Table 20 show that the ERADICANE EXTRA antidote was not effective against the combination of herbicides no. 1 and no. 4. This result is consistent with the result of Example 18. However, these results should also be compared with those of Example 16, where the herbicide combination of herbicides no. 1 and no. 4 (not present as an ERADICANE EXTRA formulation) effectively protected ^ with the antidote component (R-29148) in ERADICANE EXTRA, as well as many other antidotes, including antidote no. 1 (antidote in ERADICANE), which was also shown by the test results in Table 16 for adequate herbicide protection no. 4.

Example 21

In this case, the tests were carried out as in Examples 18 - 20, with the SUTAi ^ PLUS co-herbicide component being a commercial product containing butylate (herbicide No. 10) and antidote R-27588 (antidote no. 1). Again, there were compounds of antidotes no. 1, 2, 7, 13 and 15. Procedure II was used. The test results are shown in Table 21.

Table 21

Herbicide Antidote kg / ha_ kg / ha_ With damage

no. 1 SUTAN + no. dose wheat EC AT 1.12 8.96 - - 5 50 70 0.56 in - - 10 20 60 1.12 H 15 8.96 20 40 65 0.56 II 15 It 25 10 60 1.12 II 15 2.24 30 15 65 0.56 II 15 II 25 0 50 1.12 It 7 8.96 15 10 45 0.56 tl 7 It 20 10 65 1.12 tl 7 2.24 15 40 65 0.56 tt 7 It 5 25 45 1.12 tt 1 8.96 20 35 60 0.56 tt 1 tl 15 25 65 1.12 11 1 2.24 30 10 65 0.56 tt 1 It 15 0 40 1.12 II 2 8.96 15 5 70 0.56 II 2 II 5 10 65 1.12 II 2 2.24 0 45 70 0.56 II 2 II 10 5 55 1.12 II 13 8.96 10 70 70 0.56 II 13 II 10 50 40 1.12 tl 13 2.24 5 70 70 0.56 II 13 II 0 40 55 1.12 - - - 30 10 65 0.56 - - - 0 10 50 - 8.96 - - 15 10 0

0 0 control

As can be seen from the data in Table 21, the mixture applied before sowing provided excellent grain protection. The addition of other dichloroacetamide antidotes did not improve grain protection. Although grain protection was acceptable to a minimum, weed control was poor to moderate.

Example 22

The experiments in this case were designed as a retest of those described in Example 21 for not characteristically poor grain protection and weed suppression, which are thought to result from seasonally high greenhouse temperatures. Therefore, the temperatures were lowered for these tests. The results of the experiments are shown in Table 22.

kx

Table 22

Herbicide Antidote

kg / ha kg / h a 7. injuries no. 1 SUTAN + no. dose wheat EC AT 1.12 8.96 -. - 60 93 85 0.56 tl - - 55 93 80 1.12 II 15 8.96 45 90 80 0.56 II 15 IV 55 90 98 1.12 II 15 2.24 60 85 80 0.56 II 15 It 45 85 70 1.12 II 7 8.96 50 80 70 0.56 II 7 II 50 90 75 1.12 II 7 2.24 65 95 97 0.56 II 7 It 45 90 80 1.12 VI 1 8.96 55 90 80 0.56 II 1 II 60 90 80 1.12 II 1 2.24 50 85 80 0.56 II 1 II 45 93 80 1.12 II 2 8.96 50 90 90 0.56 II 2 U 55 90 90 1.12 II 2 2.24 40 85 93 0.56 II 2 II 45 80 80 1.12 II 13 8.96 60 93 90 0.56 II 13 II 60 90 95 1.12 II 13 2.24 75 95 95 0.56 II 13 II 70 90 85 1.12 - - - 65 70 80 0.56 - - - 60 55 65 - 8.96 - - 5 100 75

control

0 0

As can be seen from the data in Table 22, all herbicide compositions demonstrated excellent to good suppression of common grebe and excellent to moderate suppression of spleen. In cereals, a moderate decrease in the root system was observed. In these tests, antidotes did not provide adequate protection against the aforementioned reduction in the root system caused by herbicide no. 1.

Example 23

In other greenhouse tests using procedure II already described, the effectiveness of antidote protection was no.

and 17 - 21 against herbicide no. Iv cereals in the presence of flycatcher (Setaria fabergi) and spleen (Abutilon theophrasti) as representatives of one-year-old monocotyledonous or dicotyledonous weeds.

The results of the tests are shown in Tables 23 A and 23 B, where said inhibition of seedlings represents an average of two replicates, with observations being made thirteen (13) days after the use of the chemicals.

The fly and the spleen are marked with the symbols SF or. AT. The data in Table 23 A show the results of tests using 2.24 kg / ha of antidotes, while in Table 23 B the dose of the antidote was reduced to 0.56 kg / ha.

Table 23A

Herb. no. 1 kg / ha Antidote Z inhibition st. kg / ha wheat SF AT 1.12 - - 65 80 95 0.56 - - 50 60 95 0.28 - - 25 35 90 0.14 - - 15 25 90 1.12 18 2.24 10 70 95 0.56 18 2.24 10 65 95 0.28 18 2.24 0 30 95 0.14 18 2.24 0 15 90 1.12 19 2.24 15 70 95 0.56 19 2.24 5 50 95 0.28 19 2.24 0 30 85 0.14 19 2.24 0 15 90 1.12 20 2.24 15 65 90 0.56 20 2.24 0 40 85 0.28 20 2.24 0 35 90 0.14 20 2.24 0 15 90 1.12 21 2.24 30 70 95 0.56 21 2.24 5 35 95 0.28 21 2.24 0 20 85 0.14 21 2.24 0 10 85 1.12 15 2.24 20 75 98 0.56 15 2.24 5 65 90 0.28 15 2.24 0 30 90 0.14 15 2.24 5 20 90 1.12 17 2.24 25 70 95 0.56 17 2.24 15 60 95 0.28 17 2.24 0 25 85 0.14 17 2.24 0 25 95

Herb.

Wh,

1.12

0.56

0.28

0.14

1.12

0.56

0.28

0.14

1.12

0.56

0.28

0.14

1.12

0.56

0.28

0.14

1.12

0.56

0.28

0.14

1.12

0.56

0.28

0.14

1.12

0.56

0.28

0.14

Table 23B

Prot no. istrup kg / ha Z inhibition wheat SF AT - - 60 70 90 - - 40 60 90 - - 25 30 95 - - 10 30 85 18 0.56 30 60 95 18 0.56 20 60 90 18 0.56 5 20 95 18 0.56 5 15 90 19 0.56 40 65 90 19 0.56 15 60 90 19 0.56 5 40 85 19 0.56 0 25 85 20 0.56 40 75 95 20 0.56 20 60 90 20 0.56 5 20 90 20 0.56 0 15 90 21 0.56 35 75 95 21 0.56 20 50 90 21 0.56 5 45 90 21 0.56 0 20 85 15 0.56 10 70 95 15 0.56 5 60 95 15 0.56 0 30 90 15 0.56 0 20 85 17 0.56 30 65 95 17 0.56 20 55 90 17 0.56 10 40 90 17 0.56 0 15 90

According to the data in Tables 23 A and 23 B, it has been observed that the damage caused by herbicide no. 1, without the presence of antidote, decreased with each test antidote at appropriate herbicide and antidote ratios at both antidote doses.

In particular, at a dose of 2.24 kg / ha of antidote, cereals with herbicide no. 1 reduced to a commercially acceptable level (i.e.,> 15% inhibition) in all cases except antidotes no. 15 and 17 at the highest test doses of the herbicide, i.e. 1.12 kg / ha. At lower doses, however, grain protection was achieved.

Similarly, it was at a lower antidote dose, i.e. 0.56 kg / ha and herbicide doses below 0.28 kg / ha in all cases guaranteed commercially acceptable grain protection. Antidote no. 15 effectively protected the grain against herbicides at all test doses, while other antidotes reduced the grain damage by 20% to 50% at the three highest doses of herbicides.

The test results further show that, in all cases, weed suppression had no effect on weed control compared to weed control with no herbicide without antidote.

Example 24

The tests described in Example 23 were duplicated, in which case several co-herbicides were included to ensure the effectiveness of antidotes against herbicide combinations no. 1 and herbicides no. 4, 6, 7 and 12 as co-herbicides.

The test results are shown in Table 24, where the antidote dose was 2.24 kg / ha.

Table 24

Herb. no. 1 kg / ha Soherbicide no. kg / ha Antidote % inhibition no. kg / ha wheat SF AT 0.56 7 0.28 - - 45 99 95 0.28 7 0.28 - - 30 100 95 0.14 7 0.28 - - 15 100 90 0.07. 7 0.28 - - 5 100 90 0.56 7 0.28 18 2.24 10 100 98 0.28 7 0.28 18 2.24 5 100 95 0.14 7 0.28 18 2.24 10 99 95 0.07 7 0.28 18 2.24 0 99 90 0.56 7 0.28 19 2.24 10 99 98 0.28 7 0.28 19 2.24 5 99 95 0.14 7 0.28 19 2.24 0 99 90 0.07 7 0.28 19 2.24 0 99 90 0.56 7 0.28 20 2.24 5 99 95 0.28 7 0.28 20 2.24 0 100 95 0.14 7 0.28 20 2.24 0 98 90 0.07 7 0.28 20 2.24 0 98 95 0.56 7 0.28 21 2.24 15 100 98 0.28 7 0.28 21 2.24 5 98 95 0.14 7 0.28 21 2.24 0 100 90 0.07 7 0.28 21 2.24 0 100 95 0.56 7 0.28 15 2.24 5 100 98 0.28 7 0.28 15 2.24 0 100 95 0.14 7 0.28 15 2.24 0 100 95 0.07 7 0.28 15 2.24 0 100 85 0.56 7 0.28 17 2.24 15 99 98 0.28 7 0.28 17 2.24 5 100 98 0.14 7 0.28 17 2.24 0 100 95 0.07 7 0.28 17 2.24 0 100 85

- 96 Table 24 (continued)

Herb. no. 1 kg / ha Soherbicide Antidote no. kg / ha % inhibition st. kg / ha wheat SF AT 0.56 12 0.28 - - 45 99 90 0.28 12 0.28 - - 30 99 95 0.14 12 0.28 - - 10 99 90 0.07 12 0.28 - - 5 99 85 0.56 12 0.28 18 2.24 15 99 95 0.28 12 0.28 18 2.24 10 100 95 0.14 12 0.28 18 2.24 0 99 99 0.07 12 0.28 18 2.24 0 100 80 0.56 12 0.28 19 2.24 20 99 99 0.28 12 0.28 19 2.24 5 100 95 0.14 12 0.28 19 2.24 0 99 85 0.07 12 0.28 19 2.24 0 99 85 0.56 12 0.28 20 2.24 10 100 98 0.28 12 0.28 20 2.24 5 100 98 0.14 12 0.28 20 2.24 5 100 95 0.07 12 0.28 20 2.24 0 99 90 0.56 12 0.28 21 2.24 20 99 98 0.28 12 0.28 21 2.24 10 100 98 0.14 12 0.28 21 2.24 5 99 95 0.07 12 0.28 21 2.24 0 100 90 0.56 12 0.28 15 2.24 5 99 99 0.28 12 0.28 15 2.24 5 100 98 0.14 12 0.28 15 2.24 5 99 95 0.07 12 0.28 15 2.24 5 99 90 0.56 12 0.28 17 2.24 20 100 95 0.28 12 0.28 17 2.24 5 98 98 0.14 12 0.28 17 2.24 5 99 98 0.07 12 0.28 17 2.24 5 99 90

- 97 Table 24 (continued)

Herb. no. 1 kg / ha Soherbicide Antidote With inhibition no. kg / ha no. kg / ha wheat SF AT 0.56 6 0.14 - - 40 100 95 0.28 6 0.14 - - 25 100 95 0.14 6 0.14 - - 20 100 95 0.07 6 0.14 - - 5 100 85 0.56 6 0.14 18 2.24 20 100 98 0.28 6 0.14 18 2.24 5 99 95 0.14 6 0.14 18 2.24 0 99 95 0.07 6 0.14 18 2.24 0 100 90 0.56 6 0.14 19 2.24 10 99 99 0.28 6 0.14 19 2.24 5 99 95 0.14 6 0.14 19 2.24 0 100 95 0.07 6 0.14 19 2.24 0 100 90 0.56 6 0.14 20 2.24 20 100 95 0.28 6 0.14 20 2.24 5 100 98 0.14 6 0.14 20 2.24 5 99 90 0.07 6 0.14 20 2.24 0 100 95 0.56 6 0.14 21 2.24 10 100 98 0.28 6 0.14 21 2.24 5 99 95 0.14 6 0.14 21 2.24 5 100 90 0.07 6 0.14 21 2.24 0 100 85 0.56 6 0.14 15 2.24 10 99 99 0.28 6 0.14 15 2.24 10 100 98 0.14 6 0.14 15 2.24 5 100 85 0.07 6 0.14 15 2.24 5 100 95 0.56 6 0.14 17 2.24 15 99 98 0.28 6 0.14 17 2.24 15 98 95 0.14 6 0.14 17 2.24 0 100 90 0.07 6 0.14 17 2.24 5 100 90

Table 24 (continued)

Herb. no. 1 kg / ha Soherbicide Antidote With inhibition no. kg / ha no. kg / ha wheat SF AT 0.56 4 1.12 - 40 75 90 0.28 4 1.12 - - 25 85 95 0.14 4 1.12 - - 20 80 90 0.07 4 1.12 - - 10 70 90 0.56 4 1.12 18 2.24 10 65 90 0.28 4 1.12 18 2.24 5 70 95 0.14 4 1.12 18 2.24 5 55 95 0.07 4 1.12 18 2.24 5 65 90 0.56 4 1.12 19 2.24 5 70 90 0.28 4 1.12 19 2.24 5 45 95 0.14 4 1.12 19 2.24 0 60 95 0.07 4 1.12 19 2.24 0 40 90 0.56 4 1.12 20 2.24 10 65 95 0.28 4 1.12 20 2.24 0 65 90 0.14 4 1.12 20 2.24 0 40 90 0.07 4 1.12 20 2.24 0 65 90 0.56 4 1.12 21 2.24 5 70 90 0.28 4 1.12 21 2.24 0 65 95 0.14 4 1.12 21 2.24 5 60 90 0.07 4 1.12 21 2.24 5 65 90 0.56 4 1.12 15 2.24 15 60 95 0.28 4 1.12 15 2.24 5 60 95 0.14 4 1.12 15 2.24 10 65 95 0.07 4 1.12 15 2.24 0 40 90 0.56 4 1.12 17 2.24 20 70 95 0.28 4 1.12 17 2.24 5 45 90 0.14 4 1.12 17 2.24 0 50 90 0.07 4 1.12 17 2.24 0 55 90

The data in Table 24 indicate that in all cases where combinations of herbicide no. Iv test doses of 0.28 kg / ha and 0.56 kg / ha and any co-herbicide at doses between 0.14 kg / ha and 1.12 kg / ha resulted in commercially unacceptable grain damage. Also herbicide combinations no. Iv at such low doses as 0.14 kg / ha and soherbicide no. 6 at a dose of 0.14 / ha and co-herbicide no. 4 at 1.12 kg / ha caused commercially unacceptable grain damage.

In contrast, the addition of each of the test antidotes at a dose of 2.24 kg / ha to herbicide combinations no. 1 at doses less than 0.56 kg / ha and co-herbicide at that dose evenly reduced cereal damage to a commercially acceptable level. In fact, only antidotes no. 17,

18, 19 and 20 did not protect against said combinations of herbicide and co-herbicide in the case of the highest dose (0.56 kg / ha) of herbicide no. 1.

In addition, the addition of antidote has largely not affected the control of various types of weeds, especially as regards the spleen.

Mdhvic suppression was noticeably worse, with some test doses of herbicide no. 1, less than 0.56 kg / ha, and co-herbicide no. 4 at a dose of 1.12 kg / ha if antidotes no. 15 and 17 - 21.

Example 25

Additional tests were performed in the greenhouse to determine the antidote effectiveness of antidote no. 1 (dichloromide) and 2 (naphthalic anhydride) in the protection of cereals against the action of herbicides no. 1-3 (i.e. NC-319,

NC-319 EX oz. NC-311). The chemicals were tested before and after the emergence of the plant. Herbicides were prepared and used as wettable powders; dichloromide was used as a concentrate for emulsion, while naphthalic anhydride was used as a coating of cereal seed before sowing.

Cereal seeds (Pioneer 3424 variant) were sown in soil filled with compost and fertilizer containing 12 cm diameter pots. The test chemicals were sprayed with a spray gun in

100 at a spray dose of 11.2 l / ha at the time of sowing in pre-emergence tests, when the control plants were 16 - 20 cm tall and in the leaf stage 3.0 - 3.2, plants that had seed coated with naphtha the anhydrides had 14 - 16 cm and the leaf phase 2.8 - 3.0.

Data from pre-emergence tests are shown in Table 25 A and post-emergence tests in Table 25 B. The tables show the chemical concentration of the active substance in grams per hectare (g / ha); naphthalic anhydride concentrations were not specifically measured, but were present as in normal, normal liners. Cereal damage is shown with a percentage inhibition of growth.

101

Herbicide no. g / ha Table 25A - Before emergence Antidote% inhibition _g / ha_ grain 1 0.25 - - 22.3 1 0.74 - - 32.3 1 2.5 - - 49.9 2 0.25 - - 21.7 2 0.74 - - 36.4 2 2.5 - - 42.7 3 0.07 - - 19.1 3 0.25 - - 80.9 3 0.74 - - 80.9 - - 2 * 17.4 1 0.25 2 1 » 18.2 1 0.74 2 <1 31.2 1 2.5 2 tl 27.3 2 0.25 2 II 31.5 2 0.74 2 II 18.9 2 2.5 2 II 31.9 3 0.07 2 II 13.2 3 0.25 2 II 29.3 3 0.74 2 II 46.9 - - 1 7.41 21.0 1 0.25 1 7.41 23.2 1 0.74 1 7.41 28.4 1 2.5 1 7.41 26.2 2 0.25 1 7.41 26.5 2 0.74 1 7.41 28.9 2 2.5 1 7.41 37.3 3 0.07 1 7.41 9.3 3 0.25 1 7.41 43.0 3 0.74 1 7.41 83.9

The concentration of antidote for seed disinfection is not necessary.

102

Table 25β - By origin

Herbicide no. g / ha

0.25

0.74

2.5

0.25

0.74

2.5

0.07

0.25

0.74

Antidote no. g / ha

0.25

0.74

2.5

0.25

0.74

2.5

0.07

0.25

0.74

0.25

0.74

2.5

0.25

0.74

2.5

0.07

0.25

0.74 *

'' '· "

7.41

7.41

7.41

7.41

7.41

7.41

7.41

7.41

7.41

With cereal inhibition

12.4 9.2

24.5 23.7

14.9

17.6

42.2

76.5

76.1

14.5

14.1

27.3

16.7

8.0

24.9 19.0

20.4

33.7

58.8

1.4

16.1

16.3

22.4

17.6

15.9

23.7

39.8

73.9 73.1 'The concentration of antidote for seed disinfection has not been measured.

103

According to the pre-emergence test data in Table 25A, it is apparent that the addition of antidote no. 2 significantly reduced cereal damage caused by herbicides no. 1 - 3 in the two highest doses of herbicides. A similar pattern of protection against these herbicides was used for antidote no. 1 at a dose of 7.41 g / ha, especially at the highest herbicide dose, with the notable exception of herbicide no. 3 at a dose of 0.74 g / ha, where a slight increase in grain damage was observed, although the herbicide no. 3 at 0.25 g / ha markedly protected by antidote no. 1, i.e. from 80.9% to 43.0 Z inhibition.

In the post-emergence tests, the data in Table 25B show that antidote no. 2 significantly reduced cereal damage caused by herbicide no. 1 and 3 at the highest doses but not at the low doses. In these tests, antidote no. 1 was not particularly effective in protection against herbicides no. 1 - 3 if used after plant origin.

104

Example 26

A large number of field trials were conducted to better understand and confirm the results obtained in the greenhouse experiments with herbicide compositions containing representative compounds of Formula I and antidote with or without soberbicide. This example provides a summary of these field experiments.

The main purpose of the field experiments summarized here was to verify the magnitude of the grain damage caused by the compound of formula I, i.e. herbicide no. 1, with or without eye-chloroacetanilide class co-herbicide, i.e. herbicides no. 6 and 7, and the amount of the dichloroacetamide compound of the antidote, i.e. antidote no. 15, which could prevent any damage to the grain.

Cereal damage is usually reflected, roughly speaking, in reduced yields, in reduced growth, with deformed plants, and with other more specific influences. For this summary, the results of many field trials are expressed in terms of poor growth, i.e. a significant reduction in the height of cereal plants. The general criterion for commercially acceptable cereal damage is 10 Z or less deformed plants or the same percentage of reduced yield and for the present purposes, no more than 15% reduction in growth. The grain damage / protection described in these field trials refers to commercially unacceptable properties to commercially acceptable ones.

Many field locations, soil types (all had 2% too much organic matter), climatic conditions, etc. were selected in the field experiments. The test chemicals were used in the form of mixtures in a container 'applied' in different ways, i.e. before sowing (PPI) and before plant emergence - surface (PRE).

The test plots were three small billets in the marginal entire sample scheme. Observations were made and recorded over a period of 31-50 days after processing.

105

Briefly, in experiments with pre-sowing application, the herbicide no. 1, administered at doses of 0.07 and 0.14 kg / ha of active substance in combination with herbicide no. 7 (alachlor) as soherbicide and without antidote, caused 9.75% or. 13.25% growth inhibition. However, with the addition of antidote no. 15 in a 1: 1 ratio of herbicide no. 1 grain damage reduced to 7.75% or. 9.82%.

More importantly, maximum damage levels were reduced from 48% (due to herbicide No, 1 at doses of 0.07 and 0.14 kg / ha) to 22% and 26% growth inhibition, respectively.

When combining herbicide no. 6 (acetochlor) and herbicide no. At doses of 0.7, 0.14 and 0.28 kg / ha of active substance, the levels of cerebral injury, without the use of antidote, were 12.5%, 14.9% and 24.9% of growth inhibition. Antidote supplement no. 15 reduced the said levels of grain damage to this composition, i.e. at 8.6%, 10.3% and 12.5% growth inhibition.

It is also important that at the above doses, the frequency of cereal damage greater than 20% growth inhibition was reduced from 5 damaged plants from a total of 27 to 1 of 27 and 15 from a total of 27 on 2 of 27s.

In experiments with the surface application of chemicals prior to plant emergence, combinations of herbicides no. 1 and acetoclorine at active substance doses of 0.07, 0.14, and 0.28 kg / ha, respectively, resulted in 9.8%, 13.4%, and 20.3% growth inhibition, respectively. Antidote supplement no. 15 reduced the injury, i.e. inhibition of growth, to 8.7%, 8.2% or. 14.5%. Increased antidote ratios no. 15 and herbicide no. 1 to 3 '.1' further reduced crop damage.

The results of the above field experiments showed that under most conditions antidote no. 15 effectively reduces grain damage, i.e. herbicide-induced growth inhibition no. 1, representative of pyrazolylsulfonylurea. of Formula I herbicides to a commercially acceptable level.

As will be seen, the data in the tables above reflect the fact that the protective effect of different protective agents against different herbicides will be different and dependent on many factors, including relative concentrations.

106 herbicides and / or co-herbicides and / or antidotes, weather, soil, water content, etc., which is widely considered in the art.

The herbicide compositions of the present invention, including concentrates that must be dissolved before use, may contain at least one active substance and aids in liquid or solid form. These compositions are prepared by mixing the active substance and aids, including diluents, developers, carriers and conditioners, to form compositions in the form of finely divided single solids, granules, pills, solutions, dispersions or emulsions. Thus, it is believed that the active substance can be used with aids such as finely formed single particles, liquids of organic origin, water, wetting agent, dispersing agent, emulsifier or any suitable combination thereof.

Suitable wetting agents are likely to include alkyl benzene or allyl naphthalenesulfonates, sulphated fatty alcohols, amines or acid amides, long-chain sodium isothioate acid esters, sodium sulphosuccinate esters, sulphated or sulphonated, sulphated or sulphonated sulphonic acid esters, sulphonic sulphonic acids, , diterciary acetylene glycols, polyoxyethylene derivatives of alkylphenols (especially isooctylphenol and nonylphenol) and polyoxyethylene derivatives of mono-higher fatty acid esters of hexitol anhydrides (eg sorbitan). Preferred dispersing agents are methyl cellulose, polyvinyl alcohol, sodium lignin sulfonates, polymeric alkyl naphthalenesulfonates, sodium naphthalenesulfonate and polymethylene bisnaphthalenesulphonate. Water-wettable powders are water-dispersible compositions containing one or more active substances, an inactive solid developer and one or more wetting and dispersing agents. Inactive solid developers are usually of mineral origin, such as natural clays, diatomaceous earth, and synthetic minerals originating in siliceous earth, etc.

Examples of such developers include kaolinite, atapulgite clays, and synthetic magnesium silicates. The wettable powder compositions of the present invention typically contain from about 0.5 to 60 parts (preferably from 5 to 20 parts) of the active substance; from about 0.25 to 25 parts (preferably 1-15) parts of the wettable agent;

from about 0.25 to 25 parts (preferably 1.0 to 15 parts)

107 dispersant and from about 5 to about 95 parts (preferably 5-50 parts) of the inactive solid developer, all by weight in the total composition. If required, from about 0.1 to 2.0 parts of a solid inactive developer can be replaced by a corrosive inhibitor or antifoaming agent or both.

Other formulations include concentrates of powder containing from 0.1 to 60% by weight of the active substance on a suitable developer, this powder may be dissolved for use in concentrations of about 0.1 to 10% by weight.

Aqueous suspensions or emulsions may be prepared by mixing the non-aqueous solution of the water-soluble active substance and the emulsifier with water to uniformity and subsequently homogenizing to obtain a stable emulsion of very finely divided particles.

The concentrated aqueous suspension which is formed is characterized by extremely small particle sizes, so that a very uniform coating is obtained upon dilution and spraying. Suitable concentrations of these formulations contain about 0.1 - 60, preferably 5-50% by weight of the active substance, the upper limit being determined by the solubility limit of the active substance in the solvent. Concentrates are usually solutions of the active substance in water-incompatible or partially water-incompatible solvents together with the surfactant. "Suitable solvents for the active substance of the present invention include dimethylformamide, dimethylsulfoxide, N-methyl-pyrrolidone, hydrocarbons and water-incompatible ethers, esters or ketones. Other high-strength liquid concentrates may, however, be formed by dissolving the active substance in a solvent, further diluting it with e.g. kerosene to the concentration for spraying.

The concentrations that occur here typically contain from about 0.1 to 95 parts (preferably 5-60 parts) of the active substance, about 0.25 to 50 parts (preferably 1-25 parts) of the surfactant and, where required, about 5-94 parts of the solvent, and the weight of all parts is based on the total weight of the emulsive oil.

108

Granules are physically solid, special compositions that contain an active substance that adheres or is spread in the underlying mineral admixture of an inactive finely formed crushed developer. To assist in the extraction of the active substance from the crushed developer, a surfactant may also be present in the composition. Natural clays, pyrophyllites, ilite and vermiculite are examples of the operating classes of crushed mineral developers. Preferred developers are porous, absorbent, preformed particles, such as preformed and screened crushed atapulgite or thermally expanded, crushed vermiculite and finely formed clays such as e.g. kaolinskagline, hydrated atapulgite or bentonite clays.

These developers are dispersed or mixed with the active substance to form herbicide granules.

The granule compositions of the present invention may contain about 0.1 to about 30 weight percent of the active substance per 100 weight percent of the clay and 0 to about 5 weight percent of the surfactant per 100 weight percent of the crushed clay.

The compositions of the present invention may also contain other additives, e.g. fertilizers, other herbicides, other pesticides, protective agents and the like in the form of aids or in combination with any of the aids described above. The chemicals useful in combination with the active substances of the present invention contain e.g. triazines, ureas, imidazolinones, sulfonylureas, carbamates, acetamides, acetanilides, uracils, acetic acid or phenol derivatives, thiolcarbamates, triazoles, benzoic acid and its derivatives, nitriles, biphenes (ethers, nitrobenzenes, etc.

Fertilizers useful in combination with active substances include e.g. ammonium nitrate, urea, potassium carbonate and superphosphate. Other useful additives may be the materials in which organisms from plants settle and grow, such as. compost, fertilizer, humus, sand and the like.

One of ordinary skill in the art will appreciate the fact that the present invention also includes the use of antidote compounds disclosed herein and defined by claims with any herbicidally active pyrazulylsulfonylurea or compound of a derivative that may be combined with co-herbicides from many different

109 types of chemical compounds. Obviously, the above list of ideal compounds is not exhaustive, but it is representative. As mentioned earlier, not every combination of herbicide and antidote is expected to result in the protection of all crops, but it is necessary to test every given combination of herbicide and antidote in the plant nets of any plant spectrum and record the results.

The aforementioned embodiments illustrate that the combinations of herbicide and antidote of the present invention are useful in controlling weeds and at the same time reducing herbicide damage to crops under greenhouse conditions and in the field.

The herbicide, antidote or mixture thereof may be applied to the site of the plant without any aid other than solvent. As mentioned above, these mixtures can be in the form of emulsifiable concentrates, micro capsules, crushed solids, granules with different particle sizes, e.g. in water-dispersible or soluble granules or larger dry granules, pills, wettable powders, powders, solutions, aqueous dispersions or emulsions.

Examples of suitable aids are finely formed solid carriers and developers, including talc, clay, float, quartz, diatomaceous earth, flint, jacket clay, sulfur cork powder, wood powder, walnut flour, chalk, tobacco powder, charcoal and the like. Typical liquid diluents include Stoddard solvent, acetone, methylene, chloride, alcohols, glycols, ethyl acetate, benzene and the like. Liquids and wettable powders typically contain, as conditioning agents, one or more surfactants in such quantities that a composition can be made that is readily dispersible in water or in oil. The term surfactant means wetting agents, dispersing agents, suspending agents and emulsifiers. Typical surfactants are mentioned in U.S. Pat. 2,547,724.

The compositions of this invention may contain about 5-95 parts of the herbicide and antidote, about 1-50 parts of the surfactant and about 4-94 parts of the solvent, all by weight based on the total weight of the composition.

110

We can protect the field by treating the seeds with an effective amount of antidote applied before sowing. In general, smaller quantities of antidote are required to process such seeds. An already low weight ratio of 0.6 parts of antidote per 1000 parts of seeds can be effective.

If desired, the amount of seed treatment antidote used can be increased. In general, however, the weight ratio of antidote to semen ranges from 0.1 to 10.0 parts of antidote per 1000 parts of seed. As only a very small amount of antidote is usually required for seed treatment, it is best if the compound is formulated as an organic solution, powder, emulsion concentrate, aqueous solution or liquid furulation that can be diluted by the seed processor with water for use in a seed plant seed treatment. Under certain conditions, it is preferable to dissolve the antidote in an organic solvent or seed treatment carrier, or the pure compound itself may be used under appropriately controlled conditions.

For the coating of seeds with antidote and for antidotes which are introduced into the soil in granular or liquid forms, solid carriers such as e.g. talc, sand, clay, diatomaceous earth, sawdust, calcium carbonate, etc., or liquids such as e.g. water, kerosene, acetone, benzene, toluene, xylene, etc., in which the active antidote is dissolved or dispersed. Emulsifiers are used to make a suitable emulsion when two incompatible liquids are used as the carrier. Wetting agents may also be used to assist in the dispersion of the active antidote in liquids used as carriers and in which the antidote is not completely soluble. Emulsifiers and wetting agents are marketed under different trade names and labels and may be pure compounds, mixtures of compounds of the same general groups, or mixtures of compounds of different classes. Typical satisfactory surfactants that may be employed are higher alkali metal sulfaryl sulfonates, such as sodium dodecylbenzenesulfonate and sodium salts of alkylnaphthalene sulfonic acids, fatty alcohol sulfates such as e.g. sodium salts of sulfuric acid monoesters with n-aliphatic alcohols containing 8-18 carbon atoms, long chain quaternary ammonium compounds, petroleum salts of alkylsulfonic acids, polyethylene sorbitan monoleate, alkylaryl polyether alcohols, water-soluble alkaline salts casein compositions, long chain alcohols typically containing 10 - 18 carbon atoms, and the condensation products of ethylene oxide with fatty acids, alkylphenols and mercaptans.

The present invention has been specifically exemplified by the preferred class number of herbicidal compounds, pyrazolylsulfonylureas listed above in Formulas I and IA, and with many commercial herbicides as representatives of the co-herbicidal component together with many antidote compounds as representative of the compounds of formulas II and III. It is to be appreciated that other compounds within the above formulas and other chemical classes are specifically contemplated within the scope of the present invention, either as components of herbicides or as co-herbicides.

The specifically mentioned antidote compounds and herbicide compounds used alone and / or as co-herbicides are intended only as examples of the classes of compounds they represent. However, it is specifically noted that many other herbicide and antidote compounds analogous to those presented herein and having many equivalent radicals substituted in the central nucleus can be used in detail in compositions to protect different crops to a greater or lesser extent, similarly as stated here. For example, other ρς-halogenated acetamide and (X-halogenated acetanilide compounds useful as co-herbicides of the present invention are described in U.S. Patent Nos. 3,442,945 ·; 3,547,620; 3,574,746; 3,586,496; 3,830,841; 3,901,768; 4,249,935; 4,319,745; 4,517,601; 4,517,601; 4,517,918; 4,517,918; 4,517,601; No. 4,657,579 and 4,666,502 and in Australian Patent No. AU-A1-18044 / 88.

112

The herbicidally useful thiocarbamate compounds are described in U.S. Pat. 2,913,327; 3,330,643 and 3,330,821, respectively.

Other pyridine herbicide compounds are described in U.S. Pat. 4,692,184; No. 4,826,532 and 4,988,384.

Herbicidally useful heterocyclyl phenylethers (especially pyrazolyl aryl ethers) are described e.g. in U.S. Patent 4,298,749.

Herbicidal diphenyl ethers and nitrophenyl ethers Include 2,4-dichlorophenyl 4'-nitrophenyl ether (nitrophene), 2-chloro-1- (3'-ethoxy-4'-nitrophenoxy) 4-trifluoromethylbenzene (oxyfluorfen), 2 ', 4' -dichlorophenyl 3-methoxy-4-nitrophenyl ether (chloromethoxinyl), methyl 2- [4 '- (2,4-dichlorophenoxy) -phenoxy7-propionate, N- (2'-phenoxyethyl) -2- / 5 ^1- (2 chloro-4-trifluoromethyl ^ phenoxy) -fenoksi7 ^- propionamide, 2-methoxyethyl 2- / nitro-5- (2kloro-4-trifluoromethyl-phenoxy) -phenoxy-propionate and 2kloro-4-trifluoromethylphenyl 3'-oxazolin 2'-yl-4'-nitrophenyl ether.

The second generic class of agrochemically important herbicide compounds specifically considered for use as co-herbicide compounds in combination with the antidote compounds of the present invention are urea derivatives. Important herbicide ureas include: 1- (benzothiazol-2-yl) -1,3-dimethylurea; phenylureas, eg: 3- (3-chloro-p-tolyl) -1,1-dimethylurea (chlorotoluron), 1,1-dimethyl3- (o (, ot, λ-trifluoro-fli-tolyl) urea (fluometuron ), 3- (4-bromo-2-chlorophenyl) methoxy-1-methylurea (chlorobromuron), 3- (4-bromophenoyl) -1-methoxy-methylmethurea (metobromuron), 3- (3,4-dichlorophenyl) -1 -methoxy-1-methylurea (linuron), 3- (4-chlorophenyl) -1-methoxy-1-methylurea (monolinuron), 3- (3,4-dichlorophenyl) -1, 1-dimethylurea (diuron), 3- (4-chlorophenyl) -1, 1-dimethylurea (monuron) and 3- (3-chloro-4-methoxyphenyl) 1,1-dimethylurea (methoxyuron).

Important herbicidal sulfonylureas and sulfonamides, considered to be a useful component of the herbicides of the present invention, in compositions with the antidote compounds of the present invention include those listed in the following patents:

113 U.S. Pat. 4,383,113; 4,127,405; 4,343,649; 4,479,821;

4,481,029; 4,514,212; 4,420,325; 4,638,004; 4,675,046; 4,681,620; 4,741,760; 4,723,123; 4,411,690; 4,718,937; 4,620,868; 4,668,277; 4,592,776; 4,666,508; 4,696,695; 4,731,446; 4,678,498; 4,786,314; 4,889,550; 4,931,081 and 4,668,279;

EP Patent Publication Nos. 084224, 173312, 147365, 87780, 190105, 256396, 264021, 264672, 142152, 244847, 176304, 177163, 187470, 187489, 184385, 232067, 234352, 189069, 224842, 249938, 246984 and 282613 and German Patent File No. DE1818.004.

Other herbicidal compounds, i.e. imidazolinone or imidazolidinone or imidazolidion usable as components of co-herbicides in the compositions of the present invention against which various crops can be protected include the compounds listed in the following model publications:

EP no. 041623, 133310, 198552, 216360 and 298029;

JA 11009-790, JA 1197-580A, JG 1183-272A and JG 3196-750A, and Australian Patent Publication Nos. AU 8661-073A, GB2 172 886A and U.S. Pat. 4,188,487; 4,297,128; 4,562,257; 4,554,013; 4,647,301; 4,638,068; 4,650,514; 4,709,036; 4,749,403; 4,749,404; 4,776,619; No. 4,798,619 and 4,741,767.

Still other classes of herbicide compounds contemplated for combinations with the herbicide components and antidotes of the present invention include the following representative species:

Triazines and triazinones: 2,4-bis- (isopropylamino) -6-methylthio-1,3,5-triazine (promethrin), 2,4-bis- (ethylamino) -6-methylthio-1,3,5-triazine (simetryne), 2- (1 ^1, 2'-dimethylpropylamino) -4-ethylamino-6-methylthio-l, 3,5-triazine (dimethametryn), 2- (chloro-4, 6-bis- (ethylamino) - 1,3,5-triazine (simazine), 2-tert-butyl-amino-4-chloro-6-ethylamino-1,3,5-triazine (terbutylazine),

2-tert-butylamino-4-ethylamino-6-methoxy-1,3,5-triazine (terbumetone), 2-tertbutylamino-4-ethylamino-6-methylthio-1,3,5-triazine (terbutrin),

2-ethylamino-4-isopropylamino-6-methylthio-1,3,5-triazine (ametrin) and 3,4-bis- (methylamino) -6-tert-butyl-4,4-dihydro-1,2, - 4-Triazin-5-one.

114

Oxadiazolones: 5-tert-butyl-3- (2 ', 4'-dichloro-5'-isopropoxyphenyl) 1,3,4-oxadiazol-2-one (oxadiazone).

Phosphates: S-2-methylpiperidinocarbonylmethyl 0,0-dipropyl phosphorodithioate (piperophos).

Pyrazoles: 1,3-dimethyl-4- (2 ', 4'-dichlorobenzolyl) -5- (4'-tolylsulfonyloxy) -pyrazole; aryl- and heterocyclic substituted pyrazoles, e.g. as referred to in EP no. 0361114; Japanese patent Kokai no. JP 50137061 and U.S. Patent 4,008,249. Preferred types of such substituted pyrazole compounds include 4-chloro-3- (4-chloro-2-fluoro-5- (2-propynyloxy) phenyl) -1-methyl-5- (methylsulfonyl) -1H pyrazole and its analogs, e.g. wherein the substituent in the 5-position of the pyrazole ring is a halogenated alkyl radical, preferably CF3.

Also derivatives of o- (phenoxyphenoxy) -propionic acid and derivatives of tert-pyridyl-2-oxyphenoxy) -propionic acid.

Other herbicide compounds useful as co-herbicides include the aromatic and heterocyclic di- and triketones listed in U.S. Pat. 4,797,147; 4,853,028; 4,854,966; 4,855,477; 4,938,796; and 4,869,748.

Other compounds of co-herbicides discussed herein are pyrrolidinones, e.g. The 1-phenyl-3-carboxyamidopyrrolidinones listed in U.S. Patent 4,874,422 and the 1-phenyl-4-haloalkylpyrrolidinones listed in U.S. Pat. 4,515,627, etc.

Other herbicide compounds that may be used as co-herbicides include benzoic acid derivatives of 5- (2'-chloro-4'-trifluoromethyl phenoxy) -2-nitrobenzoic acid (acifluorfen), 2,6-dichlorobenzonitrile (diclobenyl), 3 , 6-dichloro-2-methoxybenzoic acid (dicamba), etc. and the compounds listed in US Patents 3,013,054; 3,027,248 and 3,979,437, etc.

115 In addition to the antidote compounds listed herein, other representative antidote compounds of formulas II and III, or other structure, are explicitly mentioned in various patents, e.g. U.S. Pat. 3,959,304; 4,072,688; 4,137,070; 4,124,372; 4,124,376; 4,483,706; 4,636,244; 4,033,756; 4,493,726; 4,708,735; 4,256,481; 4,199,506; 4,251,261; 4,070,389; 4,231,783; 4,269,775; 4,152,137; 4,755,218; 4,964,893; 4,623,727; 4,882,884; 4,851,031; 4,902,340; 4,749,406; 4,758,264; 4,785,105; 4,785,106; 4,900,350 and 4,294,764;

and EP no. 159,287; 159,290; 258,184; 94,349; 2,121,403; 0253291; 0007588; 0190105; No. 0229649 and 16618 and West German Patent File Nos. 28 28222, 28 28 293.1 and 29 30 450.5, South African patent no. 82/7681 and PRC patent file no. 102 879-87.

Although the present invention has been described with reference to specific embodiments, the details of these embodiments should not be construed as limiting. Various equivalents, changes and modifications can be made regardless of the spirit and scope of the present invention, given that it is understood that such equivalent embodiments are part of this invention.

Claims (82)

REQUIREMENTS Composition characterized in that it contains: a) a herbicidally effective amount of a compound having the formula: wherein: H is alkyl or phenyl; R ₂ is H, C ^ _ ₃ alkyl or halogen; R ^ is R ₂ »NO ₂ or COOR ^; R 1 is C 1-6 alkyl, C 1-6 alkenyl, 4 ^J 1-3 2-3 N (R ₅ ) (R _& apos ;, SO ₂ N (R _? ) (G) or SO ₂ R ₉ ; R1-C8-C8 alkyl; R ₁₀ is H or C 1-6 alkyl; R ^ and R ^ ₂ are independently C ^ _ ₃ alkyl or alkoxy, halogen, or N (R ₁₃₎ (R ^); R 1 - and R 1 are C 1-10 alkyl and A is CH or N and 13 14 1-3 ^J b) an antidote effective amount (i) of a compound of formula wherein R 1 may be. ,. . . ... 15 is selected from the group consisting of halogenated alkyl; halogenated alkenyl; alkyl; alkenyl; cycloalkyl; cycloalkyl alkyl; halogen; hydrogen ·, carboalkoxy; N-alkenylcarbamylalkyl; N-alkenylcarbamyl; N-alkyl-N-alkynylcarbamyl; N-alkyl-N-alkynylcarbamylalkyl; N-alkenylcarbamylalkoxyalkyl; N-alkyl-N-alkynylcarbamylalkoxyalkyl; 117 alkynyloxy; halogenated alkoxy; thiocyanatoalkyl; alkenylaminoalkyl; alkylcarboalkyl; cyanoalkyl; cyanatoalkyl; alkenylaminosulfonalkyl; alkylthioalkyl; haloalkylcarbonyloxyalkyl; alkoxycarboalkyl; halogenated alkenylcarbonyloxyalkyl; hydroxyhaloalkyloxyalkyl; hydroxyalkylcarboalkyloxyalkyl; hydroxyalkyl; alkoxy sulfonoalkyl; furil; thienyl; alkyldithiolenyl; thienalkyl; phenyl and substituted phenyl, wherein said substituents may be selected from: halogen, alkyl, halogenated alkyl, alkoxy, carbamyl, nitro carboxylic acids and their salts, halogenated alkylcarbamyl; phenylalkyl; phenyl halogenated alkyl; phenylalkenyl; substituted phenylalkenyl, wherein the substituents may be selected from: halogen, alkyl, alkoxy, halogenated phenoxy, phenylalkoxy; phenylalkylcarboxyalkyl; phenylcycloalkyl; halo-phenylalkenoxy; halogenated thiophenylalkyl; halogenated phenoxyalkyl; bicycloalkyl; alkenylcarbamylpyridinyl; alkynylcarbamylpyridinyl; dialkenylcarbamylbicycloalkenyl, alkynylcarbamylbicycloalkenyl; R, and R, -, may be the same or different and may be selected from the group consisting of: alkenyl; halogenated alkenyl; hydrogen; alkyl; halogenated alkyl; alkynyl; cyanoalkyl; hydroxyalkyl; hydroxyhaloalkyl; halogenated alkylcarboxyalkyl; alkylcarboxyalkyl; alkoxycarboxyalkyl; thioalkylcarboxyalkyl; alkoxycarboalkyl; alkylcarbamyloxyalkyl; amino; formyl; halogenated alkylN-alkylamido; halogenated alkylamido; halogenated alkylamidoalkyl halogenated alkyl-N-alkylamidoalkyl; halogenated alkylamidoalkenyl; alkylimino; cycloalkyl; alkylcycloalkyl; alkoxyalkyl; alkylsulfonyloxyalkyl; mercaptoalkyl; alkylaminoalkyl; alkoxy ika: rboalke nil; halogenated alkylcarbonyl; alkylcarbonyl; alkenylcarbamyloxy alkyl; cycloalkylcarbamyloxyalkyl; alkoxycarbonyl; halogenated alkoxycarbonyl; halogenated phenylcarbamyloxyalkyl; cycloalkenyl; phenyl; substituted phenyl, wherein the substituents may be the following; alkyl, halogen, halogenated alkyl; alkoxy; halogenated alkylamido; phthalamido; hydroxy, alkylcarbamyloxy, alkenylcarbamyloxy, alkylamido, halogenated alkylamido or alkylcarboalkenyl; phenylsulfonyl; substituted phenylalkyl; wherein the substituents may be selected from: halogen or alkyl; dioxyalkylene; halogenated phenoxyalkylamidoalkyl; alkylthiodiazolyl; piperidyl; piperidylalkyl; dioxolanylalkyl; thiazolyl; alkylthiazolyl; benzothiazolyl: 118 halogenated benzothiazolyl; furil; alkyl substituted furyl, furylalkyl; pyridyl; alkylpyridyl; alkyloxazolyl; tetrahydrofurylalkyl; 3-cyano, thienyl; alkyl substituted thienyl; 4,5-polyalkylene-thienyl, -halogenated alkylacetamidophenylalkyl; <% halogenated alkylacetamidonitrophenylalkyl, oc-halogenated alkylacetamidohalo-phenylalkyl; cyanoalkenyl. When used together with Rp, they can form a structure consisting of: piperidinyl; alkylpiperidinyl; pyridyl; di- or tetrahydropyridinyl; alkyltetrahydropyridyl; morpholyl; alkylmorpholyl; azabicyclononyl; diazacycloalkanyl; benzoalkylpyrrolidinyl; oxazolidinyl; perhydrooxazolidinyl, alkyloxazolidinyl, furyloxazolidinyl; thienyloxazolidinyl; pyridinyloxazolidinyl; pyridinyloxazolidinyl, alkyloxazolidinyl; furyloxazolidinyl, thienyloxazolidinyl, pyridyloxazolidinyl; pyrimidinyloxazolidinyl; benzooxazolidinyl; ? spiro cycloalkyloxazolidinyl; alkylaminoalkenyl, alkylidenimino; pyrrolidinyl; piperidonyl; perbidroazepinyl; perhydroazocinyl; pyrazolyl; dihydropyrazolyl; piperazinyl; perhydro-1,4-diazepinyl; quinolinyl; isoquinolinyl; dihydro-, tetrahydro- and perhydroquinolyl- or - isoquinolyl, indolyl and di- and perhydroindolyl, and the aforementioned combined members and R ^ substituted by the independent radicals R ^ and R _? mentioned above; or nitrile, O- / 1,3-dioxolan-2-ylmethyl7-2,2,2-trifluoromethyl4'-chloro-acetophenone oxime, Benzenmetamine, N- / 4- (dichloromethylene7-1,3-dithiolan2-ylidene) -methyl, hydrochloride, 1,8-naphthalic anhydride, 4,6-dichloro-2-phenyl-pyrimidine, 2-chloro-N- [1- (2,4,6-trimethylphenyl) -ethenyl] acetamide, Ethylene glycol acetal from 1,1-dichloroacetone 119 1,3-dioxolane, 2- (dichloromethyl) -2-methyl-, 5-Thiazolecarboxylic acid, 2-chloro-4- (trifluoromethyl) (phenyl-methyl) -ester, Phosphorothioic acid, 0,0-diethyl (- (3-methylphenyl) ester, 4- pentenitrile, 2-methyl-2-f (4-methyl-phenyl) thio / -, 5- chloro-8- (cyanomethoxy) quinoline, 1-methylhexyl-2- (5-chloro-8-quinolinoxy) -acetate, O- (methoxycarbonyl) -2- (8-quinoynoxy) -acetamide oxime, 5-oxazolecarboxylic acid, 2 - [(2,2-dimethylethyl) amino74- (trifluoro-methyl) -, ethyl ester, Acetic acid, (diphenylmethoxy) -, methyl ester, Allyl-N-methyldithiocarbonyl, 4-isoxazolecarboxylic acid, 5- (2,4-dichlorophenyl) ethyl ester, Acetonitrile, N * (5-chloro-8-quinolinyl) oxy / -, Acetamide 2- (diphenylmethoxy) -N-methyl-, Glycine, N- / bis (4-methoxyphenyl) -methyl7-, ethyl ester, Glycine, N- / bis (4-chlorophenyl) -methyl / -, ethyl ester, Acetic acid, N- (10,11-dihydro-5H-dibenzoyl) cyclohepten-5-yl) oxy7-, 1,1-dimethylethyl ester, Ethantioamide, 2- (diphenylmethoxy) -, Acetic acid, (diphenylmethoxy) -, propyl ester, Acetic acid, (diphenylmethoxy) -, 2,2,2, -trifluoroethyl ester, Acetic acid, ^ phenyl / 3- (trifluoromethyl) phenyl7methoxy] -2-methyl-2-propanamine salt, Acetic acid, (diphenylmethoxy) -, phenyl ester, Ethanethioic acid, 2- (diphenylmethoxy) -, S-ethyl ester, Acetic acid, (diphenylmethoxy) -, 2-cyanoethyl ester, Acetic acid, {phenyl / * 3- (trifluoromethyl) ) -phenyl7met ° ksi / 2,2,2-trifluroethyl ester, Acetic acid, (diphenylmethoxy) -, 2-propynyl ester, Acetic acid, (diphenylmethoxy) -, 3-furanylmethyl ester, Acetic acid / bis (2,6-dimethylphenyl) -metoksi7 ^_, pyrimidine, 4,6-dichloro- 2-phenyl-, 4-pentenenitrile, 2-methyl-2 - / (- methylphenyl) thio7-, 120 Acetic acid, (diphenylmethoxy) -, 3-nitrophenyl ester, Acetic acid, f / bis (2,6-dimethylphenyl) 7-methoxy} -, ethyl ester, Acetic acid, (diphenylmethoxy) -, 1-cyano-1-methylethyl ester, 5-Thiazolecarboxylic acid, 2-chloro-4- (trifluoromethyl) -, ethyl ester, 5-Thiazolecarboxylic acid, butyl ester, 2-chloro-, 4 (trifluoromethyl) -, 5-Thiazolecarboxylic acid, 2-chloro-, hexyl ester, 4- (trifluoromethyl) -, 5-Thiazolecarboxylic acid, 2-chloro-4- (trifluoromethyl) -, octyl ester, 5-Thiazolecarboxylic acid, 2-chloro-4- (trifluoromethyl) -, phenyl ester, 5-Thiazolecarboxylic acid, 2-chloro-4- (trifluoromethyl) -, 5-thiazolecarboxylic acid, 2- [bromo-4- (trifluoromethyl)] -, ethyl ester, 5-Thiazolecarboxylic acid, 2-iodo-4- (trifluoromethyl) -, ethyl ester, 5-Thiazolecarboxylic acid, 2-chloro-4- (trifluoromethyl) -, 1-methylethanamine: salt, Benzylamine-, (alpha-methyl-, N-4- (methyl) -1,3-dithiol-2-ylidene) hydrochloride, Pyridine, N-oxide, 2- (3,4,5,6-tetrachloro-2-pyridylthio) -, Acetic acid, / 3,5 ~ bis (trifluoromethyl) -phenoxy / ^r -, / Propanamide, 2-chloro-N- (S-iodo-4- (trifluoromethyl) -2-thiazolyl) -, Cyclopropanecarbonitrile, 1 - [(3,4-dimethylphenyl) thi7-, Propannitrile, 3 - [2- (1,1-dimethyl-ethyl) phenyl] thio] -, 4-pentenenitrile, 2-methyl-2 - // 4- (1-methylethyl) phenyl / thio / -, Ethanamide, N '- / (methoxycarbonyl) -oxq / -2- (8-quinolinyloxy) -, 1 (3H) -isobenzofuranone, 3- [2- (2,5-dimethoxyphenyl) -2-oxoethyl] -, 121 Acetic acid, 2- (diphenylmethoxy) - sodium salt, hemihydrate, Acetic acid, 2- (diphenylmethoxy) -, or Acetic acid, (diphenylmethoxy) -, 2-propanamine: salt. The composition of claim no. 1, characterized in that said antidote compound of formula II is a compound of formula III wherein R1 is hydrogen, alkyl, alkylol, halogenated alkyl or alkoxy, alkoxyalkyl, a bicyclic hydrocarbon radical of up to 10 carbon atoms, phenyl or saturated or unsaturated heterocyclic or a heterocyclomethyl radical with C, atoms 4-10 in the ring and with atoms. O, S ir / or N, or substituted phenyl and heterocyclic (methyl ..) radicals substituted with one or more C1-6alkyl, halogenated alkyl ^ alkoxy, alkoxyalkyl, halogen or nitro radicals, and R ₁₉ and R ₃₀ are independently hydrogen, alkyl or halogenated alkyl, phenyl or heterocyclic (methyl) members of R. _o or together with the carbon atom to which they are attached may form - C? a spiro-cycloalkyl group. The composition of claim no. 2, characterized in that R _{10 is} one of said heterocyclic members and R 1 and R 5 are independently methyl, trifluoromethyl, or in combination with a carbon atom to which they are attached to or a cycloalkyl radical. 122 The composition of claim no. 3, characterized in that said compound is selected from the group consisting of: 3- (dichloroacetyl) -2,2,5-trimethyl-, 3- (dichloroacetyl) -2,2-dimethyl-, 3- (dichloroacetyl) -2,2-dimethyl-5-phenyl-, 3- (dichloroacetyl) -2,2-dimethyl-5- (2-furanyl) -, 3- (dichloroacetyl) -2,2-dimethyl-5- (2-thienyl) -, - (dichloroacetyl) -2,2-dimethyl-5-oxazolidinyl7Oxazolidin, Oxazolidin, Oxazolidin, Oxazolidin, Oxazolidin, Pyridin, 3- (3 in 4- (dichloroacetyl) -1-oxa-4-azaspiro- (4,5) -decane. Composition according to claim 1, characterized in that said compound of formula II is selected from the group consisting of: 4- (dichloroacetyl) -3,4-dihydro-3-methyl-2H-2,4-benzoxazine, Ethanone, 2-2-dichloro-1- (1,2,3,4-tetrahydro-1-methyl-2isoquinolinyl) ) -, N- (dichloroacetyl) -1,2,3,4-tetrahydroquinaldine, Gis / trans-piperazine, 1,4-bis (dichloro 1,4-acetyl) -2,5 dimethyl-, N, N-di-propenyl dichloroamide, N- (2-propenyl) -N- (1,3-dioxolan-2-ylmethyl), dichloroacetamide, 1,5-diazacyclononane, 1,5-bis- (dichloroacetyl, 1-azaspiro / 4.47nonane, 1- ( dichloroacetyl), Pyrrolo-1,2-7-pyrimidin-6 (2H) 7 ^- one, 1- (dichloroacetyl) hexahydro-3, 3-8a-trimethyl, 2.2-dimethyl-3- (dichloroacetyl) -1,3-oxazole 1- (dichloroacetyl) -1,2,3,4-tetrahydroquinoline, and 2.2-dimethyl-5-methoxy-3- (dichloroacetyl) -1,3-oxazole. Composition according to claim 1, characterized in that said antidote compound is selected from the group consisting of: ot- [(cyanomethoxy) imino-7-benzenacetonitrile, 1 * - [(1,3-dioxolan-2-yl-methoxy) imino] -benzenacetonitrile, O- [3, 3-dioxolan-2-ylmethyl] -2,2,2-trifluoromethyl- 4'-chloroacetophenone oxime, 123 Benzenmetamine, N- / 4- (dichloromethylene) -1,3-dithiolan-2-ylidene 7-A-methyl, hydrochloride, 1,8-naphthalic anhydride, 4,6-dichloro-2-phenyl-pyrimidine, 2-chloro-N- [1- (2,4,6-trimethylphenyl) -ethenyl] acetamide, Ethylene glycol acetal 1,1-dichloro-acetone, 1,3-dioxolane, 2- (dichloromethyl) -2-methyl-, 5-Thiazolecarboxylic acid, 2-chloro-4- (trifluoromethyl) -, (phenylmethyl) ester, Phosphorothioic acid, 0,0-diethyl 0- (3-methylphenyl) ester, 4- pentenitrile, 2-methyl-2 - [(4-methyl-phenyl) thio] -, 5- chloro-8- (cyanomethoxy) quinoline, 1- methylhexyl-2- (5-chloro-8-quinolinoxy) -acetate, O- (methoxycarbonyl) -1- (8-quinolinoxy) -acetamide ox im, 5-Oxazolecarboxylic acid, 2 - [(2,2-dimethylethyl) amino / 4- (trifluoromethyl) -, ethyl ester, Acetic acid, (diphenylmethoxy) -, methyl ester, Allyl-N-methyldithiocarbonylate, 4-isoxazolecarboxylic acid, 5- (2,4-dichlorophenyl) -, ethyl ester, Pyrimidine, 4,6-dichloro-2-phenyl-, 4-pentenenitrile, 2-methyl-2 - / (4-methylphenyl) tiq / -, Acetonitrile, ((5-chloro-8-quinolinyl) oxy) -, Acetamide 2- (diphenylmethoxy) -N-methyl-, Glycine, N - // bis (4-methoxyphenyl) -methyl / - ethyl ester, Glycine, N- [bis (4-chlorophenyl) -methyl] -, ethyl ester, Acetic acid, N (10,11-dihydro-5H-dibenzo / 1,1,7-cyclohepten-5-yl) oxy] -, 1,1-dimethylethyl ester, Ethantioamide, 2- (diphenylmethoxy) -, Acetic acid, (diphenylmethoxy) -, propyl ester, Acetic acid, (diphenylmethoxy) -, 2,2,2-trifluoroethyl ester, Acetic acid, {phenyl / 3- (trifluoro-methyl) phenyl ^e t ° ksi) -, 2-methyl-2-propanamine salt, 124 Acetic acid, (diphenylmethoxy) -, phenyl ester, Ethanethioic acid, 2- (diphenylmethoxy) -, S-ethyl ester, Acetic acid, (diphenylmethoxy) -, 2-cyanoethyl ester, Acetic acid, N-phenyl / 3- (trifluoromethyl) -phenyl / methoxy) -, 2,2,2-trifluoroethyl ester, Acetic acid, (diphenylmethoxy) -, 2-propynyl ester, Acetic acid, (diphenylmethoxy) -, 3-furanylmethyl ester, Acetic acid, / bis (2,6-dimethylphenyl) -methoxy7-, Acetic acid, (diphenylmethoxy) -, 3-nitrophenyl ester, Acetic acid, N / bis (2,6-dimethylphenyl) 7 ^- methoxy-, ethyl ester, Acetic acid, (diphenylmethoxy) -, 1-cyano-1-methylethyl ester, 5-Thiazolecarboxylic acid, 2-chloro-4- (trifluoromethyl) -, ethyl ester, 5-Thiazolecarboxylic acid, butyl ester, 2-chloro-, 4- (trifluoromethyl) -, 5-Thiazolecarboxylic acid, 2-chlorohexyl ester, 4- (trifluoromethyl) -, 5-Thiazolecarboxylic acid, 2-chloro-4- (trifluoromethyl) -, octyl ester, 5-Thiazolecarboxylic acid, 2-chloro-4- (trifluoromethyl) -, phenyl ester, 5-Thiazolecarboxylic acid, 2-chloro-4- (trifluoromethyl) -, 5-thiazolecarboxylic acid, 2- [bromo-4- (trifluoromethyl) y-, ethyl ester, 5-Thiazolecarboxylic acid, 2-iodo-4- (trifluoromethyl) -, ethyl ester, 5- Thiazolecarboxylic acid, 2-chloro-4- (trifluoromethyl) -, 1-methylethanamine salt, Benzylamine-, (alpha-methyl-, N-4- (methyl) -1,3-dithiol-2-ylidene) hydrochloride, Pyridine, N-oxide, 2- (3,4,5,6-tetrachloro-2-pyridylthio) -, acetic acid, (3,5-bis (trifluoromethyl) -phenoxy) -, propanamide, 2-chloro-N- [5-iodo-4- (trifluoromethyl) -2-thiazolyl] -, 125 Cyclopropanecarbonitrile, 1- [(3,4-dimethylphenyl) thio] -, Propannitrile, 3 - // 2- (1,1-dimethyl-ethyl) phenyl / thio. 4-pentenenitrile, 2-methyl-2-f / 4- (1-methylethyl) phenyl / thio7-, ethanimidamide, N '- N (methoxycarbonyl) -oxo / -2- (8-quinolinyloxy) -, 1 (3H ) -isobenzofuranone, 3- / 2- (2,5-dimethoxyphenyl) -2-oxoethyl 7-, acetic acid, 2- (diphenylmethoxy) sodium salt, hemihydrate, Acetic acid, 2- (diphenylmethoxy) -, or Acetic acid, (diphenylmethoxy) -, 2-propanamine salt. Composition according to any one of claims 4, 5 or 6, characterized in that said herbicidal component (a) is a compound of formula IA O where and R1 and R6 are alkyl; R 2 is H, alkyl, chromo or chloro; R 1 and R 2 are independently alkyl or alkoxy. Composition according to claim 7, characterized in that said compounds are of formula IA R ^ and R ^ are methyl or ethyl; 126 ί <2 is Η, methyl, bromo or chloro. and and R ^ 2 ^s ^ a is independently methyl or methoxy. Composition according to claim 8, characterized in that said compound is selected from the group consisting of: N - [(4-methoxy-6-methylpyrimidin-2-yl) -aminocarbonyl] -3-chloro-4-methoxycarbonyl-1-methylpyrazole-5-sulfonamide; N- $ ^r 4,6-dimethoxypyrimidin-2-yl) amino-carbonyl73-chloro-4methoxycarbonyl-1-methylpyrazole-5-sulfonamide; N- [(4-methoxy-6-methylpyrimidin-2-yl) -aminocarbonyl] -3-chloro-4-ethoxy-carbonyl-1-methylpyrazole-5-sulfonamide; Nf (4,6-dimethoxypyrimidin-2-yl) aminokarboniU ^_ 3-chloro-4etoksikarbonil-1-methylpyrazole-5-sulfonamide; N - [(4-methoxy-6-methylpyrimidin-2-yl) aminocarbonyl7-3bromo-4-ethoxycarbonyl-1-methylpyrazole-5-sulfonamide; N - / '(4,6-dimethoxypyrimidin-2-yl) aminokarbonil7 ^_ 3-bromo-4-ethoxycarbonyl-l-methylpyrazole-5-sulfonamide. and N-L (4,6-dimethoxypyrimidin-2-yl) -aminocarbonyl7-4-ethoxycarbonyl-1-methyl-pyrazole-5-sulfonamide. Composition according to claim 8, characterized in that said compound of formula ΣΑ is selected from the group consisting of: N- (4,6-dimethoxypyrimidin-2-yl) amino-carbonyl ^- 3-chloro-4-methoxycarbonyl-1-methylpyrazole-5-sulfonamide. and N-Z4,6-dimethoxypyrimidin-2-yl) amino-carbonyl / -4-ethoxycarbonyl-1- methyl-pyrazole-5-sulfonamide. 11. A composition comprising a herbicidally effective amount of NC-319 and an antidote effective amount of oxazolidine, 3- (dichloroacetyl) -2,2-dimethyl-5- (2-furamyl) a. 127 A composition comprising an herbicidally effective amount of NC-311 and an antidote effective amount of oxazolidine, 3- (dichloroacetyl) -2,2-dimethyl-5 (2-furanyl) a. Composition according to claim 10, characterized in that said compound of the antidote of formula II is dichloromethyl. 14. The composition of claim 13, wherein said compound of formula II is selected from the group consisting of: 4- (dichloroacetyl) -3,4-dihydro-3-methyl-2H-2,4-benzoxazine, Ethanone, 2-2-dichloro-1- (1,2,3,4-tetrahydro-1-methyl-2 -isoquinolinyl) -, N- (dichloroacetyl) -1,2,3,4-tetrahydroquinoline, 1- (dichloroacetyl) -1,2,3,4-tetrahydroquinoline, Cis / trans-piperazine, 1,4-bis (dichloro 1,4-acetyl) ) -2,5dimethyl-, N, N-di-propenyl dichloroamide, N- (2-propenyl) -N- (1,3-dioxolan-2-ylmethyl) dichloroacetamide, 1,5-diazacyclononan, 1,5-bis-dificoroacetyl), 1-azaspiro / 4,47nanane, 1- (dichloroacetyl), PyrroloZ1, 2-a} -pyrimidine- [6 (2H) y-one, 1- (dichloroacetyl) hexahydro-3,3-8a-trimethyl, 2.2-dimethyl-3- (dichloroacetyl) -1,3-oxazole and 2.2-dimethyl-5-methoxy-3- (dichloroacetyl) 1,3-oxazole. 15. The composition of claim 13, wherein said compound is R-25788. 16. The composition of claim 13, wherein said compound is PPG-1292. 128 17. The composition of claim 13, wherein said antidote compound of formula II is a subset of compounds of formula III. where R ^ g, and such as are defined herein. 18. The composition of claim 17, wherein said compound of formula III is selected from the group consisting of: Oxazolidine, 3- (dichloroacetyl) -2,2,5-trimethyl-, Oxazolidine, 3- (dichloroacetyl) -2,2-dimethyl-, Oxazolidine, 3- (dichloroacetyl) -2,2-dimethyl-5-phenyl-, Oxazolidine, 3- (dichloroacetyl) -2,2-dimethyl-5- (2-furanyl) -, Oxazolidine, 3- (dichloroacetyl) - 2,2-dimethyl-5- (2-thienyl) -, pyridine, 3- / 3- (dichloroacetyl) -2,2-dimethyl-5-oxazolidinyl7in 4- (dichloroacetyl) -1-oxa-4-azaspiro- (4,5) -decane. 19. The composition of claim 17, wherein said compound is oxazolidine, 3-dichloroacetyl, 2,2-dimethyl-5- (2-furanyl). Composition according to claim 10, characterized in that said antidote compound is selected from the group (b) (ii) of the compounds formed by: > - / (cyanomethoxy) imine benzenacetonitrile, <* - / (1,3-dioxolan-2-yl-methoxy) imino / benzenacetonitrile, 0- [N, 3-dioxolan-2-ylmethyl7-2,2,2-trifluoromethyl-4'-chloro129 acetophenone oxime, Benzenmetamine, N- / 4- (dichloromethylene) -1,3-dithiolan-2-ylidene (-methyl, hydrochloride, 1,8-naphthalic anhydride, 4,6-dichloro-2-phenyl-pyrimidine, 2-chloro-N- [1- (2,4,6-trimethylphenyl) -ethenyl] acetamide, Ethylene glycol acetal 1,1-dichloroacetone, 1,3-dioxolane, 2- (dichloromethyl) -2-methyl-, 5-Thiazolecarboxylic acid, 2-chloro- (trifluoromethyl) -, (phenylmethyl) ester, Phosphorothioic acid, 0,0-diethyl 0- (3-methylphenyl) ester, 4- pentenitrile, 2-methyl-2 - / (4-methylphenyl) thio / -, 5- chloro-8- (cyanomethoxy) quinoline, 1-methylhexyl-2- (5-chloro-8-quinolinoxy) -acetate, O- (methoxycarbonyl) -2- (8-quinolinoxy) -acetamide oxime, 5-oxazolecarboxylic acid, 2 - / ”(2,2-dimethylethyl) amino / -4 (trifluoromethyl) -, ethyl ester, Acetic acid, (diphenylmethoxy) -, methyl ester, Allyl-N-methyldithiocarbonylate, 4-isoxazolecarboxylic acid, 5- (2,4-dichlorophenyl) -, ethyl ester, Pyrimidine, 4 _? 6 - dichloro-2-phenyl-, 4-pentenenitrile, 2-methyl-2 - / '(4-methylphenyl) thio / -, Acetonitrile, N (5-chloro-8-quinolinyl) oxy7-, Acetamide 2- (diphenylmethoxy) -N-methyl-, Glycine, N-bis (4-methoxyphenyl) -metil7 ^_, ethyl ester, Glycine, N- / bis (4-chlorophenyl) -methyl7 ", ethyl ester, Acetic acid, N (10,11-dihydro-5H-dibenzo / 1,1-dichlorohepten-5-yl) oxy] -, 1,1-dimethylethyl ester, Ethantioamide, 2- (diphenylmethoxy) -, Acetic acid, (diphenylmethoxy) -, propyl ester, Acetic acid, (diphenylmethoxy) -, 2,2,2-trifluoroethyl ester, Acetic acid, {phenyl / 3- (trifluoromethyl) phenyl / methoxy | -, 2-methyl-2-propanamine salt, 130 Acetic acid, (diphenylmethoxy) -, phenyl ester, Ethanethioic acid, 2- (diphenylmethoxy) -, S-ethyl ester, Acetic acid, (diphenylmethoxy) -, 2-cyanoethyl ester, Acetic acid, ^ phenyl / 3- (trifluoromethyl) -phenyl7methoxy} -, 2,2,2-trifluoroethyl ester, Acetic acid, (diphenylmethoxy) -, 2-propynyl ester, Acetic acid, (diphenylmethoxy) -, 3-furanylmethyl ester, Acetic acid, fbis (2,6-dimethylphenyl) -methoxy / -, Acetic acid, (diphenylmethoxy) -, 3-nitrophenyl ester, Acetic acid, N / bis (2,6-dimethylphenyl) 7-methoxy} -, ethyl ester, Acetic acid, (diphenylmethoxy) -, 1-cyano-1-methylethyl ester, 5-Thiazolecarboxylic acid, 2-chloro-4- (trifluoromethyl ·) -, ethyl ester, 5-Thiazolecarboxylic acid, butyl ester, 2-chloro-, 4- (trifluoromethyl) -, 5-Thiazolecarboxylic acid, 2-chloro-, hexyl ester, 4- (trifluoromethyl) -, 5-Thiazolecarboxylic acid, 2-chloro-4- (trifluoromethyl) -, octyl ester, 5-Thiazolecarboxylic acid, 2-chloro-4- (trifluoromethyl) -, phenyl ester, 5-Thiazolecarboxylic acid, 2-chloro-4- (trifluoromethyl) -, 5-thiazolecarboxylic acid, 2- [bromo-4- (trifluoromethyl)] -, ethyl ester, 5-Thiazolecarboxylic acid, 2-iodo-4- (trifluoromethyl) -, ethyl ester, 5-Thiazolecarboxylic acid, 2-chloro-4- (trifluoromethyl) -, 1-methylethanamine salt, Benzylamine-, (alpha-methyl-, N-4- (methyl) -1,3-dithiol-2-ylidene) hydrochloride, Pyridine, N-oxide, 2- (3,4,5,6-tetrachloro-2-pyridylthio) -, acetic acid, (3,5-bis (trifluoromethyl) -phenoxy) ^- , propanamide, 2-chloro-N- / 5-iodo-4- (trifluoromethyl) -2-thiazolyl-7-, 131 Cyclopropanecarbonitri, 1- [(3,4-dimethylphenyl) thio] -, Propannitrile, 3 - // 2- (1, 1-dimethylethyl) phenyl / thio / -, 4-pentenenitrile, 2-methyl-2 - [4- (1-methylethyl) phenyl] thio] -, ethanimidamide, N '- [(methoxycarbonyl) -oxo] -2- (8-quinolinyloxy) -, 1 (3H) - isobenzofuranone, 3- / 2- (2,5-dimethoxyphenyl) -2-oxoethyl / -, acetic acid, 2- (diphenylmethoxy) - sodium salt, hemihydrate, Acetic acid, 2- (diphenylmethoxy) -, Acetic acid, (diphenylmethoxy) -, 2-propanamine salt. 21. The composition of claim 10, wherein said antidote compound is 1,8 naphthalic anhydride. 22. The composition of claim 10, wherein said antidote compound is flurazole. 23. The composition of claim 10, wherein said antidote compound is MON-7400, 24. Composition characterized in that it contains a) a herbicidally effective amount of a compound of formula I; b) an antidote effective amount (s) of a compound of the formula II 132 where it may be selected from the group consisting of: halogenated alkyl; halogenated alkenyl; alkyl; alkenyl; cycloalkyl; cycloalkylalkyl; halogen; hydrogen; carboalkoxy; N-alkenylcarbamylalkyl; N-alkenylcarbamyl; N-alkyl-N-alkynylcarbamyl; N-alkyl-N-alkynylcarbamylalkyl; N-alkenylcarbamylalkoxyalkyl; N-alkyl-N-alkynylcarbamylalkoxyalkyl; alkynyloxy; halogenated alkoxy; thiocyanatoalkyl; alkenylaminoalkyl; alkylcarboalkyl; cyanoalkyl; cyanoatoalkyl; alkenylaminosulfonalkyl; alkylthioalkyl; halogenated alkylcarbonyloxyalkyl; alkoxycarboalkyl; halogenated alkenylcarbonyloxyalkyl; hydroxyhaloalkyloxyalkyl; hydroxyalkylcarboalkyloxyalkyl; hydroxyalkyl; alkoxysulfonoalkyl; furyl, thienyl; alkyldithiolenyl; thienalkyl; phenyl and substituted phenyl, wherein said substituents may be selected from: halogen, alkyl, halogenated alkyl, alkoxy, carbamyl, nitro, carboxylic acids and their salts, halogenated alkylcarbamyl phenylalkyl; phenylhaloalkyl, phenylalkenyl; substituted phenylalkenyl, wherein said substituents may be selected from: halogen, alkyl, alkoxy, halogenated phenoxy; phenylalkoxy, phenylalkylcarboxyalkyl; phenylcycloalkyl, 'halogenated phenylalkenoxy; halogenated thiophenylalkyl; halogenated phenoxyalkyl; bicycloalkyl; alkenylcarbamylpyridinyl ·, alkynylcarbamylpyridinyl; dialkenylcarbamylbicycloalkenyl; alkynylcarbamylbicycloalkenyl; R6 can be the same or different and can be selected from the group consisting of: alkenyl; halogenated alkenyl; hydrogen; alkyl; halogenated alkyl; alkynyl; cyanoalkyl; hydroxyalkyl; hydroxyhaloalkyl; halogenated alkylcarboxyalkyl; alkylcarboxyalkyl; alkoxycarboxyalkyl; thioalkylcarboxyalkyl; alkoxycarboalkyl; alkylcarbamyloxyalkyl; amino; formyl; halogenated alkylamidoalkyl; halogenated alkyl-N-alkylamidoalkyl; halogenated alkylamidoalkenyl; alkylimino; cycloalkyl; alkylcycloalkyl; alkoxyalkyl; alkylsulfonyloxyalkyl; mercaptoalkyl; alkylaminoacyl; alkoxycarboalkenyl; halogenated alkylcarbonyl; alkylcarbonyl; alkenylcarbamyloxyalkyl; cycloalkylcarbamyloxyalkyl; alkoxycarbonyl; halogenated alkoxycarbonyl; halogenated phenyl133 carbamyloxyalkyl; cycloalkenyl; phenyl; substituted phenyl wherein said substituents may be selected from: alkyl, halogen, halogenated alkyl, alkoxy, halogenated alkylamido, phthalamido, hydroxy, alkylcarbamyloxy, alkenylcarbamyloxy, alkylamido, halogenated alkylamido or alkylcarboalkenyl; phenylsulfonyl; substituted phenylalkyl wherein said substituents may be halogen or alkyl; dioxyalkylene, halogenated phenoxyalkylamidoalkyl alkylthiodiazolyl; piperidyl; piperidylalkyl; dioxolanylalkyl, thiazolyl; alkylthiazolyl; benzothiazolyl; halogenated benzothiazolyl; furil; alkyl substituted furyl; 4,5-polyalkylthienyl; c-halogenated alkylacetamidophenylalkyl; rk-halogenated alkylacetamidonitrophenylalkyl; "(-Halogenated alkylacetamidohalophenylalkyl; cyanoalkenyl; furylalkyl; pyridyl; alkylpyridyl; alkyloxazolyl; tetrahydrofurylalkyl; 3-cyano, thienyl; alkyl substituted thienyl If both R ^? used together, they may form the structure of: piperidinyl; alkylpiperidinyl; pyridyl; di- or tetrahydropyridinyl; alkyltetrahydropyridyl; morpholyl; alkylmorpholyl; azabicyclononyl; diazacycloalkanyl; benzoalkylpyrrolidinyl; oxazolidinyl; perhydrooxazolidinyl; alkyloxazolidyl; furyloxazolidinyl; thienyloxazolidinyl; pyridyloxazolidinyl; pyrimidinyloxazolidinyl; benzooxazolidinyl; ? spirocycloalkylcksazolidinyl; alkylaminoalkenyl; alkylidenimino; pyrrolidinyl; piperidonyl; perhydroazepinyl; perhydroazocinyl; pyrazolyl; dihydropyrazolyl; piperazinyl; perhydro-1,4diazepinyl; quinolinyl; isoquinolinyl; dihydro-, tetrahydro- and perhydroquinolyl- or -isoquinolyl, indolyl and di- and perhydroindolyl, and the aforementioned combined members R ^ and R,, substituted by the independent radicals R ^ and R2 listed above; or (ii) one of the following compounds: c ianomethoxy i) imino J-benzenacetonitrile i, 1 H - ((1,3-dioxolan-2-ylmethoxy) imino / -benzenacetonitrile, 0- [N, 3-dioxolan-2-ylmethyl7-2,2,2-trifluoromethyl4'-chloroacetophenone oxime, 134 Benzenmetamine, N- / 4- (dichloromethylene / -1, 3-dithiolan2-ylidene) -o (-methyl, hydrochloride, 1,8-naphthalic anhydride, 4,6-dichloro-2-phenyl-pyrimidine, 2-chloro-N - [(2,4,6-trimethylphenyl) -ethenyl] acetamide, Ethylene glycol acetal 1,1, -dichloroacetone 1,3-dioxolane, 2- (dichloromethyl) -2-methyl-, 5-thiazolecarboxylic acid, 2-chloro-4- (trifluoromethyl) -, (phenylmethyl) -ester (common name) flurazole), Phosphorothioic acid, 0,0-diethyl (- (3-methylphenyl) ester, 4- penteninitrile, 2-methyl-2- (4-methylphenyl) thio] -, 5- chloro-8- (cyanomethoxy) quinoline, 1-methylhexyl-2- (5-chloro-8-quinolinoxy) -acetate, O- (methoxycarbonyl) -2- (8-quinolinoxy) -acetamide oxime, 5-Oxazolecarboxylic acid, 2 - [(2,2-dimethylethyl) amino] 4- (trifluoromethyl) -, ethyl ester, Acetic acid, (diphenylmethoxy) -, methyl ester, Allyl-N-methyldithiocarbonylate, 4-isoxazolecarboxylic acid, 5- (2,4-dichlorophenyl) -, ethyl ester, Pyrimidine, 4,6-dichloro-2-phenyl, 4-pentenenitrile, 2-methyl-2 - [(4-methylphenyl) thio] -, acetonitrile, N (5-chloro-8-quinolinyl) oxy7-, Acetamide 2- (diphenylmethoxy) -N-methyl-, Glycine, N- [bis (4-methoxyphenyl) -methyl] -, ethyl ester, Glycine, N- [bis (4-chlorophenyl) -methyl] -, ethyl ester, Acetic acid, N (10,11-dihydro-5H-dibenzo / 1,1,1-cyclohepten-5-yl) oxy] -, 1,1-dimethylethyl ester, Ethantioamide, 2- (diphenylmethoxy) -, Acetic acid, (diphenylmethoxy) -, propyl ester, Acetic acid, (diphenylmethoxy) -, 2,2,2-trifluoroethyl ester, Acetic acid, (phenyl) 3- (trifluoromethyl) phenyl7 methoxy} -, 2-methyl-2-propanamine. salt, 135 Acetic acid, (diphenylmethoxy) -, 2-propynyl ester, Acetic acid, (diphenylmethoxy) -, phenyl ester, Ethanethioic acid, 2- (diphenylmethoxy) -, S-ethyl ester, Acetic acid, (diphenylmethoxy) -, 2-cyanoethyl ester, Acetic acid, / phenyl / 3- (trifluoromethyl) -phenyl / methoxy} -, 2,2,2-trifluoroethyl ester, Acetic acid, (diphenylmethoxy) -, 3-furanylmethyl ester, Acetic acid, fbis (2,6-dimethylphenyl) -methoxy / -, Acetic acid, (diphenylmethoxy) -, 3-nitrophenyl ester, Acetic acid, {/ bis (2,6-dimethylphenyl) 7-methoxy} -, ethyl ester, Acetic acid, (diphenylmethoxy) -, 1-cyano-1-methylethyl ester, 5-tazolecarboxylic acid, I ethyl ester, 5-Thiazolecarboxylic acid, 4- (trifluoromethyl) -, 5-Thiazole 'carboxylic acid. 4- (trifluoromethyl) -, 5-thiazolecarboxylic acid, octyl ester, 5-Thiazolecarboxylic acid, phenyl ester, 5-Thiazolecarboxylic acid, methyl) -, 5-Thiazolecarboxylic acid, methyl) - -, ethyl ester, 5-Thiazolecarboxylic acid, ethyl ester, 5- Thiazolecarboxylic acid methyl) -, 1-methylethanamine Benzylamine-, (alpha-methyl-, N 2-ylidene) hydrochloride, -chloro-4- (trifluoromethyl) -, butyl ester, 2-chloro-, 2-chloro-, hexyl ester, 2-chloro-4- (trifluoromethyl) -, 2-chloro-4- (trifluoromethyl) -, 2-chloro-4- (trifluoro-2- bromo-4- (trifluoro-2-iodo-4- (trifluoromethyl) -, 2-chloro-4- (trifluorosol, 4- (methyl) -1,3-dithiol136 Pyridine, N-oxide, 2- (3,4,5,6-tetrachloro-2-pyridylthio) acetic acid, N * 3,5-bis (trifluoromethyl) -phenoxy / -, Propanamide, 2-chloro-N / 5 -Jodo-4- (trifluoromethyl) 2-thiazolyl7 ", Cyclopropanecarbonitrile, 1- {{3,4-dimethylphenyl) thio] -, Propannitrile, 3 - // 2- (1,1-dimethylethyl) phenyl7thio7-, 4-pentenitrile, 2-methyl-2 - // 4- (1 -methylethyl) phenyl / thio-7-, Ethanimidamide, N '- / (methoxycarbonyl) -oxo / -2- (8quinolinyloxy) -, 1 (3H) -isobenzofuranone, 3- / 2- (2,5-dimethoxyphenyl) 2-oxoethyl 7 ^- ♦ Acetic acid, 2- (diphenylmethoxy) sodium salt, hemihydrate, Acetic acid, 2- (diphenylmethoxy) ~ or Acetic acid, (diphenylmethoxy) -, 2-propanamine salt and c) a herbicidally effective amount of one or more co-herbicide compounds. 25. The composition of claim 24, wherein said soherbicide compound is hal-halogenated acetamide, thiocarbamate, urea, sulfonylurea, pyridine, heterophenyl or diphenyl ether, imidazolinone, a benzoic acid derivative, triazine, azolopyrimidine sulfonamide, or glyphonamide, glyphonamide , a herbicide or a mixture of herbicidal compounds. The composition of claim 25, wherein said co-herbicide is Λ-chloroacetamide of formula IV. IV C1CH ₂ C - N 137 in which and R22 are independently hydrogen; alkyl, alkoxy, alkoxyalkyl, acylaminomethyl, acyl lower alkyl substituted aminomethyl; cycloalkyl, cycloalkylmethyl, mono- or polyunsaturated alkenyl, alkynyl, cycloalkenyl, cycloalkenylmethyl having up to 8 carbon atoms; phenyl; or heterocyclyl or heterocyclylmethyl having from 1 to 4 heteroatoms in the ring independently selected from N, S or O; and said Articles R21 and R22 'substituted with alkyl, alkenyl, alkenyl, alkenyloxy, alkynyloxy, alkoxy, alkoxyalkyl, alkoxycarbamethyl or ethyl of not more than 8 carbon atoms; nitro; halogen; cyano; amino or C. alkyl substituted amino; and R1, and R22 may be combined with the N atom to form one of said members heterocyclyl or substituted heterocyclyl. Composition according to claim 26, characterized in that the article R21 is an alkoxyalkyl radical in the structure -B-O-R2 _3> B and R2 ₃ are alkyl residues in a linear or branched chain having up to a maximum of 8 carbon atoms; or substituted or unsubstituted C. _1Λ heterocyclyl or heterocyclylmethyl radical having 1-4 4-10 heteroatoms in the ring independently selected from N atoms, S or 0. Article R22 is also one of said heterocyclyl or heterocyclylmethyl radicals or an optionally substituted phenyl radical. 28. The composition of claim 27, wherein said compound of formula IV is selected from the group consisting of: N- (2,4-dimethylthien-3-yl) -N- (1-methoxy-prop-2 -yl) -2-chloroacetamide; N- (1H-pyrazol-1-ylmethyl) -N- (2,4-dimethylthien-3-yl) -2-chloroacetamide; N- (1-pyrazol-1-ylmethyl) -N- (4,6-dimethoxypyrimidin-5-yl) -2-chloroacetamide and 2-chloro-N-isopropyl-1- (3,5,5-trimethylcyclohexen-1-yl ) acetamide. 138 29. The composition of claim 25, wherein said compound is a co-herbicide. a compound of formula V Oh II C1CH ₂ C - N - R ₂₄ (^ 2s) n in which hydrogen, alkyl, halogenated alkyl, alkoxy or alkoxyalkyl, alkenyl, halogenated alkenyl, alkynyl or halogenated alkynyl having a maximum of 6 carbon atoms, heterocyclyl or heterocyclylmethyl having atoms 0, S and / or N, and may be substituted by halogen; alkyl, carbonylalkyl or carbonylalkoxyalkyl, nitro, amino or cyano groups is hydrogen, halogen, nitro, amino, alkyl, alkoxy or alkoxyalkyl and n is 0-5. A composition according to claim 29, characterized in that said compound of formula V is selected from the group: 2-chloro-N-isopropylacetanilide; 2-chloro-2 ', 6'-diethyl-N- (methoxymethyl) -acetanilide; 2-chloro-2 ', 6'-diethyl-N- (butoxymethyl) -acetanilide; 2-chloro-N- (ethoxymethyl) -6'-ethyl-o-acetotoluidide; N-Chloroacetyl-N- (2,6-diethylphenyl) glycine ethyl ester; 2-chloro-N- (2,6-dimethylphenyl) -N- (2-methoxyethyl) acetamide; 2-chloro-N- (2-n-propoxyethyl) -2 ', 6 ¹ -diethylacethanilide; - 139 2-Chloro-N- (2 ~ methoxy-1-methylethyl) -6 ^1- ethyl-o-acetotoluidide; 2-chloro-2 ', 6'-dimethyl-N- (1-pyrazol-1-yl-methyl) acetanilide; 2-chloro-N- (2,6-dimethyl-1-cyclohexen-1-yl) -N- (1H-pyrazol-1-ylmethyl) -acetamide; 2-chloro-N-isopropyl-1- (3,5,5-trimethylcyclohexenyl-yl) acetamide; 2-chloro-2 ¹ -methyl-6 '-methoxy-N- (isopropoxymethyl) acetanilide; 2-chloro-2'-methyl-6'-trifluoromethyl-N- (ethoxymethyl) acetanilide; N- (2,4-dimethylthien-3-yl) -N- (1-methoxyprop-2-yl) -2-chloroacetamide; N- (1H-pyrazol-2-ylmethyl) -N- (2,4-dimethyl-thien-3-yl) 2-chloroacetamide, and N- (1-pyrazol-1-ylmethyl) -N- (4,6-dimethoxypyrimidin-5-yl) 2-chloroacetamide. The composition of claim 29, wherein said compound of formula V is selected from the group consisting of: acetochlor, alachlor, butachlor, metolachlor, pretilachlor, dimethachlor and metazachlor. 32. The composition of claim 25, wherein said soherbicide compound is a thiocarbamate compound. The composition of claim 32, wherein said thiocarbamate is selected from the group formed by dialate, trialate, EPTC, butylate and vernolate. 140 A composition according to any one of claims 29 to 32 or 33, characterized in that said herbicide compound of component (a) is a compound of formula IA where and R 1 is alkyl; R4 is H, alkyl, bormo or chloro; and R ^ l and R ^ 2 are independently alkyl or alkoxy » The composition of claim 34, wherein said compound is of formula IA R ^ and R ^ are methyl or ethyl; R2 is H, methyl, bromo or chloro and R 1 and R 2 are independently methyl or methoxy. 36. The composition of claim 35, wherein said compound is selected from the group consisting of: N - [(4-methoxy-6-methylpyrimidin-2-yl) -aminocarbonyl] 3-chloro-4-methoxycarbonyl-1-methylpyrazole-5sulfonamide; N- (4,6-dimethoxypyrimidin-2-yl) aminocarbonyl / 3-chloro-4-methoxycarbonyl-1-methylpyrazole-5-sulfonamide; N-f (4-Methoxy-6-methylpyrimidin-2-yl) -aminocarbonyl / 3-chloro-4-ethoxy-carbonyl-1-methylpyrazole-5-sulfonamide N- [4,6-dimethoxypyrimidin-2-yl) aminocarbonyl] -3-chloro 4-ethoxycarbonyl-1-methylpyrazole-5-sulfonamide; 141 N - [(methoxy-6-methylpyrimidin-2-yl) aminocarbonyl73-bromo-4-ethoxycarbonyl-1-methylpyrazole-5-sulfonamide N - [(4,6-dimethoxypyrimidin-2-yl) aminocarbonyl7-3-bromo4-ethoxycarbonyl-1-methylpyrazole-5-sulfonamide and N / ~ (4 _r 6-dimethoxypyrimidin-2-yl) -aminocarbonyl / -4etoksikarboni1-1-methyl-pyrazole-5-sulfonamide. A composition according to claim 35, wherein said compound of formula IA is selected from the group consisting of: N - / \ 4,6-dimethoxypyrimidin-2-yl) aminokarbonil7 ^_ 3-chloro 4-methoxycarbonyl-1-methylpyrazole-5-sulfonamide and N- [4,6-dimethoxypyrimidin-2-yl) aminocarbonyl7-4-ethoxy carbonyl-1-methylpyrazole-5-sulfonamide. . 38. The composition of claim 37, wherein said antidote compound of formula II is dichloromethyl. A composition according to claim 38, characterized in that said compound of formula II is selected from the group consisting of: 4- (dichloroacetyl) -3,4-dihydro-3-methyl-2H-2,4-benzoxazine, Ethanone, 2-2-dichloro-1- (1,2,3,4-tetrahydro-1-methyl-2isoquinolinyl) -, N- (dichloroacetyl) -1,2,3,4-tetrahydroquinoline, 1- (dichloroacetyl) -1,2,3,4-tetrahydroquinoline, Cis / trans-piperazine, 1,4-bis (dichloro 1,4-acetyl) ) 2,5-dimethyl-, N, N-di-propenyl dichloroamide, N- (2-propenyl) -N- (1,3-dioxolan-2-ylmethyl) dichloroacetamide, 142 in 1,5-diazacyclononane, 1,5-bis- (dichloroacetyl, 1-azaspiro / 4,4 / nonane, 1- (dichloroacetyl), Pyrrolo-1,2-7-pyrimidin- [6 (2H) 7-one, 1- (dichloroacetyl) hexahydro-3,3-8a-trimethyl, 2.2-dimethyl-3- (dichloroacetyl) -1,3-oxazole, 2.2-dimethyl-5-methoxy-3- (dichloroacetyl) -1,3-oxazole. The composition of claim 38, wherein said compound is R-25788. The composition of claim 38, wherein said compound is PPG-1292. The composition of claim 38, wherein said antidote compound of formula II is a subset of compounds of formula III. R, III where R ^ g, R ^ g and R ^ g are as defined herein. 43. The composition of claim 42, wherein said compound of formula III is selected from the group consisting of: Oxazolidine, 3- (dichloroacetyl) -2,2,5-trimethyl-, Oxazolidine, 3- (dichloroacetyl) -2,2-dimethyl-, Oxazolidine, 3- (dichloroacetyl) -2,2-dimethyl-5-phenyl- , Oxazolidine, 3- (dichloroacetyl) -2,2-dimethyl-5- (2furanyl) -, Oxazolidine, 3- (dichloroacetyl) -2,2-dimethyl-5- (2-thienyl) -, 143 Pyridine, 3- / 3- (dichloroacetyl) -2,2-dimethyl-5-oxazolidinyl] - in 4- (dichloroacetyl / -1-oxa-4-azaspiro- (4,5) -decane. 44. The composition of claim 42, wherein said compound is oxazolidine, 3-dichloroacetyl, 2,2-dimethyl-5- (2-furanyl). A composition according to claim 38, characterized in that said antidote compound is selected from the group of compounds (b) (ii) formed by: ot ~ cyanomethoxy i) imino / benzenacetonitrile, 3- (1, 3-dioxolan-2-yl-methoxy) imino / benzenacetonitrile, 0- / 1,3-dioxolan-2-yl IMET / ^- 2,2,2-trifluoromethyl-4 * chloroacetophenone oxime, Benzenmetamine, N- / 4- (dichloromethylene) -1,3-dithiolan-2ylidene / OC-methyl, hydrochloride, 1,8-naphthalic anhydride, 4,6-Dichloro-2-phenyl-pyrimidine, 2-chloro-N - N - (2,4,6-trimethylphenyl) -ethenylacetamide, Ethylene glycol acetal 1,1-dichloroacetone, 1,3-dioxolane, 2- (dichloromethyl) -2-methyl-, 5-Thiazolecarboxylic acid, 2-chloro-4- (trifluoromethyl) -, (phenylmethyl) ester, Phosphorothioic acid, 0,0-diethyl 0- (3-methylphenyl) ester, 4- pentenitrile, 2-methyl-2 - / (4-methylphenyl) thio / -, 5- chloro-8- (cyanomethoxy) quinoline, 1-methylhexyl-2- (5-chloro-8-quinolinoxy) -acetate. O- (methoxycarbonyl) -2- (8-quinolinoxy) -acetamide oxime, 5-Oxazolecarboxylic acid, 2 - [(2,2-dimethylethyl) amino] -4- (trifluoromethyl) -, ethyl ester, Acetic acid, (diphenylmethoxy) -, methyl ester, 144 Allyl-N-methyldithiocarbonylate, 4-isoxazolecarboxylic acid, 5- (2,4-dichlorophenyl) -, ethyl ester, Pyrimidine, 4,6-dichloro-2-phenyl-, 4-pentenitrile, 2-methyl-2-f (4-methylphenyl) thio7-, Acetonitrile, N * (5-chloro-8-quinolinyl) oxy / -, Acetamide 2- (diphenylmethoxy) -N-methyl-, Glycine, N- / bis (4-methoxyphenyl) -methyl7 'ethyl ester, Glycine, N- [bis (4-chlorophenyl) -methyl] -, ethyl ester, Acetic acid, // (10,11-dihydro-5H-dibenzo / 1,1-d / cyclohepten-5-yl) oxy}, 1,1-dimethylethyl ester, Ethantioamide, 2- (diphenylmethoxy) -, Acetic acid, (diphenylmethoxy) -, propyl ester, Acetic acid, (diphenylmethoxy) -, 2,2,2, -trifluoroethyl ester, Acetic acid, / phenyl / 3- (trifluoromethyl) phenyl / methoxy} -, 2-methyl-2-propanamine · salt, Acetic acid, (diphenylmethoxy) -, phenyl ester, Ethanethioic acid, 2- (diphenylmethoxy) -, S-ethyl ester, Acetic acid, (diphenylmethoxy) -, 2-cyanoethyl ester, Acetic acid, {phenyl / 3- (trifluoromethyl) -phenyl7 methoxy} -, 2,2,2, -trifluoroethyl ester, Acetic acid, (diphenylmethoxy) -, 2-propynyl ester, Acetic acid, (diphenylmethoxy) -, 3-furanylmethyl ester, Acetic acid, (bis (2,6-dimethylphenyl) -methoxy) -, Acetic acid, (diphenylmethoxy) -, 3-nitrophenyl ester, Acetic acid, / Y (bis (2,6-dimethylphenyl) / - methoxy} -, ethyl ester, Acetic acid, (diphenylmethoxy) -, 1-cyano-1-methylethyl ester, 5-Thiazolecarboxylic acid, 2-chloro-4- (trifluoromethyl) -, ethyl ester 145 5-Thiazolecarboxylic acid, butyl ester, 2-chloro-, 4- (trifluoromethyl) -, 5- Thiazolecarboxylic acid, 2-chloro-, hexyl ester, 4- (trifluoromethyl) -, 5-Thiazolecarboxylic acid, 2-chloro-4- (trifluoromethyl) -, octyl ester, 5-Thiazolecarboxylic acid, 2-chloro-4- (trifluoromethyl) -, phenyl ester, 5-Thiazolecarboxylic acid, 2-chloro-4- (trifluoromethyl) -, 5-Thiazolecarboxylic acid, 2- [bromo-4- (trifluoromethyl) / ethyl ester, 5-Thiazolecarboxylic acid, 2-iodo-4- (trifluoromethyl) ~, ethyl ester, 5-Thiazolecarboxylic acid, 2-chloro-4- (trifluoromethyl) -, 1- Methylethanamine salt, Benzylamine -, (alpha-methyl-, N-4- (methyl) -1,3-dithiol-2-ylidene) hydrochloride, Pyridine, N-oxide, 2- (3,4,5,6-tetrachloro-2-pyridylthio) -, acetic acid, (3,5-bis (trifluoromethyl) -phenoxy) propanamide, 2-chloro-N- / 5-iodo-4- (trifluoromethyl) 2-thiazolyl] -, Cyclopropanecarbonitrile, 1 - [(3,4-dimethylphenyl) thio] -, Propannitrile, 3 - [2- (1,1-dimethylethyl) phenyl] thio] -, 4-pentenenitrile, 2-methyl-2 - // 4 - (l-methylethyl) phenyl / thio / -, Ethanimidamide, N '- / (methoxycarbonyl) -oxsp / -2- (8-quinolinyloxy) -, 1 (3H) -isobenzofuranone, 3- [2- (2,5-dimethoxy and phenyl) 2-oxoethyl] -, Acetic acid, 2- (diphenylmethoxy) sodium salt, hemihydrate, Acetic acid, 2- (diphenylmethoxy) -, or Acetic acid, (diphenylmethoxy) -, 2-propanaminsole. 146 The composition of claim 37, wherein said antidote compound is 1,8-naphthalic anhydride. 47. The composition of claim 37, wherein said antidote compound is flurazole. 48. The composition of claim 37, wherein said compound is an MON-7400 antidote. 49. Composition characterized in that it contains: a) an herbicidally effective amount of NC-319; b) an antidote effective amount of oxazolidine, 3- (dichloroacetyl) -2,2-dimethyl-5- (2-furanyl) - and c) a co-herbicide compound selected from the group consisting of: acetochlor, alachlor, butachlor, metolachlor, pretilachlor, dimethachlor and metazachlor. The composition of claim 49, wherein said soherbicide compound is acetoclor. 51. The composition of claim 49, wherein said soherbicide compound is alachlor. 52. A method of reducing the phytotoxicity of crops by using a herbicide compound of formula N 147 wherein: R 1 is H, C 1 alkyl or phenyl; R is H, C ^ _ ₃ alkyl or halogen; R_ is R_, N0_ or COOR ,; 3 ^J 2 2 4 ^R 4 J ^ec 1-3 alkyl, C ₂₃ alkenyl, N (R ₅ ) (Rg), SC> ₂ N (R _? ) (G) or SO ₂ R ₉ ; R -R are C ^ _ ₃ alkyl; is H or alkyl; and R ₂ are independently C ^ _ ₃ alkyl or alkoxy, halogen, or N (R / (R ^); ._ and R ,, are Ld 14 A is CH or N, R, _ and R,. C, 'alkyl and 13 14 are 1-3-3 · alone or in admixture with one or more co-herbicide compounds containing, as the crop site, an antidote effective amount (i) of a compound of formula, II in which R4 can be selected from the group consisting of: alkyl, halogenated alkyl; halogenated alkenyl; alkenyl; cycloalkyl; cycloalkylalkyl; halogen; hydrogen; carboalkoxy; N-alkenylcarbamylalkyl; N-alkenylcarbamyl; N-alkyl-N-alkynylcarbamyl; N-alkyl-N-alkynylcarbamylalkyl; N-alkenylcarbamylalkoxyalkyl; N-alkyl-N-alkynylcarbamylalkoxyalkyl; alkynyloxy; halogenated alkoxy; thiocyanatoalkyl; alkenylaminoalkyl; alkylcarboalkyl; cyanoalkyl; cyanatoalkyl; alkenylaminosulfonalkyl; alkylthioalkyl; halogenated alkylcarbonyloxyalkyl, alkoxycarboalkyl; halogenated alkenyl carbonyl oxyalkyl; hydroxyhaloalkyloxyalkyl; hydroxyalkylcarboalkyloxyalkyl; hydroxyalkyl; alkoxysulfonoalkyl; furyl, thienyl; alkyldithiolenyl; thienalkyl; phenyl and substituted phenyl in which the 148 said substituents are selected from: halogen, alkyl, halogenated alkyl, alkoxy, carbamyl, nitro, carboxylic acids and their salts, halogenated alkylcarbamyl ', phenylalkyl; phenylhaloalkyl; phenylalkenyl; substituted phenylalkenyl, wherein said substituents may be selected from: halogen, alkyl, alkoxy, halogenated phenoxy, phenylalkoxy; phenylalkylcarboxyalkyl; phenylcycloalkyl; halogenated phenylalkenoxy-, halogenated thiophenylalkyl, 'halogenated phenoxyalkyl; bicycloalkyl; alkenylcarbamylpyridinyl; alkynylcarbamylpyridinyl ', dialkenylcarbamylbicycloalkenyl; alkynylcarbamylbicycloalkenyl; R 1 and R 2 may be the same or different and may be selected from the group consisting of: alkenyl, halogenated alkenyl, hydrogen, alkyl, halogenated alkyl, alkynyl, cyanoalkyl, hydroalkyl, hydroxyhaloalkyl, halogenated alkylcarboxyalkyl; alkylcarboxyalkyl; alkoxycarboxyalkyl; thioalkylcarboxylic; alkoxycarboalkyl; alkylcarbamyloxyalkyl; amino, 'form 1; halogenated alkyl-N-alkylamido; halogenated alkylamido, 'halogenated alkylamidoalkyl, halogenated alkyl-N-alkylamidoalkyl halogenated alkylamidoalkenyl, alkylimino; cycloalkyl, alkylcycloalkyl; alkoxyalkyl; alkylsulfonyloxyalkyl; mercaptoalkyl; alkylaminoalkyl; alkoxycarboalkenyl halogenated alkylcarbonyl, alkylcarbonyl, 'alkenylcarbamyloxyalkyl,' cycloalkylcarbamyloxyalkyl; alkoxycarbonyl, halogenated alkoxycarbonyl, halogenated phenylcarbamyloxyalkyl; cycloalkenyl ', phenyl and substituted phenyl in which said substituents may be selected from: alkyl, halogen, halogenated alkyl, alkoxy, halogenated alkylamido, phthalamido, hydroxy, alkylcarbamyloxy, alkenylcarbamyloxy, alkylamido, halogenated alkylamido or alkylcarboalkenyl; substituted phenylalkyl, wherein said substituents may be selected from: halogen or alkyl *, dioxyalkylene; halogenated phenoxyalkylamidoalkyl ', alkylthiodiazolyl', piperidyl, piperidylalkyl ', dioxolanylalkyl', thiazolyl; alkylthiazolyl ', benzothiazolyl, halogenated benzothiazolyl *, furyl', alkyl substituted 149 furyl; furylalkyl; pyridyl; alkylpyridyl; alkyloxzolyl; tetrahydrofurylalkyl; 3-cyano, thienyl; alkyl substituted thienyl, 4,5-polyalkylene thienyl; α-halogenated alkylacetamidophenylalkyl; Halogenated alkylacetamidonitrophenylalkyl; OG-halogenated alkylacetamidohalo-phenylalkyl; cyanoalkenyl; and used together, they can form a structure formed by: piperidinyl; alkylpiperidinyl; pyridyl; di- or tetrahydropyridinyl; alkyltetrahydropyridyl; morpholyl; alkylmorpholyl; azabicyclononyl; diazacycloalkanyl; benzoalkylpyrrolidinyl; oxazolidinyl; perhydrooxazolidinyl; alkyloxazolidyl; furyloxzolidinyl; thienyloxazolidinyl; pyridyloxyzolidinyl; pyrimidinyloxyzolidinyl; benzooxazolidinyl; .j Spirocycloalkyloxazolidinyl; alkylaminoalkenyl; alkylidenimino; pyrrolidinyl; piperidonyl; perhydroazepinyl; perhydroazocinyl; pyrazolyl; dihydropyrazolyl; piperazinyl; perhydro-1,4-diazepinyl; quinolinyl; isoquinolinyl; dihydro-, tetrahydro- and perhydroquinoline or -isoquinyl; indolyl and di- and perhydroindolyl and the aforementioned combined members and R4 substituted with those independent radicals and R2> listed above; or (ii) one of the following compounds: <RTI ID = 0.0> (cyanomethoxy) imino / benzenacetonitrile </RTI> 1,1, 3-dioxolan-2-yl-methoxy) imino-benzenacetonitrile, 0-fl, 3-dioxolan-2-ylmethyl / -2,2,2-trifluoromethyl4'-chloroacetophenone oxime, Benzenmetamine, N-Z4- (dichloromethylene) -1,3-diotolan-2ylidene 7- (k-methyl, hydrochloride, 1,8-naphthalic anhydride, 4,6-dichloro-2-phenyl-pyrimidine, 2-chloro-N- / 4- (2,4,6-trimethylphenyl) -ethenyl acetamide, Ethylene glycol acetal 1,1-dichloroacetone, 1,3-dioxolane, 2- (dichloromethyl) -2-methyl-, 5-thiazolecarboxylic acid, 2-chloro-4- (trifluoromethyl) -, (phenyl-methyl) -ester, 150 Phosphorothioic acid, 0,0-diethyl (- (3-methylphenyl) ester, 4- pentenitrile, 2-methyl-2 - / (4-methyl-phenyl) thio / -, 5- chloro-8- (cyanomethoxy) quinoline, 1-methylhexyl-2- (5-chloro-8-quinolinoxy) acetate, O- (methoxycarbonyl) -2- (8-quinolinoxy) -acetamide oxime, 5-oxazolecarboxylic acid, 2 - [(2,2-dimethylethyl) amino] -4- (trifluoromethyl) -, ethyl ester, Acetic acid, (diphenylmethoxy) -, methyl ester, Allyl-N-methyldithiocarbonylate, 4-isoxazolecarboxylic acid, 5- (2,4-dichlorophenyl) -, ethyl ester, Pyrimidine, 4,6-dichloro-2-phenyl-, 4-pentenenitrile, 2-methyl-2 - [(4-methylphenyl) thio] -, acetonitrile, N (5-chloro-8-quinolinyl) oxy] -, Acetamide 2- (diphenylmethoxy) -N-methyl-, Glycine, N- / bis (4-methoxyphenyl) -methyl7-, ethyl ester, Glycine, N- / bis (4-chlorophenyl) -methyl ^- »ethyl ester, acetic acid, [{10,11-dichloro-5H- dibenzo / 1,2-cyclohepten-5-yl) oxy-, 1,1-dimethylethyl ester, Ethantioamide, 2- (diphenylmethoxy) -, Acetic acid, (diphenylmethoxy) -, propyl ester, Acetic acid, (diphenylmethoxy) -, 2,2,2-trifluoroethyl ester, Acetic acid, Phenyl / 3- (trifluoromethyl) f enyl / methoxy 2-methyl-2-propanamine salt, Acetic acid, (diphenylmethoxy) -, phenyl ester, Ethanethioic acid, 2- (diphenylmethoxy) -, S-ethyl ester, Acetic acid, (diphenylmethoxy) -, 2-cyanoethyl ester, Acetic acid, {phenyl / 3- (trifluoromethyl) -phenyl / methoxy-, 2,2,2-trifluoroethyl ester, Acetic acid, (diphenylmethoxy) -, 2-propynyl ester, Acetic acid, (diphenylmethoxy) -, 3-furylmethyl ester, Acetic acid, (bis (2,6-dimethylphenyl) -methoxy) -, 151 Acid, (diphenylmethoxy) -, 3-nitrophenyl ester, acid, {/ bis (2,6-dimethylphenyl) / - methoxy ^ -, ester, acid, (diphenylmethoxy) -, 1-cyano-1-methylethyl Acetic Acetic Ethyl Acetic ester, 5-Thiazolecarboxylic acid, methyl) -, ethyl ester, 5-Thiazolecarboxylic acid, 4-trifluoromethyl) -, 5-thiazolecarboxylic acid, octyl ester, 5-Thiazolecarboxylic acid, methyl) -, phenyl ester, 5-Thiazolecarboxylic acid, 5-Thiazolecarboxylic acid, methyl}] -, ethyl ester, 5-Thiazolecarboxylic acid, ethyl ester, 5-thiazolecarboxylic acid, 1- Methylethanamine salt, Benzylamine-, (alpha-methyl2-ylidene) hydrochloride, 2-chloro-4- (trifluoro2-chloro-, hexyl ester, 2-chloro-4- (trifluoromethyl) -, 2-chloro-4- (trifluoro-2-chloro-4- (trifluoromethyl) -, 2- [chromo-4- (trifluoro-2-iodo-4- (trifluoromethyl) -, 2-chloro-4- (trifluoromethyl) -, N-4- (methyl) -1,3-dithiolpyridine, N-oxide, 2- (3,4,5,6-tetrachloro-2-pyridylthio) -, acetic acid, / 3,5-bis (trifluoromethyl) - phenoxy / -, propanamide, 2-chloro-N- (5-iodo-4- (trifluoromethyl) 2-thiazolyl) -, Cyclopropanecarbonitrile, 1 - [(3,4-dimethylphenyl) thio7-, Propannitrile, 3 - [2- (1,1-dimethylethyl) phenyl] thio], 4-pentenitrile, 2-methyl-2 - [4- (l -methylethyl) phenyl / thio7-, Ethanimidamide, N '- N' methoxycarbonyl) -oxo 7 '2- (8-quinolinyloxy) -, 5-Thiazolecarboxylic acid, butyl ester, 2-chloro-, 4- (trifluoromethyl) -, 152 1 (3Η) -isobenzofuranone, 3- / 2- (2,5-dimethoxyphenyl) 2-oxoethyl 7-, Acetic acid, 2- (diphenylmethoxy) sodium salt, hemihydrate, Acetic acid, 2- (diphenylmethoxy) -, or Acetic acid, (diphenylmethoxy) -, 2-propanamine salt. 53. The method of claim 52, wherein said antidote compound of formula II is dichloromethyl. 54. The method of claim 53, wherein said compound of formula II is selected from the group consisting of: 4- (dichloroacetyl) -3,4-dihydro-3-methyl-2H-2,4-benzoxazine, Ethanone, 2,2-dichloro-1- (1,2,3,4-tetrahydro-1-methyl-2 isoquinolinyl) N- (dichloroacetyl) -1,2,3,4-tetrahydroquinoline, 1- (dichloroacetyl) -1,2,3,4-tetrahydroquinoline, Cis / trans-piperazine, 1,4-bis (dichloro-1,4-acetyl) 2,5-dimethyl-, N, N-di-propenyl dichloramide, N- (2-propenyl) -N- (1,3-dioxolan-2-ylmethyl) -dichloroacetamide, 1,5-diazacyclononane, 1- (dichloroacetyl, Pyrrolo [1,2-a] pyrimidin-76 (2H) 7 ^- one, 1- (dichloroacetyl) hexahydro-3,3-8a-trimethyl, 2,2-dimethyl-3. (Dichloroacetyl) -1,3-oxazole and 2- 2-dimethyl-5-methoxy-3- (dichloroacetyl) -1,3-oxazole. 55. The method of claim 53, wherein said compound is R-25788. 153 56. The method of claim 53, wherein said compound is PPG-1292. 57. The method of claim 53, wherein said antidote compound of formula II is a subset of compounds of formula III in which R is ₁₀ , R _and and R_ _n is as defined herein. 18 19 20 ^J 58. The method of claim 57, wherein said compound of formula III is selected from the group consisting of: Oxazolidine, 3- (dichloroacetyl) -2,2,5-trimethyl-, Oxazolidine, 3- (dichloroacetyl) -2,2-dimethyl-, Oxazolidine, 3- (dichloroacetyl) -2,2-dimethyl-5-phenyl-, Oxazolidine, 3- (dichloroacetyl) -2,2-dimethyl 1-5- (2furanyl) -, Oxazolidine, 3- (dichloroacetyl) -2,2-dimethyl-1- (2-thienyl) -, Pyridine, 3- / 3- (dichloroacetyl) -2,2-dimethyl-5-oxazolidinyl / in 4- (dichloroacetyl) -1-oxa-4-azaspiro- (4,5) -decane. 59. The method of claim 57, wherein said compound is oxazolidine, 3-dichloroacetyl, 2,2-dimethyl-5- (2-furanyl). 154 60. The method of claim 52, wherein the antidote compound is selected from the group of compounds (b) (ii) formed by: <x- / (cyanomethoxy) imino7benzenacetonitrile, O (- / 1,3-dioxolan-2-yl-methoxy) imino / benzenacetonitrile, O- (1,3-dioxolan-2-ylmethyl) -2,2,2-trifluoromethyl4 ^1- chloroacetophenone oxime, Benzenmetamine, N- / 4- (dichloromethylene) -1,3-dithiolan2-yldiden7-O (- methyl, hydrochloride, 1,8-naphthalic anhydride, 4,6-dichloro-2-phenyl-pyrimidine, 2-chloro-N- [1- (2,4,6-trimethylphenyl) -ethenyl] acetamide, Ethylene glycol acetal 1,1-dichloro-acetone, 1,3-dioxolane, 2- (dichloromethyl) -2-methyl-, 5-thiazolecarboxylic acid, 2-chloro-4- (trifluoromethyl) -, (phenylmethyl) ester, Phosphorothioic acid, 0,0-diethyl 0- (3-methyl-phenyl) ester, 4- pentenitrile, 2-methyl-2 - / (4-methylphenyl) thio7-, 5-chloro-8- (cyanomethoxy) quinoline, 1-methylhexyl-2- (5-chloro-8-quinolinoxy) -acetate, 0- (methoxycarbonyl) -2- (8-quinolinoxy) -acetamide oxime, 5-oxazolecarboxylic acid , 2 - [(2,2-dimethylethyl) amino7-4- (trifluoromethyl) -, ethyl ester, Acetic acid, (diphenylmethoxy) -, methyl ester (code No MON-7400), Allyl-N-methyldithiocarbonylate, 4-isoxazolecarboxylic acid, 5- (2,4-dichlorophenyl) -, ethyl ester, Pyrimidine, 4,6-dichloro-2-phenyl-, 4-pentenitrile, 2-methyl-2 - / (4-methylphenyl) thiol ^r -, Acetonitrile, Z (5-chloro-8-quinolinyl) oxy / -, Acetamide 2- (diphenylmethoxy) -N-methyl-, Glycine, N- / bis (4-methoxyphenyl) metil7 ^-, ethyl ester, Glycine, N- [bis (4-chlorophenyl) -methyl] -, ethyl ester, Acetic acid, N (10,11-dihydro-5H-dibenzo / 1,1, d7 cyclohepten-5-yl) oxy] -, 1,1-dimethylethyl ester, 155 Ethantioamide, 2- (diphenylmethoxy) -, Acetic acid, (diphenylmethoxy) -, propyl ester, Acetic acid, (diphenylmethoxy) -, 2,2,2-trifluoroethyl ester, Acetic acid {phenyl / 3- (trifluoroacetyl) phenyl / methoxy} -, 2-methyl-2-propanamine salt Acetic acid, (diphenylmethoxy) -, phenyl ester, Ethanethioic acid, 2- (diphenylmethoxy) -, S-ethyl ester, Acetic acid, (diphenylmethoxy) -, 2-cyanoethyl ester, Acetic acid, | phenyl / 3- (trifluoromethyl) -phenyl / methoxy · -2,2,2-trifluoroethyl ester, Acetic acid, (diphenylmethoxy) -, 2-propynyl ester, Acetic acid, (diphenylmethoxy) -, 3-furanylmethyl ester, Acetic acid, / bis (2,6-dimethylphenyl) -methoxy7-, Acetic acid, (diphenylmethoxy) -, 3-nitrophenyl ester, Acetic acid,} / bis (2,6-dimethylphenyl) / - methoxy} -, ethyl ester, Acetic acid, (diphenylmethoxy) -, 1-cyano-1-methylethyl ester, 5-Thiazolecarboxylic acid, 2-chloro-4- (trifluoromethyl) -, ethyl ester, 5-Thiazolecarboxylic acid, butyl ester, 2-chloro-, 4- (trifluoromethyl) -, 5- Thiazolecarboxylic acid, 2-chloro-, hexyl ester, 4- (trifluoromethyl) -, 5-Thiazolecarboxylic acid, 2-chloro-4- (trifluoromethyl) -, phenyl ester, 5-Thiazolecarboxylic acid, 2-chloro-4- (trifluoromethyl) -, 5-thiazolecarboxylic acid, 2- [bromo-4- (trifluoromethyl)] -, ethyl ester, 5-Thiazolecarboxylic acid, 2-iodo-4- (trifluoromethyl), ethyl ester, 5-Thiazolecarboxylic acid, 2-chloro-4- (trifluoromethyl) -, octyl ester, - 156 5-Thiazolecarboxylic acid, 2-chloro-4- (trifluoromethyl) -, 1- Methylethanamine salt, Benzylamine-, (alpha-methyl-, N-4- (methyl) -1,3-dithiol-2-ylidene) hydrochloride, Pyridine, N-oxide, 2- (3,4,5,6-tetrachloro-2-pyridylthio) -, acetic acid, (3,5-bis (trifluoromethyl) -phenoxy) ^- , propanamide, 2-chloro-N- / 5-iodo-4- (trifluoromethyl) -2-tiazolil7 ^_ " Cyclopropanecarbonitrile, 1 - / (3,4-dimethylphenyl) thio7-, Propannitrile, 3 - / (2- (1,1-dimethylethyl) phenyl / thio) -, 4-pentenenitrile, 2-methyl-2 - // 4- (l-methylethyl) phenyl7 thio-, Ethanimidamide, N '- N' methoxycarbonyl) -oxo / -2- (8-quinolinyloxy) -, 1 (3H) -isobenzofuranone, 3- / 2- (2,5-dimethoxyphenyl) -2-oxoethyl 7, Acetic acid, 2- (diphenylmethoxy) -, Acetic acid, (diphenylmethoxy) -, 2-propanamine salt, or Acetic acid, 2- (diphenylmethoxy) sodium salt, hemihydrate. 61. The method of claim 52, wherein said antidote compound is 1,8-naphthalic anhydride. 62. The method of claim 52, wherein said antidote compound is flurazole. 63. The method of claim 52, wherein the antidote compound is MON-7400. 64. The method according to any of claims 54, 57 or 60, characterized in that said herbicide compound is that of formula IA, 157 in which R1 is alkyl; R4 is H, alkyl, bromo or chloro; and R ^ and R ^ 2 are independently alkyl or alkoxy. 65. The method of claim 64, wherein said compounds are of formula IA R1 and R8 are methyl or ethyl; R ₂ is H, methyl, bromo or chloro and R 1, and R ₂ are independently methyl or methoxy. 66. The method of claim 65, wherein said compound is selected from the group consisting of: N - [(4-methoxy-6-methylpyrimidin-2-yl) -aminocarbonyl] 3-chloro-4-methoxycarbonyl-1-methylpyrazole-5-sulfonamide; N - / (4,6-dimethoxypyrimidin-2-yl) anunokarbonil7 ^- 3 "Chloro-4-methoxycarbonyl-l-methylpyrazole-5-sulfonamide; N-7 (4-methoxy-6-methylpyrimidin-2-yl) -arainocarbonyl73-chloro-4-ethoxycarbonyl-1-methylpyrazole-5-sulfonamide; N- [4,6-dimethoxypyrimidin-2-yl) aminocarbonyl] -3-chloro-4-ethoxycarbonyl-1-methylpyrazole-5-sulfonamide; N-Z (4-methoxy-6-raethylpyrimidin-2-yl) -aminocarbonyl73-bromo-4-ethoxycarbonyl-1-methylpyrazole-5-sulfonamide; 158 N - [(4,6-dimethoxypyrimidin-2-yl) aminocarbonyl] -3-bromo-4-ethoxycarbonyl-1-methylpyridol-5-sulfonamide, N - [(4,6-dimethoxypyrimidin-2-yl) -aminocarbonyl] -4-ethoxycarbonyl-1-methyl-pyrazole-5-sulfonamide. 67. The method of claim 64, wherein the labeled compound of formula la is selected from the group consisting of: N - [(4,6-dimethoxypyrimidin-2-yl) amino-carbonyl7-3chloro-4-methoxycarbonyl-1-methylpyrazole-5-sulfonamide and N- [4,6-dimethoxypyrimidin-2-yl) aminocarbonyl] -4-ethoxy carbonyl-1-methylpyrazole-5-sulfonamide. 68. A method for reducing phytotoxicity in crops due to the use of NC-319, which involves the application of an antidote effective amount of oxazolidine, 3- (dichloroacetyl) -2,2-dimethyl5- (2-furanyl) at the crop site. 69. A method for reducing phytotoxicity in crops due to the use of NC-311, which involves the application of an antidote effective amount of oxazolidine, 3- (dichloroacetyl) -2,2-dimethyl5- (2-furanyl) at the crop site. 70. The method of claim 52, wherein the co-herbicide compound is halogenated acetamide, thiocarbamate, urea, sulfonylurea, pyridine, heterophenyl or diphenyl ether, imidazolinone, benzoic acid derivative, triazine, azolopyrimidine sulfonamide, glyphosate, or glyphosate, glyphosate a herbicide or a mixture of herbicide compounds. 159 71. The method of claim 70, wherein said soherbicide is Χ-chloroacetamide of formula IV, • R II C1CH ₂ C - N IV where R_. and R 1 is independently hydrogen; C 1-6 alkyl, alkoxy, alkoxyalkyl, acylaminomethyl, acyl-lower alkyl ^- substituted aminomethyl, cycloalkyl, cycloalkylmethyl, mono- or polyunsaturated alkenyl, alkynyl, cycloalkenyl, cycloalkenylmethyl having up to 8 carbon atoms; phenyl ', or heterocyclyl or heterocyclylmethyl containing in the ring 1 to 4 heteroatoms selected independently from N, S or 0; and said Articles R1 and R2 are substituted by: alkyl, alkenyl, alkynyl, alkenyloxy, alkynyloxy, alkoxy, alkoxyalkyl, alkoxycarbomethyl or ethyl having up to 8 carbon atoms; nitro; halogen; cyano; amino or C. alkyl substituted amino; and R _n . and R 2 can be combined with the N atom to form one of said heterocyclyl or substituted heterocyclyl members. 72. The method of claim 71, wherein the member R21 is an alkoxyalkyl radical of structure -B-O-R__, wherein B and R__ are residues of a linear or branched alkyl chain having up to 8 carbon atoms combined; or a substituted or unsubstituted C. heterocyclyl or heterocyclylmethyl radical, 4-10 containing in the ring 1 to 4 heteroatoms selected independently from N, S or 0 atoms, and member R22 is also one of said heterocyclyl or heterocyclylmethyl radicals or an optionally substituted phenyl radical. 160 73. The method of claim 72, wherein said compound of formula IV is selected from the group consisting of: N- (2,4-dimethylthien-3-yl) -N- (1-methoxy-prop-2-yl) 2-chloroacetamide; N- (1H-pyrazol-1-ylmethyl) -N- (2,4-dimethylthien-3-yl) 2-chloroacetamide; N- (1-pyrazol-1-ylmethyl) -N- (4,6-dimethoxypyrimidin5-yl) -2-chloroacetamide and 2-Chloro-N-isopropyl-1- (3,5,5-trimethylcycloboxen-1-yl) acetamide. 74. The method of claim 70, wherein said co-herbicide compound is a compound of formula V, (^ 25) wherein hydrogen, alkyl, halogenated alkyl, alkoxy or alkoxyalkyl, alkenyl, halogenated alkenyl, alkynyl or halogenated alkynyl having to 6 carbon ^a toms ^ 5-10 h ^eteroc iklil or heterocyclylmethyl having 0 atoms, S and / or N, which may be substituted by halogen, alkyl, carbonylalkyl or carbonylalkoxyalkyl, nitro, amino or cyano groups; R ₃ is hydrogen, halogen, nitro, amino, alkyl, alkoxy or alkoxyalkyl and n is 0 - 5. 161 75. The method of claim 74, wherein said compound of formula V is selected from the group consisting of: 2-chloro-N-isopropylacetanilide; 2-chloro-2 ', 6'-diethyl-N- (methoxymethyl) -acetanilide; 2-chloro-2 ', 6'-diethyl-N- (butoxymethyl) -acetanilide; 2-chloro-N- (ethoxymethyl) -6'-ethyl-o-acetotoluidide; N-Chloroacetyl-N- (2,6-diethylphenyl) glycine ethyl ester; 2-chloro-N- (2,6′-dimethylphenyl) -N- (2-methoxyethyl) acetamide; 2-chloro-N- (2-n-propoxyethyl) -2 ', 6'-diethylacetanilide; 2-chloro-N- (2-methoxy-1-methylethyl) -6'-ethyl-o-acetotoluidide; 2-chloro-2 ', 6'-dimethyl-N- (1-pyrazolo-1-yl-methyl) acetanilide; 2-chloro-N- (2,6-dimethyl-1-cyclohexenyl-yl) -N- (1H-pyrazol-1-ylmethyl) -acetamide; 2-chloro-N-isopropyl-1- (3,5,5-trimethylcyclohexen-1-yl) acetamide; 2-chloro-2'-methyl-6'-methoxy-N- (isopropoxymethyl) acetanilide; 2-chloro-2 ^1- methyl-6'-trifluoromethyl-N- (ethoxymethyl) acetanilide; N- (2,4-dimethylthien-3-yl) -N- (1-methoxyprop-2-yl) -2-chloroacetamide; N- (1H-pyrazol-2-ylmethyl) -N- (2,4-dimethyl-thien-3-yl) -2-chloroacetamide and N- (1-pyrazol-1-ylmethyl) -N- (4,6-dimethoxypyrimidin-5-yl) -2-chloro-acetamide. 76. The method of claim 74, wherein said compound of formula V is selected from the group consisting of: acetochlor, alachlor, butachlor, metolachlor, pretilachlor, dimethachlor and metazachlor. 162 77. The method of claim 70, wherein said soherbicide compound is a thiocarbamate compound. 78. The method of claim 77, wherein said thiocarbamate is selected from the group consisting of: dialate, trialate, EPTC, butylate and vernolate. 79. A method for reducing phytotoxicity in crops due to the use of NC-319, which includes the application of an antidote effective amount of oxazolidine, 3- (dichloroacetyl) - 2,2-dimethyl -5- (2-furanyl) - and a group of soherbicide compounds, formed by acetoclor, alachlor, butachlor, metalachlor, pretilachlor, dimethachlor and metazachlor, to the crop site. 80. The method of claim 79, wherein said crop is cereals. 81. The method of claim 80, wherein said soherbicide compound is acetochlor. 82. The method of claim 80, wherein said soherbicide compound is alachlor.