Herbicide compositions containing a nitrile derivative as antidote

FIELD OF THE INVENTION
The invention relates to a herbicide composition containing as active ingredient a urea derivative of the formula (II) ##STR2## and/or a thiolcarbamate derivative of the formula (III) ##STR3## and/or a chloroacetanilide derivative of the formula (IV) ##STR4## and as an antidote a nitrile derivative of the formula (I) ##STR5## and/or a cyanopyridine and/or a benzonitrile derivative optionally mono- or polysubstituted by halogen or C.sub.1-3 alkoxy diminishing the phytotoxicity of the active ingredient.
In the formula (I)
R.sub.1 and R.sub.2 which are the same or different, stand for hydrogen, halogen or a methyl, ethyl, allyl, vinyl, phenyl or benzyl group; or
R.sub.1 and R.sub.2 together may stand for a benzylidene group; and
R.sub.3 means chlorine or a methyl, phenyl, chlorophenyl, alkoxyphenyl, chlorophenylamino, anilino, anilinomethylene, N-alkylanilinomethylene, N,N-dialkylanilinomethylene, alkoxyanilinomethylene, benzylaminomethylene, cyclohexylaminomethylene, N-alkyl-cyclohexylaminomethylene, hexamethyleniminomethylene, phthalimidomethylene, nitrophthalimidomethylene, morpholinomethylene, piperidinomethylene, C.sub.1-3 alkylaminomethylene, allylaminomethylene or di(C.sub.1-3 alkyl)aminomethylene group.
In the formula (II)
R.sub.4 and R.sub.5 which are the same or different, stand for a methyl or methoxy group;
R.sub.6 and R.sub.7 which are the same or different, represent hydrogen, halogen, a C.sub.1-3 alkyl or a methoxy group.
In the formula (III)
R.sub.8 and R.sub.9 which are the same or different, stand for a C.sub.1-4 alkyl group or a cyclohexyl group; or
R.sub.8 and R.sub.9 together may stand for a hexamethylene group;
R.sub.10 is an ethyl, propyl, benzyl, chlorobenzyl, 2,3-dichlorobenzyl or a 2,3-dichloroallyl group.
In the formula (IV)
R.sub.11 stands for an alkoxyalkyl group containing 2 to 5 carbon atoms; and
R.sub.12 and R.sub.13 which are the same or different, stand for a methyl or ethyl group.
BACKGROUND OF THE INVENTION
The urea derivatives of the formula (II), the triolcarbamate derivatives of formula (III) and the chloroacetanilide derivatives of formula (IV) have long been known as herbicidally active agents and are widely used for plant protection.
It is known however that these active agents, when used in an effective dose for the herbicidal action, also exert a damaging action of varying extent on the cultivated plants.
In the fifties, Hoffmann recognized that some compounds such as 1,8-naphthalic acid and its salts are useful for the decrease in the phytotoxicity of these herbicides [see the U.S. Pat. Nos. 3,131,509 and 3,702,759].
Since that time, the research into antidote compounds has had an intense development.
As a result of the researches carried out in the Stauffer Chemical Company, a novel type of antidotes, i.e. the N,N-disubstituted dichloroacetamides have been recognized [see the German Pat. (DE-PS) Nos. 2,218,097 and 2,350,800]. Since then, several groups of such compounds have been developed which are useful for diminishing the phytotoxicity, although their activity is different.
The antidote effect of a newer type of compounds, i.e. dicarboxylic acid derivatives (esters and amides) is described in the Hungarian Pat. No. 176,669.
Since the mechanism of action of the phytotoxicity of the above-mentioned herbicide agents is various and contraversial and the effect of the antidotes developed up to now is varying, this research is being continued.
In addition to the esters and amines, among the dicarboxylic acid derivatives as antidotes, the dinitrile derivatives [e.g. phthalic acid dinitrile (phthalonitrile) and terephthalic acid dinitrile (terephthalonitrile)] are also mentioned as substances diminishing phytotoxicity (Hungarian Pat. No. 176,669).
Likewise, the antidote effect of dinitrile derivatives is disclosed in the U.S. Pat. No. 4,260,555 and in the Soviet Pat. No. 880,242. The structure of these compounds is rather complicated. Thus, the preparation of them is difficult and expensive.
DESCRIPTION OF THE INVENTION
Now we have found, in our research aimed at the development of antidotes that the phytotoxicity of the urea derivatives of formula (II), thiolcarbamate derivatives of the formula (III) and chloroacetanilide derivatives of the formula (IV) as herbicide agents can effectively be decreased without influencing their herbicide effects by using the nitrile derivatives of the formula (I) or cyanopyridines or benzonitriles mono- or polysubstituted by halogen or alkoxy.
In the formula (I)
R.sub.1 and R.sub.2 which are the same or different, stand for hydrogen, halogen or a methyl, ethyl, allyl, vinyl, phenyl, or benzyl group; or
R.sub.1 and R.sub.2 together may stand for a benzylidene group; and
R.sub.3 is chlorine or a methyl, phenyl, chlorophenyl, alkoxyphenyl, chlorophenylamino, anilino, anilinomethylene, N-alkylanilinomethylene, N,N-dialkylanilinomethylene, alkoxyanilinomethylene, benzylaminomethylene, cyclohexylaminomethylene, N-alkyl-cyclohexylaminomethylene, hexamethyleniminomethylene, phthalimidomethylene, nitro-phthalimidomethylene, morpholinomethylene, piperidinomethylene, C.sub.1-3 alkylaminomethylene, allylaminomethylene or a di(C.sub.1-3 alkyl)aminomethylene group.
The most important compounds of the formula (I) together with the substituents as well as the physical characteristics (melting point, refractive index) of these compounds and the cyanopyridines and substituted benzonitriles are summarized in Table 1.
TABLE I__________________________________________________________________________ Physical characteristics Substituents m.p.No. Compound R.sub.1 R.sub.2 R.sub.3 .degree.C. Refractive index1 2 3 4 5 6 7__________________________________________________________________________ 1 Pivalonitrile methyl methyl methyl 15 -- 2 Trichloroacetonitrile Cl Cl Cl -- 1.440 3 4-Ethoxyphenylaceto- H H 4-ethoxy- 39-43 -- nitrile phenyl 4 2-(4-Ethoxyphenyl)butyro- H ethyl 4-ethoxy- -- 1.5117 nitrile phenyl 5 2-Phenyl-2-methylpropio- methyl methyl phenyl -- 1.5041 nitrile 6 2-Phenylbutyronitrile H ethyl phenyl -- 1.5065 7 2-Benzyl-2-phenylbutyro- ethyl benzyl phenyl -- 1.5607 nitrile 8 2-(4-Ethoxyphenyl)-2- methyl methyl 4-ethoxyphenyl 56-58 -- methylpropionitrile 9 2,3-Diphenylacrylonitrile benzylidene phenyl 86-88 --10 2-Cyanopyridine -- -- -- 212-215 --11 3-Cyanopyridine -- -- -- 50-52 --12 4-Cyanopyridine -- -- -- 78-80 --13 2-Ethyl-2-phenylbutyro- ethyl ethyl phenyl -- 1.5039 nitrile14 2-(4-Chlorophenyl)-2-ethyl- ethyl ethyl 4-chloro- 53-57 -- butyronitrile phenyl15 2-(4-Chlorophenyl)-2- methyl methyl 4-chloro- -- 1.5204 methylpropionitrile phenyl16 2-Chlorophenylaceto- H H 2-chloro- -- 1.5440 nitrile phenyl17 3-Chlorophenylaceto- H H 3-chloro- -- 1.5437 nitrile phenyl18 4-Chlorophenylaceto- H H 4-chloro- 265-267 -- nitrile phenyl19 Diphenylacetonitrile H phenyl phenyl 71-73 --20 3-Phthalimidopropionitrile H H phthalimido- 153-154 -- methylene21 3-(3-Nitrophthalimido)- H H 3-nitro- 132-134 -- propionitrile phthalimido- methylene22 3-(4-Nitrophthalimido)- H H 4-nitro- 136-138 -- propionitrile phthalimido- methylene23 2-Allyl-2-phenyl-4-pentene- allyl allyl phenyl -- 1.5243 nitrile24 3-Anilinopropionitrile H H anilino- 48-49 -- methylene25 3-Cyclohexylaminopropio- H H cyclohexyl- -- 1.4737 nitrile aminomethylene26 3-Benzylaminopropio- H H benzylamino- -- 1.5272 nitrile methylene27 3-N--(Ethylcyclohexyl)- H H N--ethylcyclohexyl- -- 1.4709 aminopropionitrile aminomethylene28 3-N--(Methylanilino)- H H N--methylanilino- -- 1.5591 propionitrile methylene29 3-N--(Ethylanilino)- H H N--ethylanilino- -- 1.5528 nitrile methylene30 3-N--(Isopropylanilino)- H H N--ispropyl- -- 1.5418 propionitrile anilino- methylene31 3-Hexamethylenimino- H H hexamethylen- -- 1.4727 propionitrile iminomethylene32 3-Morpholinopropio- H H morpholino- -- 1.4698 nitrile methylene33 3-Piperidinopropionitrile H H piperidinomethylene -- 1.469034 3-(4-Methoxyanilino)- H H 4-methoxy- 62-64 -- propionitrile anilino- methylene35 3-(2,6-Diethylanilino)- H H 2,6-diethyl- -- 1.5431 propionitrile anilino- methylene36 2-Anilinoacetonitrile H H Anilino 45-47 --37 2-(4-Chlorophenyl)- H H 4-chloro- 92-95 -- aminoacetonitrile phenylamino38 Phenylacetonitrile H H phenyl -- 1.523639 2-Anilinopropionitrile H methyl anilino 86-88 --40 (4-Methoxyphenyl)aceto- H H 4-methoxy- -- 1.5318 nitrile phenyl41 3-Methylaminopropio- H H methylamino- -- 1.4348 nitrile methylene42 3-Diethylaminopropio- H H diethylamino- -- 1.4358 nitrile methylene43 3-Phthalimido-2-methylpro- H H phthalimido- 94-96 -- pionitrile methylene44 2-Methyl-3-(4-nitro- H methyl 4-nitrophthal- -- -- phthalimido)propionitrile imidomethylene45 2-Methyl-3-(3-nitrophthal- H methyl 3-nitro-phthal- -- imido)-propionitrile imidomethylene46 3-Anilino-2-methylpropio- H methyl anilinomethylene 1.4714 nitrile47 3-Benzylamino-2-methyl- H methyl benzylamino- -- 1.5312 propionitrile methylene48 3-N--Methylanilino-2- H methyl N--methyl- -- 1.5510 methylpropionitrile anilino- ethylene49 3-Cyclohexylamino-2- H methyl ciklohexyl- -- 1.4797 methylpropionitrile aminomethylene50 3-N--Ethylanilino-2- H methyl N--ethylanilino- 1.5484 methylpropionitrile methylene51 3-N--Isopropylanilino- H methyl N--isopropyl- 1.5392 2-methylpropionitrile anilinomethylene52 2-Chlorobenzonitrile -- -- -- 44-45 --53 2,4,6-Trimethoxy- -- -- -- 92-94 -- benzonitrile54 3-Chlorobenzonitrile -- -- -- 38-40 --55 4-Chlorobenzonitrile -- -- -- 91-93 --56 3-(2,6-Dimethylanilino)- H H 2,6-dimethyl- -- 1.4832 propionitrile anilinomethylene57 3-(6-Ethyl-2-methyl- H H 6-ethyl-2- -- 1.4916 anilino)propionitrile methylanilino- methylene58 3-(n-Propylamino)- H H propylamino- -- 1.4354 propionitrile methylene59 3-Allylaminopropio- H H allylamino- -- 1.4547 nitrile methylene__________________________________________________________________________
For the preparation of the nitrile derivatives of the formula (I), several processes are known in the literature.
Pivalonitrile, item No. 1 in Table I, which is the simplest derivative can be prepared by reacting pivalic acid with ammonia under dehydrating conditions [see the German Pat. No. 3,216,382]. However, pivalonitrile (trimethylacetoritrile) can also be prepared by reacting the appropriate olefin, i.e. isobutylene with hydrogen cyanide at an elevated temperature [see the U.S. Pat. No. 2,455,995].
According to K. Rokrig et al., 4-ethoxyphenylacetonitrile is prepared by reacting 4-ethoxybenzyl chloride with sodium cyanide (Org. Synth. Coll. Vol. IV., p. 576).
M. Lora et al. transformed pivalic acid to the acid chloride by using thionyl chloride in the first step, and the acid chloride was then reacted with ammonia to give pivalic acid amide. This amide was reacted with phosphorus pentoxide in a solvent to yield pivalonitrile (Anales Real. Soc. Espan. 48B, p. 414-420).
Among the urea derivatives of the formula (II), the phytotoxicity of which is decreased by the nitrile derivatives of the formula (I), 3-(4-chlorophenyl)-1,1-dimethylurea (monuron), 3-(3,4-dichlorophenyl)-1,1-dimethylurea (diuron), 3-(3-chloro-4-methoxyphenyl)-1,1-dimethylurea (metoxuron), 3-(3-chloro-4-methylphenyl)-1,1-dimethylurea (chlortoluron), 3-(4-chlorophenyl)-1-methyl-1-methoxyurea (monoliruror), 3-(3,4-dichlorophenyl)-1-methyl-1-methoxyurea (linuron), 3-(4-bromophenyl)-1-methyl-1-methoxyurea (metobromuron), 3-(4-bromo-3-chloropheryl)-1-methyl-1-methoxyurea (chlorbromuron), 3-[3-(trifluormethyl)phenyl]-1,1-dimethylurea (fluometuron), 1,1-dimethyl-3-phenylurea (fenuron) and 1,1-dimethyl-3-(4-isopropylphenyl)urea (isoproturon) are well known substances.
Among the thiolcarbamate derivatives of the formula (III), for which the nitrile derivatives of the formula (I) are useful antidotes, the following compounds are well known and widely used in the practice: S-ethyl N,N-diisobutylthiolcarbamate (butylate), S-ethyl N,N-di(n-propyl)thiolcarbamate (EPTC), S-ethyl N,N-hexamethylenethiolcarbamate (molinate), S-ethyl N-cyclohexyl-N-ethylthiolcarbamate (cycloate), S-propyl N,N-di(n-propyl)thiolcarbamate (vernolate), S-(2,3-dichloroallyl) N,N-diisopropylthiolcarbamate (diallate), S-(4-chlorobenzyl)-N,N-diethylthiolcarbamate (thiobencarb) and S-benzyl N,N-di(secundary-butyl)thiolcarbamate.
Among the chloroacetanilide derivatives of the formula (IV), the phytotoxicity of which is diminished by the nitrile derivatives of the formula (I), the most known substances are as follows:
2-chloro-2',6'-diethyl-N(methoxymethyl)acetanilide (alachlor),
2-chloro-2'-ethyl-6'-methyl-N-(ethoxymethyl)acetanilide (acetochlor),
2-chloro-2'-ethyl-6'-methyl-N-(1-methyl-2-methoxyethyl)acetanilide (metolachlor) and
2-chloro-2',6'-diethyl-N-(butoxymethyl)acetanilide (butachlor).
As clearly seen from Table I, the nitrile derivatives of the formula (I) are partly solids and partly liquids.
The solid nitrile derivatives can be formulated e.g. to wettable powders (WP) by using the common additives of plant protective compositions (carriers, surface active agents), which may be applied together with herbicide compositions of a similar formulation in the form of tank mixtures.
Both the liquid and solid nitrile derivatives can be formulated e.g. to stable emulsifiable concentrates by selecting a suitable solvent and emulsifying agent which may be mixed with herbicide emulsifiable concentrates and may be applied in the form of tank mixtures.
The nitrile derivatives may also be formulated together with the urea derivatives and/or thiolcarbamate derivatives and/or chloroacetanilide derivatives.

SPECIFIC EXAMPLES
The formulations containing the nitrile derivatives alone as well as the compositions formulated together with herbicide agents are illustrated in detail in the following non-limiting Examples.
EXAMPLE 1
Composition of an emulsifiable concentrate containing 2,3-diphenylacrylonitrile (compound No. 9) as antidote
______________________________________ % by mass______________________________________2,3-Diphenylacrylonitrile 10Atlox 4857B emulsifying agent 10Xylene 80______________________________________
EXAMPLE 2
Composition of an emulsifiable concentrate containing trichloroacetonitrile (compound No. 2) as antidote
______________________________________ % by mass______________________________________Trichloroacetonitrile 20Emulsogen IP 400 10Xylene 70______________________________________
EXAMPLE 3
Composition of an emulsifiable concentrate containing 2-benzyl-2-phenylbutyronitrile (compound No. 7) as antidote
______________________________________ % by mass______________________________________2-Benzyl-2-phenylbutyronitrile 30Atlox 4857B emulsifying agent 10Xylene 60______________________________________
Emulsifiable concentrates with a similar composition may be prepared by using 4-chlorophenylacetonitrile (compound No. 18), 2-(4-chlorophenyl)-2-methylpropionitrile (compound No. 15), or 2-(4-ethoxyphenyl)butyronitrile (compound No. 4) as antidotes.
EXAMPLE 4
Composition of an emulsifiable concentrate containing pivaloritrile (compound No. 1) as antidote
______________________________________ % by mass______________________________________Pivalonitrile 50Emulsogen IP 400 emulsifying agent 10Xylene 40______________________________________
EXAMPLE 5
Composition of an emulsifiable concentrate containing 2-cyanopyridine (compound No. 10) as antidote
______________________________________ % by mass______________________________________2-Cyanopyridine 50Emulsogen IP 400 emulsifying agent 10Xylene 40______________________________________
EXAMPLE 6
Composition of a wettable powder containing 2-methyl-2-phenylpropionitrile (compound No. 5) as antidote
______________________________________ % by mass______________________________________2-Methyl-2-phenylpropionitrile 20Arkopon T 5Dispergiermittel SI dispersing agent 5Zeolit 424 carrier 70______________________________________
EXAMPLE 7
Composition of a wettable powder containing (4-ethoxyphenyl)acetonitrile (compound No. 3) as antidote
______________________________________ % by mass______________________________________(4-Ethoxyphenyl)acetonitrile 40Arkopon T 5Dispergiermittel SI dispersing agent 5Zeolit 424 carrier 50______________________________________
EXAMPLE 8
Composition of a wettable powder containing 3-cyanopyridine (compound No. 11) as antidote
______________________________________ % by mass______________________________________3-Cyanopyridine 70Arkopon T 5Dispergiermittel SI dispersing agent 5Zeolex 424 carrier 20______________________________________
EXAMPLE 9
Composition of a water-soluble concentrate (WSC) containing pivalonitrile (compound No. 1) as antidote
______________________________________ % by mass______________________________________Pivalonitrile 90Emulsogen IP 400 emulsifying agent 10______________________________________
EXAMPLE 10
Composition of an emulsifiable concentrate containing 4-cyanopyridine (compound No. 12) as antidote
______________________________________ % by mass______________________________________4-Cyanopyridine 10Atlox 4857B emulsifying agent 10Chlorobenzene 80______________________________________
EXAMPLE 11
Composition of an emulsifiable concentrate containing 2-(4-ethoxyphenyl)-2-methylpropionitrile (compound No. 8) as antidote
______________________________________ % by mass______________________________________2-(4-Ethoxyphenyl)-2-methylpropionitrile 40Atlox 4857B emulsifying agent 15Xylene 45______________________________________
The nitrile derivatives of the formula (I) can be well formulated together with the urea derivatives of the formula (II) and/or the thiolcarbamate derivatives of the formula (III) and/or with chloroacetanilide derivatives of the formula (IV) as illustrated in the following Examples.
EXAMPLE 12
Composition of a wettable powder containing an antidote and an urea as active ingredient
______________________________________ % by mass______________________________________N--(3,4-Dichlorphenyl)-N'--methyl-N'-- 50methoxyureaTrichloroacetonitrile (compound No. 2) 25Amorphous silicic acid carrier 20Fatty alcohol sulfonate 2.5Sodium lignin sulfonate 2.5______________________________________
The above components are homogenized in a powder mixer, then finely ground in an Alpine 100 LU type laboratory mill. The floatability of the composition amounts to 88%.
EXAMPLE 13
Composition of an emulsifiable concentrate containing an antidote and a thiolcarbamate as active ingredient
______________________________________ % by mass______________________________________S--Ethyl N,N--di(n-propyl)thiolcarbamate 64.82-Ethyl-2-phenylbutyronitrile (compound 10.0No. 13)Atlox 4857B emulsifying agent 4.3Atlox 3400 B emulsifying agent 2.9Kerosine 18.0______________________________________
EXAMPLE 14
Composition of an emulsifiable concentrate containing an antidote and a thiolcarbamate as active ingredient
______________________________________ % by mass______________________________________S--Propyl N,N--di(n-propyl)thiolcarbamate 67.5Trichloroacetonitrile (compound No. 2) 10.0Tensiofix AS emulsifying agent 4.3Tensiofix IS emulsifying agent 2.9Kerosine 15.3______________________________________
EXAMPLE 15
Composition of a wettable powder containing an antidote and an urea as active ingredient
______________________________________ % by mass______________________________________1,1-Dimethyl-3-phenylurea 503-Cyanopyridine (compound No. 11) 10Zeolit 424 carrier 20Siliceous earth carrier 20Netzer IS wetting agent 2Dispergiermittel 3Sulfite waste powder 5______________________________________
The above components are homogenized in a powder mixer, then finely ground in an Alpine 100 LU type laboratory mill. The floatability of the composition amounts to 88%.
EXAMPLE 16
Composition of a wettable powder containing an antidote and an urea as active ingredient
______________________________________ % by mass______________________________________3-(3,4-Dichlorophenyl)-1,1-dimethylurea 402,3-Diphenylacrylonitrile (compound No. 9) 40Zeolit 424 carrier 12Netzer IS wetting agent 1.5Dispergiermittel 2.5Sulfite waste powder 4.0______________________________________
The above components are treated as described in Example 15 to give a powder composition with a floatability of 82.5%.
EXAMPLE 17
Composition of a wettable powder containing an antidote and an urea as active ingredient
______________________________________ % by mass______________________________________1,1-Dimethyl-3-[(3-(trifluoromethyl)- 50phenyl]-urea4-Cyanopyridine (compound No. 12) 25Zeolit 424 carrier 15Netzer IS 2Dispergiermittel 3Sulfite waste powder 5______________________________________
The above components are treated as described in Example 15 to give a powder composition with a floatability of 86.4%.
EXAMPLE 18
Composition of a wettable powder containing an antidote and an urea as active ingredient
______________________________________ % by mass______________________________________3-(3,4-Dichlorophenyl)-1-methyl-1- 48methoxyureaPremix containing pivalonitrile 20Siliceous earth carrier 22Netzer IS wetting agent 2Dispergiermittel 3Sulfite waste powder 5______________________________________
The above components are treated as described in Example 15 to give a powder composition with a floatability of 76%.
The premix containing the above antidote was prepared in such a way that 2 parts by mass of pivalonitrile (compound No. 1) as antidote were dissolved in 5 parts by mass of dichloromethane as solvent, then the thus-obtained solution was sprayed onto 18 parts by mass of Sipermat 50 synthetic silicate carrier under stirring, then the solvent was evaporated at 50.degree. C.
EXAMPLE 19
Composition of a wettable powder containing an antidote and an urea as active ingredient
______________________________________ % by mass______________________________________3-(4-Bromo-3-chlorophenyl)-1-methyl-1- 50methoxyureaPremix containing 2-benzyl-2-phenyl- 25butyronitrileSiliceous earth carrier 15Netzer IS wetting agent 2Dispergiermittel 3Sulfite waste powder 5______________________________________
The above components are treated as described in Example 15 to give a powder composition with a floatability of 78.4%.
The premix containing the above antidote was prepared in such a way that 5 parts by mass of 2-benzyl-2-phenylbutyronitrile (compound No. 7) as antidote were dissolved in 5 parts by mass of dichloromethane, then the thus-obtained solution was sprayed onto 20 part by mass of Sipermat 50 synthetic silicate carrier and the solvent was evaporated at 50.degree. C.
EXAMPLE 20
Composition of an emulsifiable concentrate containing an antidote and an urea as active ingredient
______________________________________ % by mass______________________________________1,1-Dimethyl-3-phenylurea 18Pivalonitrile (compound No. 1) 2Emulsogen IP 400 emulsifying agent 6.4Emulsogen EL 400 emulsifying agent 1.61:1 mixture of xylene with dichloro- 72.0methane______________________________________
EXAMPLE 21
Composition of an emulsifiable concentrate containing an antidote and an urea as active ingredient
______________________________________ % by mass______________________________________3-(4-Bromo-3-chlorophenyl)-1-methyl-1- 35methoxyurea4-Ethoxyphenylacetonitrile (compound 5No. 3)Emulsogen IP 400 emulsifying agent 7.2Emulsogen EL 400 emulsifying agent 0.82:2:1 mixture of xylene with dichloro- 52.0methane and dimethylformamide______________________________________
EXAMPLE 22
Composition of an emulsifiable concentrate containing an antidote and an urea as active ingredient
______________________________________ % by mass______________________________________3-(4-Bromophenyl)-1-methyl-1-methoxy- 24urea2-(4-Chlorophenyl)-2-ethylbutyro- 3nitrile (compound No. 14)Emulsogen IP 400 emulsifying agent 6.4Emulsogen EL 400 emulsifying agent 1.62:2:1 mixture of xylene with dichloro- 62.0methane and dimethylformamide______________________________________
EXAMPLE 23
Composition of an emulsifiable concentrate containing an antidote and an urea as active ingredient
______________________________________ % by mass______________________________________1,1-Dimethyl-3-[3-(trifluoromethyl)- 23phenyl]-urea3-Cyanopyridine (compound No. 11) 2Emulsogen IP 400 emulsifying agent 6.4Emulsogen EL 400 emulsifying agent 1.61:1 mixture of xylene with dimethyl- 67.0formamide______________________________________
EXAMPLE 24
Composition of an emulsifiable concentrate containing an antidote and a chloroacetanilide as active ingredient
______________________________________ % by mass______________________________________2-Chloro-2',6'-diethyl-N--methoxymethyl- 35acetanilide2-(4-Chlorophenyl)-2-ethylbutyronitrile 5(compound No. 14)Emulsogen IP 400 emulsifying agent 6.4Emulsogen EL 400 emulsifying agent 1.63:1 mixture of Aromatol with dimethyl- 52.0formamide______________________________________
EXAMPLE 25
Composition of an emulsifiable concentrate containing antidote with a chloroacetanilide and an urea as active ingredients
______________________________________ % by mass______________________________________2-Chloro-2',6'-diethyl-N--methoxy- 32methylacetanilide3-(4-Bromophenyl)-1-methyl-1-methoxy- 15ureaPivalonitrile (compound No. 1) 3Emulsogen IP 400 emulsifying agent 7.2Emulsogen EL 400 emulsifying agent 0.82:2:1 mixture of xylene with dichloro- 42methane and dimethylformamide______________________________________
EXAMPLE 26
Composition of an emulsifiable concentrate containing an antidote with a chloroacetanilide and an urea as active ingredients
______________________________________ % by mass______________________________________2-Chloro-2',6'-diethyl-N--methoxy- 31methylacetanilide3-(4-Bromo-3-chlorophenyl)-1-methyl-1- 15methoxyurea3-Cyanopyridine (compound No. 11) 2Emulsogen IP 400 emulsifying agent 7.2Emulsogen EL 400 emulsifying agent 0.81:1 mixture of cyclohexanone with 44Aromatol______________________________________
EXAMPLE 27
Composition of an emulsifiable concentrate containing an antidote and a thiolcarbamate as active ingredient
______________________________________ % by mass______________________________________S--Ethyl N,N--diisobutylthiolcarbamate 90.02-(4-Ethoxyphenyl)butyronitrile (com- 1.0pound No. 4)Atlox 3400 B emulsifying agent 2.0Atlox 4857B emulsifying agent 4.0Kerosine 3.0______________________________________
EXAMPLE 28
Composition of a granulate containing an antidote and a thiolcarbamate as active ingredient
______________________________________ % by mass______________________________________S--Ethyl N,N--hexamethylenethiolcarbamate 5.03-Cyclohexylaminopropionitrile 3.0(compound No. 25)Calcined siliceous earth granulate 92.0carrier______________________________________
The above thiolcarbamate active ingredient and the antidote are dissolved in 10% by mass of dichloromethane and sprayed onto the carrier in a rotary granulating equipment under stirring, then the solvent is evaporated at 50.degree. C. to give a granulate with a particle size of 0.2 to 1.0 mm.
EXAMPLE 29
Composition of a suspension (suspendable) concentrate containing an antidote with a thiolcarbamate and an urea as active ingredients
______________________________________ % by mass______________________________________S--Ethyl N--cyclohexyl-N--ethylthiol- 40.0carbamate3-(3,4-Dichlorophenyl)-1,1-dimethyl 40.0urea3-Phthalimidopropionitrile (compound 5.0No. 20)Atlox 4896 B emulsifying agent 6.0Atlox 4857 B emulsifying agent 2.0Aqueous thickening solution of 2% by 7.0mass of a polysaccharide______________________________________
The tiolcarbamate active ingredient and the emulsifying agents are homogenized by stirring, then the urea active ingredient and the antidote are suspended in the mixture under stirring. The thus-obtained coarse disperse system is finely ground in a laboratory pearl mill and then homogenized with the thickening solution to give a suspension (suspendable) concentrate with a particle size lower than 10.mu. (in 92%) and having a floatability of 88.2%.
EXAMPLE 30
Composition of an emulsifiable concentrate containing an antidote and a thiolcarbamate active ingredient
______________________________________ % by mass______________________________________S--(2,3-Dichloroallyl) N,N--diisopropyl- 40.0thioIcarbamate4-Methoxyphenylacetonitrile (compound 4.0No. 40)Atlox 3400 B emulsifying agent 2.2Atlox 4857 B emulsifying agent 3.84:1 mixture of xylene with isophorone 50.0______________________________________
EXAMPLE 31
Composition of an emulsifiable concentrate containing an antidote with a thiolcarbamate and a chloroacetanilide as active ingredients
______________________________________ % by mass______________________________________S--(4-Chlorobenzyl) N,N--diethylthiol- 75.0carbamate2-Chloro-2'-ethyl-6'-methyl-N--ethoxy- 5.0methylacetanilide3-Cyclohexylamino-2-methylpropionitrile 2.0(compound No 49)Tensiofix AS emulsifying agent 2.5Tensiofix IS emulsifying agent 5.5Xylene 10.0______________________________________
EXAMPLE 32
Composition of a wettable powder containing an antidote and an urea as active ingredient
______________________________________ % by mass______________________________________3-(3,4-Dichlorophenyl)-1,1-dimethyl- 80.0urea4-Chlorophenylacetonitrile (compound 2.0No. 18)Netzer IS wetting agent 2.0Dispergiermittel 1494 dispersing agent 4.0Wessalon S carrier 12.0______________________________________
The above components are treated as described in Example 15 to give a powder composition with a floatability of 86.4%.
EXAMPLE 33
Composition of an emulsifiable concentrate containing an antidote with an urea and a chloroacetanilide as active ingredients
______________________________________ % by mass______________________________________2-Chloro-2'-ethyl-6'-methyl-N--(1-methyl- 60.02-methoxyethyl)acetanilide3-(3-Chloro-4-methoxyphenyl)-1,1- 5.0dimethylurea3-N--Isopropylanilino-2-methylpropio- 5.0nitrile (compound No. 51)Tensiofix AS emulsifying agent 6.5Tensiofix IS emulsifying agent 1.51:1 mixture of xylene with cyclohexanone 22.0______________________________________
EXAMPLE 34
Composition of an equeous suspension (suspendable) concentrate containing an antidote and an urea as active ingredient
______________________________________ % by mass______________________________________3-(3-Chloro-4-methylphenyl)-1,1-di- 46.0methylurea2-Chlorobenzonitrile (compound No. 52) 4.0Atlox 4853 B emulsifying agent 5.0Atlox 4896 B emulsifying agent 3.0Water 35.0Aqueous thickening solution of 2% by 7.0mass of a polysaccharide______________________________________
The emulsifying agents are dissolved in the water, then the urea active ingredient and the antidote are suspended in the solution. Thereafter, the coarse disperse system is finely ground in a laboratory pearl mill and then homogenized with the thickening solution to give an aqueous suspension concentrate with a particle size lower than 10.mu. (in 93.6%) and having a floatability of 91.4%.
EXAMPLE 35
Composition of a wettable powder containing an antidote and an urea as active ingredient
______________________________________ % by mass______________________________________1,1-Dimethyl-3-(4-isopropylphenyl)urea 72.02,4,6-Trimethoxybenzonitrile (compound 8.0No. 53)Netzer IS wetting agent 2.5Dispergiermittel 1494 dispersing agent 3.5Ultrasyl VN 3 carrier 14.0______________________________________
The above components are treated as described in Example 15 to give a powder composition with a floatability of 87.2%.
EXAMPLE 36
Composition of a wettable powder containing an antidote and an urea as active ingredient
______________________________________ % by mass______________________________________3-(4-Chlorophenyl)-1,1-dimethylurea 76.02-(4-Chlorophenylamino)acetonitrile 4.0(compound No. 37)Netzer IS wetting agent 2.0Dispergiermittel 1494 dispersing agent 4.0Ultrasyl VN 3 carrier 14.0______________________________________
The above components are treated as described in Example 15 to give a powder composition with a floatability of 85.9%.
EXAMPLE 37
Composition of an emulsifiable concentrate containing an antidote and a chloroacetanilide as active ingredient
______________________________________ % by mass______________________________________2-Chloro-2',6'-diethyl-N--butoxymethyl- 78.0acetanilide2-Methyl-2-phenylpropionitrile (compound 2.0No. 5)Tensiofix AS emulsifying agent 3.6Tensiofix IS emulsifying agent 2.41:1 mixture of xylene with dimethyl- 14.0formamide______________________________________
The auxiliary materials used in the above formulation Examples were as follows:
Emulsogen: a mixture of calcium dodecylbenzenesulfonate with fatty acid polyglycol esters (product of Hoechst)
Netzer: sodium alkylsulfonate (product of Hoechst)
Arkopon T: sodium oleylmethyltauride (product of Hoechst)
Dispergiermittel: a forecondensate of cresol and formaldehyde (product of Hoechst)
Atlox: a mixture of calcium dodecylbenzenesulfonate with poly(oxyethylene)alkylphenols (product of Atlas Chemie)
Tensiofix: octylphenyol polyglycol ether or nonylphenol polyglycol ether, respectively (product of Tensia)
Zeolex: a synthetic silicate carrier (product of Zeofinn Org. Hamine)
Wessalon S: a synthetic silicate carrier (product of Degussa)
Ultrasyl VN 3: a synthetic silicate carrier (product of Degussa)
Aromatol: a solvent mixture containing 98% of aromatic compounds with a boiling point of 145.degree. to 190.degree. C. (product of the Dunai Koolajipari Vallalat) (Duna Petroleum Industry Comp.).
The phytotoxicity decreasing effect of the nitrile derivatives of the formula (I) were investigated both in greenhouse as well as in field experiments.
During our inventigations, the percentage value of sprouting of the cultivated plant, the damaging effect observed on the cultivated plant and the herbicide action were measured by using the internationally accepted EWRC scores. These data are summarized in Table II.
TABLE II______________________________________ Herbi- Phytotoxic symptoms General appearance cideEWRC observed on of effectscore cultivated plants %______________________________________1 none excellent 1002 very mild very good 983 mild symptoms good 954 strong but transient satisfactory 90 symptoms, decrease in crop5 symptoms of unknown problematic 82 origin6 observable harmful unsatisfactory 70 symptoms7 symptoms of a strong poor 55 damage8 symptoms of a very very poor 30 strong damage9 total perishment unsuitable 0______________________________________
EXAMPLE 38
Study of the antidote effect on urea-type herbicides in greenhouse tests
These tests were carried out in cultivating pots with 4-fold repetitions. The pots of 14 cm in diameter were filled with soil, then 10 maize grains each were sown in the pots and covered with a soil layer of 4 cm in height. Then, the pots were treated with the appropriate amount of an urea-type herbicide and the formulated antidote. The plants were cultivated in a greenhouse and sprinkled when necessary. The sprouting plants were evaluated at the end of the fourth week following the sowing. The percentage of the sprouting and the EWRC score of the maize were determined.
TABLE III______________________________________ Treatment withNitrile Antidote Herbicide Sprout-compound Herbicide kg/hec- kg/hec- ing EWRCNo. agent tare tare % score______________________________________1 Fenuron 2.5 2.0 93.3 11 Fenuron 2.5 1.0 93.3 21 Fenuron 0.5 2.0 96.6 11 Fenuron 0.5 1.0 93.3 12 Fenuron 0.5 2.0 95.0 211 Fenuron 0.5 2.0 93.0 21 Linuron 2.5 2.5 96.6 31 Linuron 2.5 1.25 95.3 31 Linuron 0.5 2.5 94.0 11 Linuron 0.5 1.25 93.5 12 Linuron 0.5 1.25 96.6 12 Linuron 0.5 2.50 95.0 22 Linuron 2.5 1.25 96.6 12 Linuron 2.5 2.50 92.5 23 Linuron 0.5 1.25 97.5 23 Linuron 0.5 2.50 96.6 33 Linuron 2.5 1.25 94.3 23 Linuron 2.5 2.50 93.5 24 Linuron 0.5 1.25 97.5 14 Linuron 0.5 2.50 95.0 24 Linuron 2.5 1.25 96.6 14 Linuron 2.5 2.50 94.0 26 Linuron 0.5 1.25 97.5 16 Linuron 0.5 2.50 96.6 26 Linuron 2.5 1.25 96.6 26 Linuron 2.5 2.50 92.0 38 Linuron 0.5 1.25 95.0 28 Linuron 0.5 2.50 93.5 28 Linuron 2.5 1.25 94.0 28 Linuron 2.5 2.50 92.0 29 Linuron 0.5 1.25 96.6 19 Linuron 0.5 2.50 92.5 29 Linuron 2.5 1.25 96.6 29 Linuron 2.5 2.50 92.5 211 Linuron 0.5 1.25 100.0 111 Linuron 0.5 2.50 96.6 111 Linuron 2.5 1.25 96.6 111 Linuron 2.5 2.50 96.6 112 Linuron 0.5 1.25 97.5 112 Linuron 0.5 2.50 95.0 212 Linuron 2.5 1.25 96.6 212 Linuron 2.5 2.50 92.5 313 Linuron 0.5 1.25 97.5 113 Linuron 0.5 2.50 97.5 113 Linuron 2.5 1.25 97.5 113 Linuron 2.5 2.50 97.5 114 Linuron 0.5 1.25 96.6 114 Linuron 0.5 2.50 95.0 214 Linuron 2.5 1.25 95.0 214 Linuron 2.5 2.50 92.5 215 Linuron 0.5 1.25 97.5 115 Linuron 0.5 2.50 95.0 215 Linuron 2.5 1.25 95.0 115 Linuron 2.5 2.50 92.5 216 Linuron 0.5 1.25 95.0 216 Linuron 0.5 2.50 95.0 216 Linuron 2.5 1.25 95.0 216 Linuron 2.5 2.50 95.0 217 Linuron 0.5 1.25 97.5 117 Linuron 0.5 2.50 95.0 217 Linuron 2.5 1.25 95.0 217 Linuron 2.5 2.50 92.5 318 Linuron 0.5 1.25 97.5 118 Linuron 0.5 2.50 97.5 118 Linuron 2.5 1.25 95.0 218 Linuron 2.5 2.50 95.0 219 Linuron 0.5 1.25 95.0 219 Linuron 0.5 2.50 95.0 219 Linuron 2.5 1.25 92.5 319 Linuron 2.5 2.50 92.5 323 Linuron 0.5 1.25 97.5 123 Linuron 0.5 2.50 97.5 123 Linuron 2.5 1.25 97.5 123 Linuron 2.5 2.50 97.5 152 Linuron 0.5 1.25 97.5 152 Linuron 0.5 2.50 95.0 252 Linuron 2.5 1.25 96.5 152 Linuron 2.5 2.50 95.0 2CGA 43.089 Linuron 0.5 1.25 92.5 3CGA 43.089 Linuron 0.5 2.50 90.0 3CGA 43.089 Linuron 2.5 1.25 89.0 3CGA 43.089 Linuron 2.5 2.50 89.0 3-- Linuron -- 2.0 88.0 7-- Fenuron -- 1.0 90.0 5-- Linuron -- 2.5 86.0 7-- Linuron -- 1.25 89.0 5-- untreated -- -- 96.6 1 control______________________________________
A known antidote, cyanomethoxy-iminophenylacetonitrile (code number: CGA 43,089: was used as reference agent in these experiments.
The data of Table III prove that the toxicity of both fenuron and linuron is diminished and the sprouting percentage of the maize is improved by using the nitrile derivatives.
EXAMPLE 39
Study of the antidote effect in the case of thiolcarbamate-type herbicides in greenhouse tests
These tests were carried out in pots of 14 cm in diameter with 5-fold repetitions. The pots were filled with sandy adobe soil to the two-thirds of their volume and 10 grains of maize each were placed in the pots. Then, the grains were covered with treated or untreated, respectively soil of 5 cm in height according to the given experiment. The soil was treated in such a way that the composition containing both the antidote and herbicide as calculated for the soil with a given surface area was diluted with a water amount corresponding to 400 liters/hectare and then, this mixture was sprayed onto the soil by using a rotary, small concrete mixer. In addition to the experimental samples treated with the herbicide alone or treated, respectively with both the antidote and herbicide, an untreated control was also used.
The plants were cultivated in a greenhouse and sprinkled when necessary. The evaluation was carried out at the end of the fourth week following the sowing. The percentage of sprouting and the EWRC score were determined; furthermore, the green weight of the sprouting plant was measured and related to that of the untreated control. The results are summarized in Table IV.
TABLE IV______________________________________Treatment withNitrile Antidote Herbicide Greencompound kg/ EPTC Sprouting EWRC weightNo. hectare kg/hectare % score %______________________________________1 2.50 -- 83.3 1 85.81 2.50 8.0 80.0 1 99.71 0.50 8.0 76.6 1 100.810 2.50 -- 83.3 1 98.710 2.50 8.0 83.3 1 87.513 0.50 8.0 80.0 1 92.121 0.50 8.0 80.0 3 94.521 1.00 8.0 83.3 2 94.419 0.50 8.0 83.3 1 96.019 0.75 8.0 76.6 3 91.018 0.50 8.0 76.6 3 90.018 0.75 8.0 83.3 1 97.9-- -- 8.0 63.3 5 70.8R 25788 0.5 8.0 63.3 2 88.3-- -- -- 83.3 1 100.0______________________________________
It can clearly be seen from Table IV that, on using the nitrile antidotes according to the invention, both the percentage of sprouting and the green weight became more advantageous on comparison to the known antidote N,N-diallyldichloroacetamide (R 25788).
EXAMPLE 40
Study of the antidote effect in the case of chloroacetanilide-type herbicides in greenhouse tests
These tests were carried out in pots of 14 cm in diameter with 4-fold repetitions. The pots were filled with soil to the two-thirds of their volume and 10 sugar beet seeds each were sown in the pots, then covered with soil of 4 cm in height. The treatment was carried out with a tank mixture containing both the antidote and the chloroacetanilide-type herbicide.
The plants were cultivated in a greenhouse and sprinkled when necessary. The experiments were evaluated after sowing. The results are summarized in Table V.
TABLE V______________________________________ Treatment withNitrile Herbicidecompound Antidote Acenit 50 EC Sprouting EWRCNo. kg/hectare kg/hectare % %______________________________________1 2.5 -- 73.3 11 2.5 10 53.3 11 2.5 5 76.6 11 0.5 -- 90.0 11 0.5 10 43.3 11 0.5 5 73.3 110 2.5 -- 80.0 110 2.5 10 50.0 510 2.5 5 73.3 110 0.5 -- 76.6 110 0.5 10 46.6 510 0.5 5 80.0 111 2.5 -- 73.3 111 2.5 10 46.6 511 2.5 5 73.3 111 0.5 -- 76.6 111 0.5 10 46.6 511 0.5 5 43.3 520 0.5 -- 80.0 120 0.5 5 73.5 120 0.5 10 46.6 320 2.5 -- 76.6 120 2.5 5 73.3 120 2.5 10 53.3 221 0.5 -- 76.6 121 0.5 5 76.6 121 0.5 10 66.6 221 2.5 -- 73.3 121 2.5 5 66.6 221 2.5 10 63.3 222 0.5 -- 76.6 122 0.5 5 76.6 122 0.5 10 66.6 222 2.5 -- 76.6 122 2.5 5 73.3 222 2.5 10 60.0 324 0.5 -- 73.3 124 0.5 5 76.6 124 0.5 10 63.3 224 2.5 -- 76.6 124 2.5 5 56.6 324 2.5 10 46.6 325 0.5 -- 76.6 125 0.5 5 76.6 125 0.5 10 70.0 225 2.5 -- 76.6 125 2.5 5 76.6 125 2.5 10 73.3 130 0.5 -- 76.6 130 0.5 5 73.3 130 0.5 10 60.0 230 2.5 -- 73.3 130 2.5 5 70.0 230 2.5 10 56.6 332 0.5 -- 76.6 132 0.5 5 73.6 232 0.5 10 60.0 232 2.5 -- 76.6 132 2.5 5 60.0 332 2.5 10 46.6 333 0.5 -- 76.6 133 0.5 5 70.0 133 0.5 10 56.6 233 2.5 -- 80.0 133 2.5 5 73.6 133 2.5 10 70.0 134 0.5 -- 76.6 134 0.5 5 76.6 134 0.5 10 73.6 134 2.5 -- 76.6 134 2.5 5 63.3 234 2.5 10 46.6 436 0.5 -- 76.6 136 0.5 5 73.3 136 0.5 10 66.6 236 2.5 -- 76.6 136 2.5 5 66.6 236 2.5 10 53.3 237 0.5 -- 76.6 137 0.5 5 66.6 237 0.5 10 50.0 337 2.5 -- 76.6 137 2.5 5 46.6 337 2.5 10 43.3 439 0.5 -- 76.6 139 0.5 5 76.6 139 0.5 10 66.6 239 2.5 -- 76.6 139 2.5 5 53.3 339 2.5 10 53.3 340 0.5 -- 76.6 140 0.5 5 73.3 140 0.5 10 56.6 240 2.5 -- 80.0 140 2.5 5 53.3 240 2.5 10 46.6 341 0.5 -- 76.6 141 0.5 5 73.3 141 0.5 10 60.0 241 2.5 -- 73.6 141 2.5 5 66.6 241 2.5 10 43.3 342 0.5 -- 76.6 142 0.5 5 73.3 142 0.5 10 66.6 142 2.5 -- 73.3 142 2.5 5 56.6 242 2.5 10 46.6 343 0.5 -- 76.6 143 0.5 5 76.6 143 0.5 10 63.3 243 2.5 -- 76.6 143 2.5 5 66.6 143 2.5 10 53.3 344 0.5 -- 76.6 144 0.5 5 63.3 244 0.5 10 43.3 344 2.5 -- 70.0 244 2.5 5 56.6 344 2.5 10 40.0 445 0.5 -- 76.6 145 0.5 5 76.6 145 0.5 10 76.6 245 2.5 -- 76.6 145 2.5 5 63.3 245 2.5 10 50.0 346 0.5 -- 80.0 146 0.5 5 73.3 146 0.5 10 60.0 246 2.5 -- 70.0 246 2.5 5 56.6 346 2.5 10 43.3 447 0.5 -- 73.3 147 0.5 5 66.6 247 0.5 10 43.3 447 2.5 -- 66.6 247 2.5 5 43.3 447 2.5 10 43.3 448 0.5 -- 76.6 148 0.5 5 73.3 148 0.5 10 56.6 348 2.5 -- 76.6 148 2.5 5 56.6 348 2.5 10 43.3 349 0.5 -- 76.6 149 0.5 5 76.6 149 0.5 10 73.3 149 2.5 -- 76.6 149 2.5 5 73.3 149 2.5 10 70.0 150 0.5 -- 76.6 150 0.5 5 70.0 150 0.5 10 56.6 250 2.5 -- 73.3 150 2.5 5 66.6 250 2.5 10 53.3 251 0.5 -- 76.6 151 0.5 5 73.3 151 0.5 10 60.0 151 2.5 -- 76.6 151 2.5 5 60.0 151 2.5 10 46.6 3-- -- 10 0.0 9-- -- 5 10.0 8R 25788 2.5 10 10.0 8R 25788 0.5 5 36.6 8CGA 43.089 0.5 -- 73.3 1CGA 43.089 0.5 5 46.6 3CGA 43.089 0.5 10 33.3 4CGA 43.089 2.5 -- 66.6 2CGA 43.089 2.5 5 43.3 4CGA 43.089 2.5 10 36.6 5-- -- -- 76.6 1______________________________________
The data of Table V show that, on the treatment with Acenit 50 EC containing 50% of acetochlor [chemically 2-chloro-2'-ethyl-6'-methyl-N-ethoxymethylacetanilide], the sugar beet sprouted to a very little extent (10%) or not at all. The sprouting was also low when the well known N,N-diallyldichloroacetamide (code number: R 25788) herbicide agent and cyanomethoxy-iminophenylacetonitrile (code number: CGA 43.089) antidote were used, whereas the phytotoxic effects of acetochlor were significantly diminished by using the nitrile compounds of the invention.
EXAMPLE 41
Study of the antidote effect in the case of urea-type herbicides by using various cultivated plants
These tests were carried out in plastic pots lined with a plastic foil which were capable of receiving 800 g of soil. 400 g of air-dry field soil each were weighed in the cultivating pots. The soil had a pH value of 4.67, a cledginess of 46 according to Arany and an organic substance content of 1.97%. As test plants, 10 grains of Pi-3707 maize, 5 seeds of soy and 20 grains of wheat each were sown onto the soil in the pots. After sowing, the seeds were covered with 100 g of soil and the treatments were carried out in 4-fold repetitions. The plants were cultivated at 28.+-.4.degree. C. by using an illumination period lasting 16 hours. The water was daily supplied up to the total capacity.
The evaluation was carried out at the 12th day calculated from the sowing, i.e. at the 8th day calculated from the sprouting. The sprout height of the maize as well as the green weight of the soy and wheat were measured. The results are summarized in Tables VI, VII and VIII.
TABLE VI______________________________________ MaizeNitrile Treatment with sproutcompound Antidote Herbicide heightNo. Herbicide kg/hectare kg/hectare cm______________________________________1 Isoproturon 0.25 4.0 36.01 Isoproturon 1.0 4.0 31.55 Isoproturon 0.25 4.0 34.85 Isoproturon 1.0 4.0 36.77 Isoproturon 0.25 2.0 40.17 Isoproturon 1.0 2.0 39.310 Isoproturon 0.25 4.0 34.410 Isoproturon 1.0 4.0 36.111 Isoproturon 0.25 4.0 36.811 Isoproturon 1.0 4.0 36.213 Isoproturon 0.25 4.0 37.113 Isoproturon 1.0 4.0 36.025 Isoproturon 0.25 2.0 40.425 Isoproturon 1.0 2.0 37.126 Isoproturon 0.25 2.0 39.426 Isoproturon 1.0 2.0 40.327 Isoproturon 0.25 2.0 40.527 Isoproturon 1.0 2.0 36.927 Isoproturon 0.25 4.0 37.327 Isoproturon 1.0 4.0 32.728 Isoproturon 0.25 2.0 42.228 Isoproturon 1.0 2.0 39.328 Isoproturon 0.25 4.0 32.228 Isoproturon 1.0 4.0 36.429 Isoproturon 0.25 2.0 39.629 Isoproturon 1.0 2.0 35.729 Isoproturon 0.25 4.0 37.129 Isoproturon 1.0 4.0 37.431 Isoproturon 0.25 2.0 37.231 Isoproturon 1.0 2.0 41.835 Isoproturon 0.25 2.0 41.035 Isoproturon 1.0 2.0 38.438 Isoproturon 0.25 4.0 35.638 Isoproturon 1.0 4.0 32.453 Isoproturon 0.25 2.0 41.553 Isoproturon 1.0 2.0 38.056 Isoproturon 0.25 2.0 36.956 Isoproturon 1.0 2.0 40.957 Isoproturon 0.25 2.0 39.957 Isoproturon 1.0 2.0 35.658 Isoproturon 0.25 2.0 39.558 Isoproturon 1.0 2.0 40.9-- -- -- -- 36.9-- Isoproturon -- 2.0 34.7-- Isoproturon -- 4.0 29.65 Diuron 0.25 4.0 34.85 Diuron 1.0 4.0 30.37 Diuron 0.25 4.0 34.87 Diuron 1.0 4.0 33.510 Diuron 0.25 4.0 34.810 Diuron 1.0 4.0 31.028 Diuron 0.25 4.0 35.628 Diuron 1.0 4.0 31.131 Diuron 0.25 4.0 30.131 Diuron 1.0 4.0 34.753 Diuron 0.25 4.0 36.453 Diuron 1.0 4.0 33.9-- Diuron -- 4.0 29.428 Chlorbromuron 0.25 2.0 37.428 Chlorbromuron 1.0 2.0 41.228 Chlorbromuron 0.25 4.0 43.428 Chlorbromuron 1.0 4.0 39.835 Chlorbromuron 0.25 2.0 42.335 Chlorbromuron 1.0 2.0 44.753 Chlorbromuron 0.25 2.0 39.653 Chlorbromuron 1.0 2.0 41.653 Chlorbromuron 0.25 4.0 44.453 Chlorbromuron 1.0 4.0 42.156 Chlorbromuron 0.25 2.0 43.156 Chlorbromuron 1.0 2.0 44.556 Chlorbromuron 0.25 4.0 40.856 Chlorbromuron 1.0 4.0 39.658 Chlorbromuron 0.25 2.0 43.858 Chlorbromuron 1.0 2.0 41.858 Chlorbromuron 0.25 4.0 40.058 Chlorbromuron 1.0 4.0 38.9-- Chlorbromuron -- 2.0 36.9-- Chlorbromuron -- 4.0 34.8______________________________________
It can be seen from Table VI that the maize was protected from the harmful effects of the various urea-type herbicides by using the nitrile derivatives according to the invention as antidotes.
TABLE VII______________________________________ Green weightNitrile of wheat ascom- Treatment with % of the un-pound Antidote Herbicide treated con-No. Herbicide kg/hectare kg/hectare trol______________________________________1 Isoproturon 0.25 4.0 821 Isoproturon 1.0 4.0 1245 Isoproturon 0.25 4.0 1165 Isoproturon 1.0 4.0 1527 Isoproturon 0.25 4.0 1247 Isoproturon 1.0 4.0 12711 Isoproturon 0.25 4.0 8611 Isoproturon 1.0 4.0 10313 Isoproturon 0.25 4.0 10013 Isoproturon 1.0 4.0 13626 Isoproturon 0.25 4.0 9726 Isoproturon 1.0 4.0 10927 Isoproturon 0.25 4.0 12327 Isoproturon 1.0 4.0 13728 Isoproturon 0.25 4.0 8328 Isoproturon 1.0 4.0 11329 Isoproturon 0.25 4.0 10129 Isoproturon 1.0 4.0 14431 Isoproturon 0.25 4.0 12331 Isoproturon 1.0 4.0 13032 Isoproturon 0.25 4.0 19332 Isoproturon 1.0 4.0 28835 Isoproturon 0.25 4.0 13635 Isoproturon 1.0 4.0 15353 Isoproturon 0.25 4.0 18253 Isoproturon 1.0 4.0 7557 Isoproturon 0.25 4.0 14757 Isoproturon 1.0 4.0 14158 Isoproturon 0.25 4.0 13658 Isoproturon 1.0 4.0 141-- Isoproturon -- 4.0 786 Diuron 0.25 2.0 1066 Diuron 1.0 2.0 11125 Diuron 0.25 2.0 8225 Diuron 1.0 2.0 10726 Diuron 0.25 2.0 8626 Diuron 1.0 2.0 10328 Diuron 0.25 2.0 11028 Diuron 1.0 2.0 6531 Diuron 0.25 2.0 11331 Diuron 1.0 2.0 10232 Diuron 0.25 2.0 8532 Diuron 1.0 2.0 10038 Diuron 0.25 2.0 9938 Diuron 1.0 2.0 10653 Diuron 0.25 2.0 9253 Diuron 1.0 2.0 10756 Diuron 0.25 2.0 9556 Diuron 1.0 2.0 11657 Diuron 0.25 2.0 9157 Diuron 1.0 2.0 146-- Diuron -- 2.0 641 Chlorbromuron 0.25 2.0 911 Chlorbromuron 1.0 2.0 1211 Chlorbromuron 0.25 4.0 1071 Chlorbromuron 1.0 4.0 1055 Chlorbromuron 0.25 2.0 895 Chlorbromuron 1.0 2.0 625 Chlorbromuron 0.25 4.0 1045 Chlorbromuron 1.0 4.0 887 Chlorbromuron 0.25 2.0 1817 Chlorbromuron 1.0 2.0 1217 Chlorbromuron 0.25 4.0 597 Chlorbromuron 1.0 4.0 9613 Chlorbromuron 0.25 2.0 6713 Chlorbromuron 1.0 2.0 5213 Chlorbromuron 0.25 4.0 10813 Chlorbromuron 1.0 4.0 10626 Chlorbromuron 0.25 2.0 11226 Chlorbromuron 1.0 2.0 10726 Chlorbromuron 0.25 4.0 10826 Chlorbromuron 1.0 4.0 10827 Chlorbromuron 0.25 2.0 11327 Chlorbromuron 1.0 2.0 7727 Chlorbromuron 0.25 4.0 9927 Chlorbromuron 1.0 4.0 10558 Chlorbromuron 0.25 2.0 10058 Chlorbromuron 1.0 2.0 10658 Chlorbromuron 0.25 4.0 13458 Chlorbromuron 1.0 4.0 12859 Chlorbromuron 0.25 2.0 10659 Chlorbromuron 1.0 2.0 7559 Chlorbromuron 0.25 4.0 14159 Chlorbromuron 1.0 4.0 112-- Chlorbromuron -- 2.0 60-- Chlorbromuron -- 4.0 44______________________________________
It is evident from the data of Table VII that the wheat was effectively protected from the harmful effect of various herbicidal urea derivatives such as isoproturon, diuron and chlorbromuron by using the nitrile derivatives of the invention as antidotes.
TABLE VIII______________________________________Nitrile Green weightcom- Treatment with of soy as %pound Antidote Herbicide of the un-No. Herbicide kg/hectare kg/hectare treated control______________________________________1 Isoproturon 0.25 2.0 1041 Isoproturon 1.0 2.0 10325 Isoproturon 0.25 2.0 8925 Isoproturon 1.0 2.0 11132 Isoproturon 0.25 2.0 10432 Isoproturon 1.0 2.0 9256 Isoproturon 0.25 2.0 8856 Isoproturon 1.0 2.0 11157 Isoproturon 0.25 2.0 12657 Isoproturon 1.0 2.0 119-- Isoproturon -- 2.0 851 Diuron 0.25 2.0 861 Diuron 1.0 2.0 1451 Diuron 0.25 4.0 1061 Diuron 1.0 4.0 1047 Diuron 0.25 2.0 997 Diuron 1.0 2.0 1197 Diuron 0.25 4.0 917 Diuron 1.0 4.0 11210 Diuron 0.25 2.0 11610 Diuron 1.0 2.0 10510 Diuron 0.25 4.0 9810 Diuron 1.0 4.0 10311 Diuron 0.25 2.0 10611 Diuron 1.0 2.0 8411 Diuron 0.25 4.0 10611 Diuron 1.0 4.0 9413 Diuron 0.25 2.0 11813 Diuron 1.0 2.0 10613 Diuron 0.25 4.0 9713 Diuron 1.0 4.0 14125 Diuron 0.25 2.0 10025 Diuron 1.0 2.0 11825 Diuron 0.25 4.0 9225 Diuron 1.0 4.0 10427 Diuron 0.25 2.0 12327 Diuron 1.0 2.0 12327 Diuron 0.25 4.0 9227 Diuron 1.0 4.0 10332 Diuron 0.25 2.0 11932 Diuron 1.0 2.0 13332 Diuron 0.25 4.0 13432 Diuron 1.0 4.0 9956 Diuron 0.25 2.0 12456 Diuron 1.0 2.0 9456 Diuron 0.25 4.0 8956 Diuron 1.0 4.0 11257 Diuron 0.25 2.0 16957 Diuron 1.0 2.0 10857 Diuron 0.25 4.0 8857 Diuron 1.0 4.0 102-- Diuron -- 2.0 82-- Diuron -- 4.0 881 Chlorbromuron 0.25 2.0 881 Chlorbromuron 1.0 2.0 1105 Chlorbromuron 0.25 2.0 1085 Chlorbromuron 1.0 2.0 8210 Chlorbromuron 0.25 2.0 11010 Chlorbromuron 1.0 2.0 10111 Chlorbromuron 0.25 2.0 10211 Chlorbromuron 1.0 2.0 13713 Chlorbromuron 0.25 2.0 11213 Chlorbromuron 1.0 2.0 11127 Chlorbromuron 0.25 2.0 13127 Chlorbromuron 1.0 2.0 9728 Chlorbromuron 0.25 2.0 8528 Chlorbromuron 1.0 2.0 11131 Chlorbromuron 0.25 2.0 12231 Chlorbromuron 1.0 2.0 12632 Chlorbromuron 0.25 2.0 12232 Chlorbromuron 1.0 2.0 11838 Chlorbromuron 0.25 2.0 11138 Chlorbromuron 1.0 2.0 9253 Chlorbromuron 0.25 2.0 12653 Chlorbromuron 1.0 2.0 12356 Chlorbromuron 0.25 2.0 13556 Chlorbromuron 1.0 2.0 10257 Chlorbromuron 0.25 2.0 13757 Chlorbromuron 1.0 2.0 116-- Chlorbromuron -- 2.0 80______________________________________
The results summarized in Table VIII also support that the soy was effectively protected from the harmful effect of various herbicidal urea derivatives such as isoproturor, diuron and chlorbromuron by using the nitrile derivatives of the invention as antidotes.
EXAMPLE 42
Study of the antidote effect in the case of urea-type herbicides on maize species with various sensitivity
These tests were carried cut in pots of 14 cm in diameter with 5-fold repetitions. The pots were filled with a sandy adobe soil to the two-thirds of their volume and 10 grains of maize each of the species ETA-TC, Pi-3901, Pi-3965 and Pi-3839, respectively were sown in the pots, then the grains were covered with a treated or untreated soil of 5 cm in height according to the given experiment.
The soil was treated with 6 kg/hectare of linuron together with various amounts of the nitrile antidotes. The height of the sprout was determined and compared to the untreated control. The results are summarized in Table IX.
TABLE IX______________________________________Nitrile Antidote Sprout heightcompound dose Maize as % of the un-No. kg/hectare species treated control______________________________________1 0.1 Pi-3901 84.01 0.5 Pi-3901 89.91 1.0 Pi-3901 99.31 1.5 Pi-3901 89.27 0.1 Pi-3901 85.77 0.5 Pi-3901 94.47 1.0 Pi-3901 101.77 1.5 Pi-3901 97.210 0.1 Pi-3901 90.210 0.5 Pi-3901 86.810 1.0 Pi-3901 91.810 1.5 Pi-3901 91.613 0.1 Pi-3901 96.113 0.5 Pi-3901 106.313 1.0 Pi-3901 94.413 1.5 Pi-3901 84.718 0.1 Pi-3901 85.418 0.5 Pi-3901 104.218 1.0 Pi-3901 114.318 1.5 Pi-3901 99.3-- -- Pi-3901 81.56 0.1 ETA-TC 98.86 0.5 ETA-TC 100.86 1.0 ETA-TC 89.26 1.5 ETA-TC 93.07 0.1 ETA-TC 101.47 0.5 ETA-TC 89.67 1.0 ETA-TC 94.87 1.5 ETA-TC 94.713 0.1 ETA-TC 98.013 0.5 ETA-TC 101.413 1.0 ETA-TC 97.313 1.5 ETA-TC 91.4-- -- ETA-TC 89.11 0.1 Pi-3965 106.81 0.5 Pi-3965 98.91 1.0 Pi-3965 112.91 1.5 Pi-3965 109.06 0.1 Pi-3965 111.56 0.5 Pi-3965 97.56 1.0 Pi-3965 96.16 1.5 Pi-3965 109.37 0.1 Pi-3965 100.57 0.5 Pi-3965 119.77 1.0 Pi-3965 97.57 1.5 Pi-3965 117.210 0.1 Pi-3965 111.110 0.5 Pi-3965 118.310 1.0 Pi-3965 121.510 1.5 Pi-3965 101.413 0.1 Pi-3965 107.913 0.5 Pi-3965 112.213 1.0 Pi-3965 121.913 1.5 Pi-3965 109.018 0.1 Pi-3965 120.418 0.5 Pi-3965 101.118 1.0 Pi-3965 96.418 1.5 Pi-3965 97.8-- -- Pi-3965 96.11 0.1 Pi-3839 79.51 0.5 Pi-3839 86.81 1.0 Pi-3839 96.01 1.5 Pi-3839 86.23 0.1 Pi-3839 111.63 0.5 Pi-3839 104.23 1.0 Pi-3839 106.83 1.5 Pi-3839 104.87 0.1 Pi-3839 94.27 0.5 Pi-3839 87.87 1.0 Pi-3839 84.97 1.5 Pi-3839 92.610 0.1 Pi-3839 92.410 0.5 Pi-3839 96.810 1.0 Pi-3839 92.310 1.5 Pi-3839 97.113 0.1 Pi-3839 100.313 0.5 Pi-3839 90.013 1.0 Pi-3839 97.413 1.5 Pi-3839 89.118 0.1 Pi-3839 96.118 0.5 Pi-3839 105.618 1.0 Pi-3839 105.118 1.5 Pi-3839 103.9-- -- Pi-3839 78.5______________________________________
It can be seen from Table IX that maize species with various sensitivity were also protected by using the antidotes of the invention.
After the greenhouse tests, the phytotoxicity-diminishing effect of the nitrile derivatives according to the invention was investigated in small-parcel experiments.
In these tests, the antidote and herbicide compositions were used partly in the form of a tank mixture and partly in a formulation containing both the herbicide agent and the nitrile derivative.
The experiments were continuously evaluated by determining the percentage of sprouting of the cultivated plants, by observing the damages caused by the herbicides as well as by evaluating the amount of the crop and registering the herbicide action. From an economical point of view, the water content of the crop has a high significance: this water content is increased on the use of herbicides. Thus, on the assessment of our field experiments, a real extent of the antidote action also appears in the decrease of the water content.
EXAMPLE 43
Study of the antidote effect in the case of urea-type herbicides in small-parcel tests
The phytotoxicity-decreasing effect in the case of an urea-type herbicide was studied with pivalonitrile (compound No. 1) in small-parcel tests. The antidote was formulated together with linuron as active ingredient in a common formulation according to four ratios. The formulation was applied by spraying with water in the form of a wettable powder composition (as described in Example 15).
These tests were carried out on parcels of 20 m.sup.2 with 4-fold repetitions by using Pioner-3950 maize cultivated on an adobe soil of Mezoseg containing 1.46% of organic substances.
The results of the measurements, i.e. the number of plants/parcel, the height of the plants, the length of the maize-ear covered by grains, the amount of grain-crop/parcel and the water content of the harvested crop are summarized in Table X.
TABLE X__________________________________________________________________________ Maize-ear Linuron covered compound Dose No. of Plant withNitrile Dose kg/hec- plants height grains Crop amount Water contentNo. kg/hectare tare pc. cm cm kg %__________________________________________________________________________1 0.5 4 150 186.7 17.3 6.95 29.41 0.5 2 148 194.5 16.3 6.66 30.21 0.25 4 147 178.2 16.4 6.37 30.41 0.25 2 147 186.2 15.0 5.49 28.2-- -- 4 140 172.5 15.1 4.45 31.7-- -- 2 142 178.4 15.6 4.80 31.0untreated control 151 196.1 15.8 5.98 28.3__________________________________________________________________________
Simultaneously, the occurrance of seven weeds in these parcels was investigated and the extent of the weed control was characterized by EWRC scoring in Table XI.
The weeds investigated were as follows:
1: Echinochloa crusgalli;
2: Amaranthus chlorostachis;
3: Chenopodium album;
4: Polygonum lopathiofolium;
5: Equisetum arvense;
6: Chenopodium hybridum;
7: Setaria glauca
TABLE XI______________________________________Nitrilecompound LinuronDose Dose Time of Herbicide effect inkg/ kg/hec- evalua- EWRC scoreNo. hectare tare tion 1 2 3 4 5 6 7______________________________________1 0.5 4 01.06. 1 1 1 1 1 1 1 04.07. 1 1 1 3 3 1 1 06.08. 2 1 1 6 7 1 11 0.5 2 01.06. 1 1 1 1 1 1 1 04.07. 1 1 1 4 3 1 1 06.08. 2 1 1 6 7 1 11 0.25 4 01.06. 1 1 1 1 1 1 1 04.07. 1 1 1 3 4 1 1 06.08. 2 1 1 6 7 1 11 0.25 2 01.06. 1 1 1 1 1 1 1 04.07. 1 1 1 3 3 1 1 06.08. 2 1 1 6 7 1 1-- -- 4 01.06. 1 1 1 1 1 1 1 04.07. 1 1 1 2 3 1 1 06.08. 1 1 1 5 5 1 1-- -- 2 01.06. 1 1 1 1 1 1 1 04.07. 1 1 1 3 3 1 1 06.08. 2 1 1 6 7 1 1untreated control 01.06. 9 8 7 8 8 7 8 04.07. 9 9 8 9 9 8 9untreated control 06.08. 9 9 9 9 9 8 9______________________________________
It is evident from Table XI, that the herbicide effect of linuron was not decreased, whereas the phytotoxicity exerted or the maize was eliminated by using the antidote of the invention.
EXAMPLE 44
Similarly to the preceding Example, the diminishing effect of the nitrile derivatives of the invention on the phytotoxicity of the commonly known thiolcarbamate (EPTC) herbicide as well as the development of the herbicide action were investigated in small-parcel field experiments.
The tests were carried out in parcels of 20 m.sup.2 by cultivating NK-PI-20 maize in 4-fold repetitions.
For the treatments, EPTC and two nitrile derivatives (compounds Nos. 1 and 11) were applied by spraying with water before sowing in the form of an emulsifiable concentrate as described in Example 13 and 14 and worked into the soil. The results of these experiments are summarized in Table XII.
TABLE XII__________________________________________________________________________ Maize-earNitrile antidote EPTC No. of Plant covered Water Dose kg/ Dose plants height with grains Crop amount contentNo. hectare kg/hectare pc cm cm kg %__________________________________________________________________________1 1.25 8 167 192.1 21.8 8.27 24.81 0.25 8 158 185.3 22.8 6.15 30.411 1.25 8 163 187.2 21.6 5.85 25.811 0.25 8 157 182.6 20.5 7.60 31.7-- -- 8 145 171.6 19.9 5.12 33.6R-25788 1.25 8 160 186.1 21.4 5.71 33.6untreated control 165 188.7 20.4 6.63 29.2__________________________________________________________________________ Likewise, the herbicide effect was also studied in the parcels by using the EWRC scores. The results are summarized in Table XIII.
TABLE XIII__________________________________________________________________________Nitrile antidote EPTCDose Dose Time of Herbicide effect in EWRC scoreNo. kg/hectare kg/hectare evaluation 1 2 3 4 5 6 7__________________________________________________________________________1 1.25 8 11.06 1 1 1 2 3 1 1 13.07. 1 1 1 5 6 1 1 12.08. 1 1 1 7 8 1 11 0.25 8 11.06. 1 1 1 2 2 1 1 13.07. 1 1 1 6 6 1 1 12.08. 1 1 1 7 8 1 111 1.25 8 11.06 1 1 1 2 2 1 1 13.07. 1 1 1 5 5 1 1 12.08. 1 1 1 7 8 1 111 0.25 8 11.06. 1 1 1 2 2 1 1 13.07. 1 1 1 6 5 1 1 12.08. 1 1 1 7 8 1 1-- -- 8 11.06. 1 1 1 2 3 1 1 13.07. 1 1 1 4 6 1 1 12.08. 1 1 1 5 8 1 1R-25788 1.25 8 11.06. 1 1 1 2 2 1 1 13.07. 1 1 1 4 5 1 1 12.08. 1 1 1 6 8 1 1untreated control 11.06. 8 7 7 8 8 6 7 13.07. 9 8 8 9 9 7 8 12.08. 9 8 9 9 9 7 8__________________________________________________________________________
EXAMPLE 45
Study of the antidote effect in the case of a chlortoluron herbicide in small-parcel experiment
The antidote effect of the compounds according to the invention was studied in a small-parcel field experiment on a wheat of Rana 2 species.
These experiments were carried out in parcels of 20 m.sup.2 on a loose sandy soil with 4-fold repetitions.
The treatments were performed by spraying out an appropriate amount of the antidote and herbicide in the form of a tank mixture in the middle of March.
The evaluation was made by using an EWRC score, twice during the cultivating period. Both the damages caused by the herbicide as well as the herbicide effect were determined. The results are summarized in Table XIV.
TABLE XIV______________________________________ Chlor- toluron 80Nitrile compound WP EWRC score Dose kg/ Dose kg/ Wheat Apera spica ventiNo. hectare hectare 1 2 1 2______________________________________-- -- 2.0 1 1 1 1-- -- 4.0 4 3 1 1-- -- 6.0 6 5 1 11 0.2 2.0 1 1 1 11 0.4 2.0 1 1 1 11 0.4 4.0 1 1 1 11 0.8 4.0 1 1 1 11 0.6 6.0 2 1 1 11 1.2 6.0 1 1 1 111 0.2 2.0 1 1 1 111 0.4 2.0 1 1 1 111 0.4 4.0 1 1 1 111 0.8 4.0 1 1 1 111 0.6 6.0 2 1 1 111 1.2 6.0 2 1 1 123 0.2 2.0 1 1 1 123 0.4 2.0 1 1 1 123 0.4 4.0 1 1 1 123 0.8 4.0 1 1 2 223 0.6 6.0 1 1 1 123 1.2 6.0 1 1 2 323 0.2 2.0 1 1 1 125 0.4 2.0 1 1 1 125 0.4 4.0 2 2 1 125 0.8 4.0 2 1 1 125 0.6 6.0 3 2 1 125 1.2 6.0 3 1 1 130 0.2 2.0 1 1 1 130 0.4 2.0 1 1 1 130 0.4 4.0 2 1 1 130 0.8 4.0 2 2 1 130 0.6 6.0 3 2 1 130 1.2 6.0 3 2 1 141 0.2 2.0 1 1 1 141 0.4 2.0 1 1 1 141 0.4 4.0 3 2 1 141 0.8 4.0 2 1 1 141 0.6 6.0 3 2 1 141 1.2 6.0 2 1 1 1CGA.43.089 0.2 2.0 1 1 1 1CGA 43.089 0.4 2.0 1 1 1 1CGA 43.089 0.4 4.0 3 2 1 1CGA 43.089 0.8 4.0 3 2 1 1CGA 43.089 0.6 6.0 5 4 1 1CGA 43.089 1.2 6.0 4 3 1 1______________________________________
It is evident from the data of Table XIV that, in comparison to cyanomethoxy-iminophenylacetonitrile (code number: 43.089), a known antidote, the antidote nitrile derivatives of the invention were more effective in the decrease or elimination, respectively of the harmful effect of the chlortoluron herbicide.
EXAMPLE 46
Study of the antidote effect in the case of a metobromuron herbicide in small-parcel experiment
The antidote effect of the compounds according to the invention was studied in a small-parcel field experiment on a potato of Desiree species.
These experiments were carried out in parcels of 20 m.sup.2 on a loose sandy soil with 4-fold repetitions.
The treatments were postemergently carried out after hilling. The evaluation was performed by using an EWRC score, twice during the cultivating period. Both the damages caused by the herbicide as well as the herbicide effect were determined. The results are summarized in Table XV.
TABLE XV______________________________________ Meto- bromuronNitrile compound 50 WP Dose Dose EWRC score kg/ kg/ Potato Echinocloa SetariaNo. hectare hectare 1 2 1 2 1 2______________________________________-- -- 3.0 1 1 2 3 2 2-- -- 6.0 4 2 1 1 1 1-- -- 9.0 6 2 1 1 1 15 0.15 3.0 1 1 2 3 2 25 0.30 3.0 1 1 2 3 2 25 0.30 6.0 2 2 1 1 1 15 0.60 6.0 1 1 1 1 1 15 0.45 9.0 2 2 1 1 1 15 0.90 9.0 1 1 1 1 1 120 0.15 3.0 1 1 2 3 2 220 0.30 3.0 1 1 2 3 2 320 0.30 6.0 3 2 1 1 1 120 0.60 6.0 2 1 1 1 1 120 0.45 9.0 3 2 1 1 1 120 0.90 9.0 2 1 1 1 1 128 0.15 3.0 1 1 2 3 2 228 0.30 3.0 1 1 2 3 2 328 0.30 6.0 2 2 1 1 1 128 0.60 6.0 2 1 1 1 1 128 0.45 9.0 3 2 1 1 1 128 0.90 9.0 2 1 1 1 1 1CGA 43.089 0.15 3.0 1 1 2 3 2 2CGA 43.089 0.30 3.0 1 1 2 3 2 2CGA 43.089 0.30 6.0 3 2 1 1 1 1CGA 43.089 0.60 6.0 3 2 1 1 1 1CGA 43.089 0.45 9.0 5 2 1 1 1 1CGA 43.089 0.90 9.0 4 2 1 1 1 1______________________________________
It is evident from the data of Table XV that, in comparison to cyanomethoxy-iminophenylacetonitrile (code number: 43.089:, a known antidote, the antidote nitrile derivatives of the invention were more effective in the decrease or elimination, respectively of the harmful effect of the metobromuron herbicide.
EXAMPLE 47
Study of the antidote effect in the case of a chlorbormuron herbicide in small-parcel experiment
This field experiment was carried out or sun-flower of NSA-26 species in parcels of 20 m.sup.2 with 4-fold repetitions on a mildly humified soil containing 1% of organic materials.
The treatments were performed preemergently by applying the antidote and herbicide in the form of a tank mixture. In the experimental area no weediness was developed thus, the phytotoxic effect caused by the herbicide was only evaluated. The results are summarized in Table XVI.
TABLE XVI______________________________________Nitrile compound Chlorbromuron Dose 50 WP kg/hec- Dose EWRC scoreNo. tare kg/hectare 1 2______________________________________ 2.5 2 1 7.5 6 533 0.1 2.5 2 133 0.3 2.5 1 133 0.3 7.5 4 233 0.9 7.5 3 235 0.1 2.5 2 135 0.3 2.5 1 135 0.3 7.5 3 335 0.9 7.5 3 240 0.1 2.5 2 140 0.3 2.5 1 140 0.3 7.5 3 340 0.9 7.5 3 342 0.1 2.5 1 142 0.3 2.5 1 142 0.3 7.5 2 142 0.9 7.5 1 144 0.1 2.5 2 144 0.3 2.5 1 144 0.3 7.5 3 144 0.9 7.5 2 148 0.1 2.5 1 148 0.3 2.5 1 148 0.3 7.5 3 148 0.9 7.5 2 149 0.1 2.5 1 149 0.3 2.5 1 149 0.3 7.5 2 149 0.9 7.5 1 151 0.1 2.5 2 151 0.3 2.5 1 151 0.3 7.5 2 251 0.9 7.5 2 2GCA 43.089 0.1 2.5 2 1CGA 43.089 0.3 2.5 2 1CGA 43.089 0.3 7.5 4 3CGA 43.089 0.9 7.5 4 3______________________________________
The results of Table XVI also support that, in comparison to cyanomethoxy-iminophenylacetonitrile (code number: 43.089) a known antidote, the antidote according to the invention showed a better protective action.

Number	Name	Date
2960534	Scherer et al.	Nov 1960
4070389	Martin	Jan 1978
4309210	Quadranti et al.	Jan 1982

Herbicide compositions containing a nitrile derivative as antidote

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