CS207722B2 - Means for protection of cultural plants before aggresive agrochemicals - Google Patents

Description

The present invention relates to compositions for the protection of crop plants from aggressive agrochemicals comprising as an antidote an antibody of at least one oxime-carbamate or oxime-carbonate of the formula I

Ar — C — X (I)

N — O — CO — R wherein

Ar is optional - a phenyl or naphthyl radical of formula

- optionally substituted by a halogen, nitro or lower alkyl group having 1 to 4 carbon atoms, a furan or thiophene ring, - one of the radicals COOR4 or -CO-Re,

X is cyano, C 2 -C 5 alkanoyl, C 2 -C 5 carboxylic acid ester, -COOH, hydrogen, C 1 -C 9 carboxylic acid amide, halogen or C 1 -C 4 alkyl carbon,

R 1 is hydrogen, halogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy or optionally at most twice halogen, cyano, nitro or trifluoromethyl substituted with para-phenoxy;

R 2 and R 3 are each independently hydrogen, halogen, nitro, C 1 -C 4 alkyl, C 1 -C 8 haloalkyl, C 1 -C 4 alkoxy,

R 4 represents an aliphatic group of up to 8 carbon atoms, a cycloaliphatic group of 3 to 7 carbon atoms, an araliphatic group of 7 to 18 carbon atoms, wherein the aromatic radical may be substantially substituted as mentioned for the radicals R 2 and R 3 and additionally may be substituted with cyano;

R is arbitrary and j is -N (R 5) (R 6) where

R 5 is hydrogen or C 1 -C 4 alkoxy or the radical R 6,

R 6 represents an aliphatic group of up to 8 carbon atoms, a cycloaliphatic group of 3 to 7 carbon atoms, an araliphatic group of 7 to 18 carbon atoms, an aromatic group of 6 or 10 carbon atoms or a heterocyclic group of 5- to 10-membered ring system 1 or 2 rings and with at most 3 heteroatoms from the group consisting of nitrogen, oxygen or sulfur, the aromatic radical may be substantially substituted as indicated for the radicals R2 and R3, b) the radical —YR7 in which:

Y is oxygen or sulfur; and

R7 is as defined for Re,

R 6 is optionally a) the radical -N (R 8) (R 10) in which

R 9 is hydrogen, C 1 -C 4 alkyl or C 3 -C 7 cycloalkyl; and

R 10 has the same meaning as R 9 or is hydrogen, or

R ₉ and R ₁₀ together with the nitrogen form a 3- to 7-membered ring which may be substituted with C 1 -C 4 alkyl groups, bj is the moiety -NH-CONHR 10, wherein:

R10 is as defined above.

Accordingly, the compounds of formula I are also carbamates and bj (thio carbonate).

In formula I, halogen is fluorine, chlorine, brooch or iodine.

Carboxylic acid esters are alkyl esters of carboxylic acid having 1 to 4 carbon atoms in the alkyl; carboxylic acid amides are in addition to —CONH2: also monoalkyl-substituted or symmetrically or unsymmetrically dialkyl-substituted amides, wherein the alkyl groups are C1 -C4 alkyl groups.

The term "alkyl" alone or as part of a substituent includes branched or unbranched alkyl groups of 1 to 8 carbon atoms. Lower alkyl means alkyl of 1 to 4 carbon atoms. Examples are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, as well as the higher honiologues aimyl, isoamyl, hexyl, heptyl, octyl, including their isomers. Correspondingly, alkanoyl or cyanalkyl groups additionally contain one carbon atom.

The term "aliphatic" includes saturated (alkyl) as well as unsaturated (alkenyl, alkadienyl or alkynyl, halogen-substituted, cyano-substituted, and oxygen-interrupted radicals having up to 8 carbon atoms. The term aromatic group in the definition of R 4, R 5 and R 6 includes phenyl and naphthyl, the term "araliphatic" is to be interpreted accordingly.

The araliphatic moiety includes an aryl group, such as an optionally substituted one to three times phenyl or also naphthyl, which is bonded via an alkyl group having 1 to 4 carbon atoms or an alkenyl group having up to carbon atoms to the remainder of the molecule. Examples of the backbone include benzyl, phenylethyl, phenylallyl, and homologues thereof.

The term "heterocyclic radical" includes 5- to 10-membered ring systems with 1 or 2 rings and with up to 3 heteroatoms from the group consisting of nitrogen, oxygen or; sulfur.

C 3-7 Cycloalkyl groups are cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cycloheptyl. Cycloaliphatic residues correspond to these ring systems, but may additionally, if possible, contain one or more double bonds.

Arylglyoxixnitriloximes of the general formula

OH

C = N in which

X is hydrogen, chloro, bromo or nitro, proposed in U.S. Pat. No. 3,799,757, have insufficient activity as growth inhibitors and plant growth regulators. In addition, they are not; substances are stable and decompose after a short time.

The effect as an herbicidal antibody (antidote) is not known for this substance.

On the other hand, oximes of the formula I are excellent in protecting crop plants such as millet, rice, maize, various cereals (wheat, rye, barley, oats), cotton, sugar beet, cane, soybean etc. agrochemicals aggressive to plants, in particular to herbicides of a wide variety of groups, such as triazines, phenylurea derivatives, carbamates, thiolcarbamates, haloacetanilides, halogenated phenoxyphenoxyacetic acid esters, substituted phenoxyphenoxy esters and substituted phenoxyphenoxy esters, substituted phenoxyphenoxy esters, substituted phenoxyphenoxy esters benzoic acid derivatives, etc., when these substances do not act selectively or are only insufficiently selective, that is, in addition to weed control, they also damage crop plants to a lesser or greater extent. The invention also encompasses compositions comprising these oximethers of formula I together with herbicides.

Various substances have already been proposed as antibodies or antidotes which are able to specifically antagonize the harmful effect of the herbicide on the crop plant, i.e. to protect the crop plant without appreciably affecting the herbicidal effect on the weeds to be controlled. Depending on their properties, such antibodies can be used for the pre-treatment of seed of crop plants (seed dressing or seedlings) or before sowing in the soil or as a mixture prepared immediately in a tank, alone or together with the herbicide before or after emergence. Pre-emergence treatment includes both treatment of areas on which crops will be grown before sowing (ppi = pre plant incorporation), and also treatment of sown but not yet grown areas.

Thus, British Patent Specification 1 277 557 discloses the treatment of seeds and / or shoots of wheat and sorghum with certain esters and " oxamic acid amides prior to attack by N-methoxymethyl-2 ', 6 " -diethylchloroacetanilide (Alachlor). In other places in the literature (DOS 1 952 910, DOS 2 245 471, French patent 2 021 611), antibodies are proposed for the treatment of cereals, corn seeds and rice to protect against herbicidally active thiolcarbamates. In German patent 1 576 676 and in U.S. patent 3131509, hydroxyaminoacetanilides and hydantolines are proposed for the protection of grain seeds against carbamates such as IPC, CIPC etc. However, over time, all of these preparations have proved to be insufficiently effective.

In particular, compounds of the formula I in which

Ar is any of the above defined phenyl or naphthyl radicals, the other symbols having the following meanings:

X is cyano, hydrogen, C 2 -C 5 alkanoyl, C 2 -C 5 carboxylic acid ester residue, C 1 -C 9 carboxylic acid amide residue or C 1 -C 4 alkyl, c R 1 is hydrogen , halogen or, optionally, at most twice phenoxy substituted in the para-position by a halogen, cyano or trifluoromethyl group,

R 2 and R 3 are each independently hydrogen, halogen, C 1 -C 4 alkyl, C 1 -C 8 haloalkyl, C 1 -C 4 alkoxy, while

Y, R 5, R 6 and R 7 are as defined above.

This subgroup of compounds will be referred to as compound group 1a.

From the group of compounds Ia, a preferred position as an antidote is the group of compounds Ib ₎ in which

Ar represents a phenyl radical as defined above,

X is cyano, hydrogen, acetyl, C1-C4 alkyl (C1-C4) alkyl, -COONH2, -COONH (alkyl) wherein C1-C4 alkyl, -COON (alkyl) 12 wherein the alkyl group contains 1 to 4 carbon atoms, a methyl group,

R1 is hydrogen,

R 2 and R 3 are hydrogen, halogen, C 1 -C 4 alkyl, trifluoromethyl, methoxy or ethoxy,

R 5 is hydrogen, C 1 -C 4 alkyl or C 1 -C 4 alkoxy,

R 6 represents an aliphatic group of up to 8 carbon atoms or optionally a halogen, an alkyl group of 1 to 4 carbon atoms, a trifluoromethyl group, a methoxy group or an ethoxy group substituted with a phenyl group,

Y is oxygen or sulfur; and

R ₇ is as defined above for R e.

An important group of antidotes are those compounds of formula I in which

Ar is optionally a halogen or a C 1 -C 4 alkyl group substituted with a thiophene ring, and

X, Y, R 5, R 6 and R 7 have the meanings indicated for the subgroup of compounds Ia and preferably the meanings given for the subgroup of compounds 1b.

Another important class of antidotes to protect crop plants from herbicides is the subgroup of compounds of formula I wherein

Ar is --COOR 6 or - CORs, wherein

R 4 represents an aliphatic group of up to 4 carbon atoms or a phenyl group, and in the meaning of R 5, the substituents R 9 and R 10 independently of one another are hydrogen, alkyl of 1 to 4 carbon atoms or optionally halogen, trifluoromethyl or alkyl of 1 to 4 carbon substituted phenyl groups, while substituents

X, Y, R 5, R 6, R 7 have the meaning given for subgroup 1a and preferably for subgroup 1b.

Surprisingly, the oximes of the formula I have the property of protecting crops against attack by agrochemicals which attack plants, in particular against herbicides from various groups, including 1,3,5-triazines, 1,2,4-triazinones, phenylurea derivatives, carbamates , thiolcarbamates, phenoxyacetic acid esters, phenoxypropionic acid esters, haloacetanilides, halophenoxyacetic acid esters, substituted phenoxyphenoxyacetic acid and -propionic acid esters, substituted pyridinoxyphenoxyacetic acid esters and -propionic acids are not sufficiently tolerated by the plants, benzo derivatives are not sufficiently .

Depending on the intended use, such an antibody or antidote of the formula I can be applied for pre-treating the seed of a crop plant (seed dressing) or can be applied before or after sowing to the soil or alone or together with the herbicide before or after emergence. Thus, treatment of the plant or seed with an antidote can in principle be carried out independently of the time of application of the phytotoxic chemical. However, the application can also be carried out simultaneously. Pre-emergent treatment includes both pre-sowing treatment (ppi = 'pre plant incorporation') and treatment of sown but not yet grown areas.

The amount of antidote applied relative to the herbicide is largely controlled by the mode of administration. If the treatment of the field plot is carried out, the ratio of the antidote to the phytotoxic chemical is 1: 100 to 5: 1, preferably 1: 20 to 1: 1. However, in seed dressing and similar protective measures, smaller amounts are used compared to the amount of herbicide used later per 1 ha of cultivated area (for example about 1: 3000 to 1: 1000 J. Protective treatments such as seed dressing with an antidote of Formula I and possible later treatment of the land with agrochemicals are usually in little context. Pretreated seeds and plants can then come into contact agriculture, horticulture and forestry with various chemicals.

The invention therefore also relates to protective agents for the treatment of crop plants which contain, as active ingredient, an antidote of the formula I together with customary carriers. Such compositions may optionally be additionally mixed with those agrochemicals from whose influence the crop plant is to be protected, for example with a herbicide.

Cultivated plants are within the scope of the present invention all plants which in any form produce substances to be harvested (seeds, roots, stems, tubers, leaves, flowers, stocks such as oils, sugar, starch, protein, etc.) and grown for this purpose. . These include all kinds of cereals, corn, rice, millet, soybeans, beans, beans, peas, potatoes, vegetables, cotton, sugar beet, cane, peanuts, tobacco hops, as well as ornamental plants, fruit trees, such as banana trees, cocoa trees and rubber trees. However, this list is not limiting. In principle, the antidote can be used wherever a crop plant is to be protected from the phytotoxicity of a chemical.

The compounds of formula (I) can be prepared according to a plurality of processes from free oximes. These procedures are schematically illustrated below:

and carbamates

Ar

C — NOH + O = C = N — Re /

X

Ar

C = NO — CO — NHRe

X

Ar

C = NO — Na + Cl — CO — N — Re / I

X Rs

Ar

C = NO — CO — NRe / I

X R5

Ar

C = NO — CO — Cl + NH — Re- »

X

Ar

C = NO — CO — NHRe

X bj (thiocarbamates

Ar

C = NO - Na + Cl - CO - YR 7 ->

X

Ar

C = NO — CO — YR7

Ar

C = NO - CO - Cl + HO - R 7 ->

X

Ar

C = NO — CO — OR7

X g

Ar

C = NO — CO — Cl + Na — S — R7

X

Ar

N-O-C0-WH- <O>

C = NO — CO — SR7

X (In the above schemes, Na is sodium or other alkali metal).

In principle, all solvents which are inert under the reaction conditions are suitable for obtaining the compounds of the formula I. By way of example, hydrocarbons, in particular polar solvents such as acetonitrile, dioxane, cellosolve, dimethylformamide, but also ketohols such as methyl ethyl ketone, acetone, etc. Solvents containing hydroxyl groups are excluded.

The temperatures range from -10 to about 150 ° C, preferably between 20 and 120 ° C.

Bases such as t-amines (triethylamine, triethylenediamine, piperidine and others) can be used as hydrogen halide cleavage agents. In some cases, suspending sodium carbonate in the anhydrous reaction medium is also sufficient. Oximes exist in two stereoisomeric forms, i.e., syn and anti. Thus, within the scope of the present description, the two stereoisomeric forms are understood to be per se and as mixtures in any desired proportions.

The following examples illustrate the preparation of the new oximes. Temperatures are given in degrees Celsius

He did

Preparation of Compound of Formula << 5 - _cn

N-O-CO-NHC 1 - [compound 1]

23.5 g (0.16 mol) of benzyl cyanidoxime in 100 ml of acetonitrile are introduced. Thereafter, 25 ml of methyl isocyanate and a catalytically effective amount of diazabicyclooctane are added, and the reaction mixture is heated to 50 DEG C. whereupon the reaction product precipitates after a short time. The mixture was allowed to stir overnight, filtered, the product was washed with acetonitrile and then dried at 60 ° C with hexane. Yield: 29.2 g (89.8% of theory). Melting point 172-175 ° C. Example 1 a d 2

Preparation of Compound of Formula [Compound 53]

14.6 g (0.1 mol) of benzyl cyanidoxime in 100 ml of acetonitrile are introduced, then 18.7 g (0.1 mol) of 3-trifluoromethylphenyl isocyanate and catalytic amount of diazabicyclooctane are added. The reaction is started immediately and the reaction mixture is heated to about 50 degrees Celsius. The reaction mixture was then further stirred for 4 hours in a water bath. The precipitated reaction product is filtered off, washed with acetonitrile and dried under vacuum at 50 ° C. 25.5 g of the reaction product is obtained. Melting point 172-173 ° C.

Example 3

Preparation of the compound of formula cKO

Ct

C-CN

II

N-O-CO-S-C 1 H 4 [compound. 379]

6.3 g (0.05 mol) of chlorothioformic acid S-ethyl ester were added dropwise to a mixture of 11.9 g (0.05 mol) of 3,4-dichlorobenzylcyanidoxime sodium salt in 50 ml of acetonitrile. The reaction mixture was then heated, refluxed for 4 hours and concentrated in vacuo. Methylene chloride is added to the residue, the methylene chloride solution is stirred with activated carbon. and filtered. The filtrate was evaporated. 11.2 g (= 73.7% of theory) of the reaction product are obtained in the form of an oil.

Example 4

Preparation of compound H ₅ OOC-C _£ C-CN

II

N-O-CO ct (Compound 138)

14.2 g (0.1 mol) of cyanoethanoic acid ethyl ester oxime in 100 ml of acetonitrile are introduced into round-bottomed flasks. While stirring, a solution of 15.3 g of p-chlorophenyl isocyanate in 20 ml of acetonitrile was added dropwise and the reaction mixture was stirred at 60-70 ° C for 5 hours. The solution was filtered hot while the filtrate was cooled with ice water. The crystallized reaction product was filtered off, washed with a mixture of acetonitrile and hexane and dried. Melting point 147-148 ° C.

The following carbamates of the formula can be produced in this manner or according to any of the above methods:

C-CN

NO-CO-N-Rg · ¹⁶ Compound No. R1 Rz

Rs

R6 physical constants

1 H H H CH3 m.p. 172-175 ° 2 H H H CjzHs mp 93-96 ° 3 H H H n-C3H7 mp 89-91 ° 4 H H H ÍS0C3H7 m.p. 92-94 ° 5 H H H n-C4H9 m.p. 98-101 ° 6 H H H terc.C4H9 solid product 7 H H H —CH2CH2 — Cl m.p. 138-141 ° 8 H H H —CH2—O — CH3 9 H H H - <I 10 H 4-C1 H n-C4Hg m.p. 124-112 ° 11 H 4-C1 H —CH2—— —CH3 m.p. 110-114 ° 12 H 4-C1 H terc.C4H9 m.p. 102-105 ° 13 H 4-C1 H ÍS0C3H7 m.p. 140-144 ° 14 H 4-C1 H CH3 m.p. 191-193 ° 15 Dec H 4-C1 H C2H5 m.p. 105-108 ° 16 H 4-C1 H 11-C3H7 mp 112-113 ° 17 2-C1 4-C1 H CH3 m.p. 152-154 ° 18 2-C1 4-C1 H CH3 mp 124-128 ° 19 Dec 3-C1 4-C1 H terc.C4H9 solid product 20 May H 4-Br CHs CH3 m.p. 143-115 ° 21 2-iCl 4-C1 H ÍS0C3H7 m.p. 92-93 ° 22nd H 4-C1 CH3 CH3 m.p. 131-132 ° 23 2-C1 4-C1 CH3 CH3 solid product 24 4-t H H CH3 mp 162-165 ° 25 4-t.C4Hg H H C2H5 solid product 26 4-t.C4Hg H H 11-C3H7 solid product 27 Mar: 4-t.C4H9 H H terc.C4Hg oil 28 H 4 «Η3θ H H 29 H 4-CH3O H CH3 m.p. 182-184 ° 30 H 4-CH3O H C2H5 m.p. 106-110 ° 31 H 4-GH3O H ÍSO1C3H7 mp 129-131 ° 32 H 4- (CH3) 2 N - H CH3 33 H 4-C2H5O H CH3 34 H 4-C2H5O H ÍSOC3H7 35 H 4-NCte H CH3 36 H 3-CF3 H CH3 m.p. 150-151 ° 37 H 3-CF3 H C2H5 38 H 3-CF3 H H 39 H 3-CF3 CH3 CHs 40 H H O2H5 C2H5 oil 41 H 3-CF3 H n-C4H9 42 H H H -CeH5 m.p. 132-134 ° 43 H H H -C6H4Cl (4) mp 184-186 ° 44 H H H —CeHá — CH3 (3) m.p. 153-154 ° 45 H 4-t.C4Hg H -C6H5 m.p. 131-133 ° 46 3-C1 4-C1 H -CeHáClH) 47 3-C1 4-C1 H -C6H4Cl2 (3.4) m.p. 210-213 °

slou-

valuables no. Rl Rž Rs Re physical constants 48 3-C1 4-C1 H -C6H3Cl (3) iso- C3H7 (3) m.p. 172-175 ° 49 H H H -C6H4-CF3 mp 188-190 ° 50 H H H -C6H3Cl (3) CF3 (3) m.p. 207-208 ° 51 H H H -C 6 H ₃ {CF 3) 2 (3,5j m.p. 196-198 ° 52 H H H -CeH4-F (3) mp 159-161 ° 53 H H H -C6H4-CF3 m.p. 172-173 ° 54 H 4-C1 H -C6H4-CF3 mp 187-190 ° 55 H 4-C1 H -C6H4Cl (4) m.p. 204-205 ° 56 H 4-C1 H -C6H3Cl2 (3.4j m.p. 204-205 ° 57 H 4-C1 H -C6H3Cl (3) cis-C ₃ H7 (4) m.p. 150-151 ° 58 H 4-C1 H -CeH5 m.p. 148-150 ° 59 2-0 4-C1 H -C6H3Cl2 (3.5) solid product 60 4-t.C4Hg H H -C6H4Cl (4) m.p. 131-133 ° 61 4-t.C4Hg H H -C6H3Cl2 (3.4j m.p. 68-71 ° 62 é-t.CáHg H H -C6H3 _(CF3) 2 (3.5 j m.p. 58-60 ° 63 H 3-CF3 H -CeHrfCGs) (3 i 64 H 3-CFs H -CeHrfCFs) (4) 65 H 4-CH3O H _-C6 H3Cl2 (3,4) 66 H 4-C2H5O H -C6H4-CF3 67 H 3-CF3 H -C6H5 m.p. 141-143 ° 68 H 3-CFs H -ÍS0C3H7 mp 116-118 ° 69 2-C1 4-C1 H -CeHs m.p. 163-164 ° 70 2-C1 4-C1 H _-C6 H3 (CF3) 2 (3.5) m.p. 110-113 ° 71 2-C1 4-C1 H -C6H3Cl2 (2.4) m.p. 152-153 ° 72 4-t.C4Hg Η H -C ₆ H4 (CF ₃ ) (3) as well as the following carbamates of the formula: m.p. 136-140 °

^R <

compound no. X Rl 5 ^ -c-x N-Q-CO-N-Rg · Rz «6. R5 Re' physical constants 73 CH3 H H H CHs m.p. 97-99 ° 74 COCH3 H H H CHs 75 H 2-C1 4-C1 H CH3 mp 137 ° 76 H H H H CH3 mp 92-94 ° 77 H H 4-C1 H CH3 m.p. 133-136 ° 78 H H 4- (CH 3) 2 N H CH3 79 CH3 H 4- (C 2 H 5) 1 2N H CHs 80 CH3 3-NO2 H H CH3 81 H 3-CF3 H H CHs 82 -COOC2H5 3-CF3 H H CHs 83 H 4-CH3O H H CHs 84 CHs 4-CH3O H H CHs 85 H 3-NO2 H H CHs 86 H 2-NO2 H H CH3 87 -COCH3 H H H -C6H3Cl2 (3.4) 88 -COCH3 H H H -C6H5 (CH3) 2 (2.4) 89 H H H H -CeH4Cl (3) m.p. 145-146 ° 90 H 2-C1 6-C1 H -CeH4Cl (4j m.p. 142-144 ° 91 CH ₃ H H H -CeH4Cl (3) m.p. 105-106 ° 92 -COCH3 H H H _-C6 H4Cl (4) m.p. 297-298 °

slou- fyzikální

valuables no. X Ri SS Rs Re constants 93 H H 4-C1 H -CeH4Cl (3) mp 151-152 ° 94 H H 4-C1 H -CeHs m.p. 106-109 ° 95 H H 4-C1 H -C 6 H 4 -CH 3 (3j mp 119-121 ° 96 H H 4-C1 H -CeH4-F (3) m.p. 130-132 ° 97 H H 4-C1 H -CeH4NO2 (3) 98 -COOC2H5 H H H CH3 99 -COOCH3 H H H CH3 100 ALIGN! -COOt.CáHg H H H CH3 101 -COOCH3 H 4-Br H CH3 102 -COOC2H5 H 3-CF3 H CH3 103 -COOCH3 H 4-C1 H -CeHs 104 -CONHCH3 H H H CH3 105 -CONH2 H H H CH3 106 -CONHISO1C3H7 H H H CH3 107 -CONHCH3 H 4-CH3O  H CH3 108 -CONHCH3 H 4-C1 CH3 CH3 109 -CONHISOC4H9 H H H CH3 110 -CONHt.CáHg H 4-C1 H CH3 As well as the following carbamates formulas Ar — C II -X II N- -O — CO — N — R 5

Re

compound no. Ar X Rs Re physical constants 111 α-naphthyl -CN H CH3 m.p. 154-158 ° 112 α-naphthyl -CN CfeHs C2H5 m.p. 162-164 ° 113 N-naphthyl -CN H terc.C4H _g 114 / 3-Naphthyl -CN H ÍS0C3H7 115 / 3-Naphthyl -CN H -CeH4Cl (3) 116 2-furanyl -CN H CH3 117 2-furanyl -CN H -CH2 — OCH 118 2-furanyl -CN H -CeH 5 Cl (3.4) 119 2-thienyl -CN H CHS 120 2-thlenyl -CN H C2H5 121 2-thienyl -CH3 H CH3 122 (p) CeH5 — O — CeH4— NOS ¹ H CHs 123 (p) CeH5 — O — CeH4— -COCH3 H -CeH4CF3 (3) 124 HfeN— CO— -CN H -CeH 4 Cl (3j m.p. 203-204 ° 125 H2N — CO— -CN H -CeH4Cl (3) m.p. 201-203 ° 126 H'2'N — what— -CN H -CeH ₃ Cl 2 (2.5j m.p. 176-177 ° 127 HžN— CO— -CN H -C 6 H 4 CF 3 (2j m.p. 179-183 ° 128 HjzN — CO— -CN H -CeH4CF3 (3) m.p. 170-180 ° 129 H2N — what— -CN H -CeH 3 Cl (3) CH 3 (4) m.p. 163-164 ° 130 H2'N — what— -CN H CH3 m.p. 176-177 ° 131 HaN — CO— -CN H C2H5 mp 116-120 ° 132 H-2N — CO— -CN H -CH 2 CH 2 —Cl mp 141-142 ° 133 1Ϊ2Ν — what— -CN H n-C3H7 b; mp 113-116 ° 134 H2N — what— -CN H -1S0C3H7 m.p. 125-126 ° 135 H2N — CO— -CN H -nC4H9 m.p. 92-96 ° 136 H2N — what— -CN H -CeHs m.p. 174-175 ° 137 H2N — what— -CN H -C 6 H 3 CF 3 (3) Cl (4j m.p. 182-183 ° 138 C2H5OOC— -CN H -CeH4Cl (3) m.p. 147-148 ° 139 C2H5OOC— -CN H CH3 m.p. 101-103 ° 140 2-thienyl -CN H -CeH ₃ Cl2 (3.4) oil 141 (5R) 2-Thienyl -CN H CH3 mp 186 ° 142 (5Cl) 2-thienyl -CN H -CeH4Cl (3) mp 186 ° 143 (5Cl) 2-thienyl -CN H -CeH 3 Cl (4) CF 3 (3) mp 184 °

as well as the following carbamates of the formula:

O

II

R 4 -O-C-C-CN R 5

II /

N — O — C — N

O Re

compound no. R4 Rs Re physical constants 144 CH3O— H CeH 3 CF 3 (3) Cl (4) m.p. 162-163 ° 145 CH3O— H C6H4CF ₃ m.p. 147-148 ° 146 CH3O— H CeHs mp 149-150 ° 147 CH3O— H CeH4NO2 (2) m.p. 166-167 ° 148 CH3O— H CeH4Cl (2) bt 162—163 ^p 149 CH3O— H CeH4Cl (3) mp 157-158 ° 150 CH3O— H CeH4Cl (1) m.p. 136-138 ° 151 CH3O— H CeH4CF3 (3) m.p. 127-128 ° 152 CH3O— H CeH4 [OC4H9 (i)] (3) m.p. 139-140 ° 153 CHsO— H CeH3Cl2 (3.4) b. 162-163 ° (decomposition) 154 CH3O— H CeH3Cl (3Br (4) m.p. 170-171 ° 155 CH3O— H CeH3Cl2 (2.5) mp 164-165 ° 156 CH3O— H CeH 3 CH 3 (2) m.p. 118-120 ° 157 CH3O— H CeH 3 CH 3 (2) m.p. 119-120 ° 158 CH3O— H CeH3Br (2) m.p. 134-135 ° 159 CH3O— H CeH3 (CH3) 2 (2.4) m.p. 115-117 ° 160 CH3O— H CeH3Cl (2) NO2 (1) b. 165-166 ° (decomposition) 161 CH3O— H CeH3Cl2 (2.4) mp 143-145 ° 162 CH3O— H -CH3 m.p. 122 DEG -123 DEG 163 CH3O— H -CH2GH2Cl m.p. 72-74 ° 164 O2H5 — O H -CeHs m.p. 130-132 ° 165 C2H5—0 H -CeH4Cl (1) m.p. 81-82 ° 166 C2H5-O H -CeH4Cl (2) m.p. 139-141 ° 167 C2H5—0 H -CeH4Cl (3) mp 156-157 ° 168 O2H5 — O H -CeH4CF3 (3) mp 117-119 ° 169 C2H5-O H -CeH4CF3 (3) m.p. 136-137 ° 170 C2H5—0 H -CeH4NO2 (2) m.p. 145-147 ° 171 C2H5-O H -CeH4CH3 (3) mp 121-122 ° 172 C2H5-O H -CeH4 [O-C4H9 (i)] (3) m.p. 127-128 ° 173 G2H5 — O H -CeH3Gl2 (3.4) m.p. 160-161 ° 174 C2H5-O H -CeH3Cl2 (2.5) m.p. 136-137 ° 175 G2H5 — O H -CeH 3 CF 3 (3) Cl (4) mp 141-142 ° 176 G2H5-O H -CeH3Cl (2) NO2 (3) m.p. 133-134 ° 177 C2H5—0 H -CeH3 (CF3) 2 (3.5) mp 155-157 ° 178 C2H5—0 H -CeH 3 CH 3 (2) Cl (4) m.p. 90-91 ° 179 C2H5-O H -CeHzCbf 2,4,5) m.p. 137-139 ° 180 O2H5—0 H -CH3 m.p. 104-106 ° 181 C2H5-O H -CH 2 Cl 2 m.p. 73-75 ° 182 (s) C 4 H 9 -O H -CeH4Cl (3) m.p. 128-130 ° 183 (S) C 4 H 9 -O H -CeH4CF3 (3) mp 93-95 ° 184 (s) C4H9-O H -CeH4CF3 (3) m.p. 109-110 ° 185 (S) C 4 H 9 -O H -CeH3Cl2 (3.4) m.p. 140-141 ° 186 (s) C 4 H 9 -O H -CeH3Cl2 (2.5) m.p. 100-101 ° 187 (s) C4H9-O H -CeH 3 CF 3 (3) Cl (4) mp 126-127 ° 188 (sjCiHg — O H -CH3 m.p. 80-81 ° 189 [S] C 4 H 9 -O H -CH2CH2Cl m.p. 57-59 ° 190 CH 2 = CH-CH 2 -O H CeHs m.p. 103-105 ° 191 CH2-CH-CH2-O H CeH4Cl (2) m.p. 118-120 ° 192 CH 2 = CH-CH 2 -O H CeH4Cl (3) m.p. 131-132 ° 193 CH 2 = CH-CH ₂ -O H CeH4CF2 (3) m.p. 106-107 ° 194 CH2 = _CH-CH2 -O H CeH4CF3 (3) b. 121-1123? 195 CH2-CH2-CH2-O H CeH3Cl2 (3.4) mp 126-127 °

slou-

čenlna č. R4 R5 Re 196 CH2 = CH-CH2-O H CeH3Cl2 (2.5) 197 CH 2 = CH-CH 2 - O H CeH2Cl3 (2,4,5) 198 CH 2 = CH ₂ CH ₂ - O H -CH2CH2Cl 199 H -CeH4Cl (3) 200 0- ° - H -CeH4CF3 (3) 201 0-O- H -CeH4Cl (3) 202 0- ° - H -C ₆ H ₃ CF ₃ (3) 203 <E> ° - H -CeH2Cl3 (2,4,5) 204 0- ° - H -CH3 205 CeHs | H -CeH4Cl (2) 206 CH - CH - CH2O CeHs 1 H -CeH3Cl ₂ (3.4) 207 CH = CH = CH 2 O CeHs H -CeH2Cl3 (2,4,5) CH = CH = CH 2 O CH3O CH3 -CH3 208 CH3O H CeH3Cl2 (3.5) 209 0-O- H CeH3Cl2 (3.5) 210 0- ° - H CeH ₃ Cl2 (3.4) 211 CH3O- H CeH3Cl2 (3.4)

physical constants

130 DEG -131 DEG C. 124 DEG -126 DEG C. 61 DEG -63 DEG

mp 141-142 °

m.p. 94-96 °

m.p. 162-163 °

b. 131-132 ° b, 124-126 °

m.p. 99-101 °

b. i 36 ° (decomposition)

b. 138 ° (decomposition) b. 161 ° (decomposition)

105 ° -106 ° 156 ° (decomposition)

mp 107-108 °

m.p. 162-163 °

b. mp 162-163 ° as well as the following carbamates of formula O CN

II /

Rio — N — C — G O Rs

I II II /

Rg n-o-c-n

-.................... \

Re Compound No. Rs R6 R9 R10

212

213

214

215

216

H

H

H

H

H

CeH3Cl2 (3.4)

CeH 3 CF 3 (3) Cl (4)

CeHs

CsH4C1

CeH4Cl (3)

-CH 3 -CH 3

-CH3 -CH3 physical constants

bp 153-154 ° bp 154-156 °

mp, 143-144 °

m.p. 120-1123 °

b. mp 142-144 ° compound No. R 5 R 6

Rg

Rio physical constants

217 H C6H ₄ CF3 0 m.p. 160-162 ° 218 H C6H3Cl2 (3.4) m.p. 153-154 ° 219 H CgH4CH3 (3) 3 m.p. 133-135 ° 220 H C6H3CF3 (3) 3 b. 140 ° (decomposition) 221 H C ₆ H3Cl (2) NO2 '(4) 3 b. 165 ° (decomposition) 222 H C6H2Cl3 (2,4,5) 3 m.p. 143-145 ° 223 H -CHs 3 b. 113 ° (decomposition) 224 H C6H5 mp 124-125 ° 225 H C6HiCl (4) mp 125-127 ° 226 H C6H3Cl2 (3.4) mp 155-157 ° 227 H C6H3CF3 (3) 0 b. 145 ° (decomposition) 228 H -CH3 b. 90 ° (decomposition) 229 H C3H7 CH3 CH3 b. 46-50 ° 230 H CH (CH 3) 2 CHs CH3 m.p. 62-66 ° 231 H C4H9 CH3 CH3 oil 232 H O2'H5 ch ₃ CH3 b. 90 ° 233 H CH (CH 3) 2 H H m.p. 206-207 ° 234 H CH3 CH3 CH3 m.p. 72-76 ° 235 H CH2CH2Cl CHs CH3 m.p. 99-101 ° 236 H C6H ₄ C1 / ~ Y . 0 \ _ / f ~ \ mp 159-161 ° 237 H C6H4CF2 (3) V 0 \_of m.p. 130-132 ° 238 H C6H3CF3 (3) . 0 \ ~~ / m.p. 176-178 ° 239 H CeHs H -CHCF (2) b. 163 ° (decomposition) 240 H C5HdCl (3) H -C6H ₄ CF ₃ b. 180 ° (decomposition) 241 H C6H3Cl2 (3.4) H -C6H4CF3 [2] b. 161 ° (decomposition) 242 H C6H3CF3 (3) H _-C6 H4CF ₃ (2) b. 169 ° (decomposition) 243 H CeH5 H -C 6 H ₃ C 1 ₂ (2.4) b. 179 ° (decomposition) 244 H CsH ₄ C1 H -C 6 H ₃ Cl 2 (2,4) b. 154 ° (decomposition) 245 H CeH 4 Cl (4j H -C6H3Cl2 (2.4) b. 172 ° (decomposition) 246 H CeH ₄ CF3 H -C6H3Cl2 (2.4) b. 165 ° (decomposition) 247 H CeH4CH3 (2) H -C 6 H ₃ Cl 2 (2,4) b. t, 152 ° (decomposition)

Rs Re Rg R10 physical constants H C6H3Cl2 (3.4) H -C 6 H ₃ Cl 2 (2,4) b. 176 ° (decomposition) H C ₆ H ₃ Cl 2 (2.5) H -C 6 H ₃ Cl 2 (2,4) b. 185 ° (decomposition) H C6H3CFs (3) H _-C6 H3Cl2 (2.4) b. 162 ° (decomposition) H C6H3CH3 (2) H -C6H3C1 ₂ (2.4) b. 154 ° (decomposition) H CeH 3 CH 3 (2) H -C 6 H ₃ Cl 2 (2,4) b. 140 ° (decomposition) H CeH3Cl2 (2.4) H -CeH ₃ Cl2 (2.4) b. 172 ° (decomposition) H CeHgCl (2) H -CeH3 (CF3) 2 (3.5) b. 165 ° (decomposition) H CeH4Cl (3) H -CeH3 (CF3) 2 (3.5) b. 179 ° (decomposition) H CeH4CF3 (3) H -CeH3 (CF3) 2 (3.5) b. 188 ° (decomposition) H C ₆ H4C1 H -CeH3Cl (2) NO2 (3) b. 187 ° (decomposition) H CeH4CF3 H -C6H3Cl (2) NO2 (1) b. 198 ° (decomposition) H C6H3Cl2 (3.4) H -CeH3Cl (2) NO2 (3) b. 198 ° (decomposition) H CeH3Cl (2) NO2 (1) H -CeH3Cl (2) NO2 (3) b. 185 ° (decomposition) -CH3 -CH3 H 0 m.p. 104-105 ° -CH3 -CH3 H -C6H3CH3 (2) b. 164 ° (decomposition) -CH3 -CH3 H -CeH4CF3 (3) m.p. 115-117 ° -CH3 -CH3 H -C6H3Cl2 (2.5) m.p. 162-164 ° -CH3 -CH3 H Br m.p. 71-72 ° H CeH3Cl2 (2.5) H Br b. 120 ° (decomposition) H CeH4Cl (2) H CH2CH = CH2 b. 154 ° (decomposition) H CeH ₃ CF3 (2) H CH2CH = CH2 b. 175 ° (decomposition) H CeH3Cl (3) H CH2CH = CH2 b. 139 ° (decomposition) H CsH4C1 H CH2CH = CH2 b. 170 ° (decomposition) H CeH3Cl2 (3.4) H CHaCH = CH2 b. 164 ° (decomposition) H -CH3 H CH ₂ CH = CH 2 mp 111-113 ° H CH _(CH3) 2 H O2H5 m.p. 103-105 ° H C3I-I7 H C2H5 b. 78-90 ° H C4H9 H C2H5 mp 70.5—74 ° H O3H7 H C1i3 m.p. 67-70 ° H CH (CH 3) 2 H CH3. mp 116-118.5 ° H C4H9 H CH3 m.p. 107-109 ° H CH2-CH2-Cl H CH3 m.p. 105-106 ° H CeH4Cl (3) H nC3H5 m.p. 177-178 ° H CeH3Cl2 (3.4) H nC3H5 b. 180 ° (decomposition) H C6H3Cl (3) CH3 (4) H 11C3H5 m.p. 166-167 ° H -C1-3 H 11C3H5 m.p. 124-112 ° H C ₆ H4C1 H CeH3Cl2 (3.5) b. 190 ° (decomposition) H CeH 3 CF 3 (3) Cl (4) H C6H3Cl2 (3.5) oil H CeH3Cl2 (3.4) H CeH3Cl2 (3.5) b. 173 ° (decomposition) H C6H3Cl (3) CF ₃ (4) H CeH3Cl2 (3.5) b. 182 ° (decomposition) H CeH4CF3 (3) H CeH3Cl2 (3.5) b. 169 ° (decomposition) H CH3CH2Cl H H mp 141-142 ° H -CH3 H CH3 m.p. 167-168 °

Rg on cn \ II /

N— OF Rio Re C — c II NO- 0 II -C — NHRe Rg R10 physical constants CeH4Cl (2) H CH3 m.p. 177-178 ° CeH4Cl (2) H C2H5 m.p. 166-167 ° CeH4Cl (2) H H b, 203 ° (dec.) CeH4Cl (2) CH ₃ CHs m.p. 125-128 ° CeH4Cl (3) H CH ₃ m.p. 198-200 ° CeH4Cl (3) H H b. 203 ° (dec.) CeH4Cl (3) H C2H5 b. 180 ° (dec.) CeH4Cl (3) CH ₃ CHs m.p. 161-162 ° CeH3CH ₃ (4) Cl (3) H CH3 b. 180 ° (dec.) CeH ₃ CH ₃ (3) CH3 CH3 m.p. 144-146 ° CeH3CH ₃ (4) Cl (3) H C ₂ H ₅ mp 163-163.5 ° CeH ₃ CH ₃ (3) H C4H9 m.p. 142-145 ° CeH3CH ₃ (4) Cl (3) H H m.p. 163-166 ° CeH ₃ Cl2 (3.4) H CH3 b. 195 ° (dec.) CeH ₃ Cl ₂ (3.4) H C2H5 b. 175.5 ° (dec.) CeH3Cl2 (3.4) H C4H9 m.p. 167.5-170 ° CeH ₃ Cl2 (3.4) H H mp 192-193 ° CeH ₃ CFs (2) H CH3 b. 198 ° (dec.) CeH ₃ CF ₃ (3) Cl (4) H C2H5 b. 185 ° (dec.) CeH ₃ CF3 (2) H H b. 183 ° (dec.) CeH ₃ CF3 (2) H C ₃ H7 b. 172 ° (dec.) CeH ₃ CF3 (2) H O4H9 mp 174-177 ° CeH ₃ Cl (2) CF ₃ (2) CH ₃ CH ₃ mp 156-158 ° CeH ₃ Cl (2) CF ₃ (2) H H b. 191 ° (dec.) CeH ₃ Cl (2) CF ₃ (2) H CH ₃ mp 183-185 ° CeH ₃ Cl (2) CF ₃ (2) H CbH5 m.p. 167-169 ° CeH ₃ Cl (2) CF ₃ (2) H C4H9 mp 149-150 ° CeH4CF ₃ H H b. 183 ° (dec.) CeH4CF ₃ H CH ₃ b. 193 ° (dec.) CeH4CF3 (3) H H b. 180 ° (dec.) CeH4CF3 (3) H CH ₃ b. 189 ° (dec.) CeH4CF3 (3) CH ₃ CH3 m.p. 134-135 ° CeH4Cl (2) H CsH7 (n) mp 155-157 ° CeH 4 Cl (4) H C ₃ H7 (nj b. 170 ° (dec.) CeH4Cl (3) H C4H9 b ’. mp 170-174 ° C 6 H ₃ Cl 2 (3,5) H H b. 200 ° (dec.) CeH ₃ Cl2 (3.5) H C2H5 b. 159 ° (dec.) C 6 H ₃ Cl 2 (3,5) H ch ₃ b. 194 ° C CeH4CF ₃ H CHs b. 190 ° (dec.) CeH4CF2 (3) CH3 CH3 mp 109-110 ° CeH5 H H b. 175 ° (decomposition) CeHs H CH3 m.p. 162-163.5 ° C ₆ H3Cl ₂ (2,3) H H b. 156 ° (decomposition) CH ₃ H H b. 177 ° (decomposition) CH2CH3 H H mp 116-120 ° CH ₃ H C2H5 mp 119.5-124 ° C3H7 (n) H H mp 113-116 ° CeH ₃ Cl (3) CH ₃ (4) H H m.p. 163-164 ° CeH ₃ CH 3 (4) Cl (3) H CONH2 b. 197 ° (decomposition) CeH ₃ Cl2 (3.4) H CONH2 b. 205 ° (decomposition) CeH ₃ CF ₃ (3) Cl (4) H CONH2 b. 200 ° (decomposition) CeH4Cl (2) H CONH2 b. 206 ° (decomposition) CeH ₃ Cl (3) CH ₃ (4) H CONH2 b. 197 ° (decomposition) CeH ₃ Cl2 (3.5) H CONH2 b. 197 ° (decomposition) CeH4CF ₃ H CONH2 b. 208 ° (decomposition) C6H5 H CONH2 mp 214-215 ° C 6 H ₃ Cl 2 (2,3) H CONH2 b. 203 ° (decomposition) CHs H CONH2 b. 216 ° (decomposition)

as well as the following carbamates of the formula

H2N — CO — NH — CO — C — CN

II

N — O — CO — NH — Re Compound No. R6 physical constants

349 C4Hg (n) b. 131 ° (decomposition) 350 C3H7 (n) b. 133 ° (decomposition) 351 C3H7 (ISO) b. 207 ° (decomposition) 352 —CH2 — CH2 —Cl b. 140-145 ° (decomposition) 353 C3H7 (ISO) b. 207 ° (decomposition)

According to Example 3 or one of the above methods, the following is produced [tlilo] carbonates: R 10 —NH — C — C — CN

II

N — O — C — YR7 o

Compound No. YR7 R10 physical constants

354 OC6H5 H b. 149 ° (decomposition) 355 OCH3 H b. 170 ° (decomposition) 356 OC3H6 (iso) H m.p. 171-173 ° 357 OCH3 CH3 mp 97-198.5 ° 358 OCaH9 (n) H m.p. 165-167 ° 359 OC ₃ H7 CH3 m.p. 109-110 ° 360 O (CH 12) 3 CH 3 CHs m.p. 75-76 ° 361 OCH3 H m.p. 120-121 ° 362 OCH3 CH3 m.p. 73-74 ° 363 OC & H5 —CONH ₂ b. 168 ° (decomposition) 364 OCH3 - CONH ₂ m.p. 171-172 ° 365 SC12H5 H mp 124-125 ° 366 OC4H9 —CONH ₂ b. 173 ° (decomposition) 367 OC3H6 (iso) —CONH ₂ b. 173 ° (decomposition) 368 SC2H5 —Conh ₂ b. 179 ° (decomposition) 369 SC2H5 CH3 m.p. 76-78 °

The following carbonates can be produced by the method of Example 3 or any of the above methods:

..............

comp.

N-O-CO-G physical constants

370 H H —O — C6H5 m.p. 105-108 ° 371 H H —O — SO2C3H7 m.p. 108-110 ° 372 H • H —O — CH2CH2OCH3 oil 373 H H —O — CH ₃ m.p. 108-110 ° 374 H H —O — CH2 — CC1 ₃ solid product 375 H H - 0 — C6H4NO2 (3) solid product 376 H H —S — nCaHg 377 H H —0 — tertC ₄ H _g m.p. 85-86 ° 378 H H —S — C2H5 mp 59-62 ° 379 3-C1 4-C1 —S — C2H5 oil 380 H 4-C1 —S — C2H5 oil 381 2-C1 4-C1 —S — C2H5 oil 382 H _4-CH3 —S — C2H5 oil 383 H H —0 — CeH4Cl (3) 384 H 4-C1 —0 — sec.C4H9 385 H 3-CF ₃ —0 — CH3 386 H 3-CF ₃ —0 — CeH5 387 H 3-CF3 —S — C2H5 388 H 3-CFs —S — ch ₃ 389 H 4-Br —S — C2H5 390 H 4-CH3O -0-CeH4-OCH ₃ (4) oil 391 H 4-CH3O —0 — CbH4Cl (4) viscous product 392 H 4-C2H5O O — IC 50 C 3 H 7 oil

as well as the following carbonates of the formula compound no. N-O-CO-G Ri R2 X G physical constants 393 H 4- _(CH3) 2N H —OC ₂ H ₅ oil 394 H 4-CH 2 O H —S — O2H5 oil 395 H 4-C1 —0CH3 oil —COOCHg as well as the following compounds: No. 396 H2N — CO — NH — CO — C — CN mp 184 ° (decomposition)

NO — CO — N — O — CH _{3 and 3}

No. 397 NHz — CO — C — CN m.p. 144-146 ° (decomposition)

II

NO — CO — N — O — CH3

CH ₃

No. 398 HsCe — C (Clj — NO — CO — NHCH3 oil No. 399 H5C2O — CO — C (CN) = NO — CO — SC2H5 oil No. 400 H 5 C 2 O-CO-C (CH 3) = NO-CO-NHCH 3 m.p. 83-85 ° No. 401 (O / -NH-CO-CH = no-gonhch ₃ b. 126 ° (dec.

No. 402

No 403 cf ₃ d, - ^ O - N - D - CO - CH = NO - CONHCH ₃ ^Cr 3,

NH-CO-CH = _NO-5 CONHCH

b. 145 ° (dec.)

b. 170 ° (decomposition)

As already mentioned, various methods and techniques are contemplated for use of the compounds of formula I to protect crop plants from the effects of agrochemicals:

af · * ·, *> * 3,.

1) Seed pickling

a) Pickling the seeds with the active ingredient in the form of a wettable powder by shaking them in the container until they are evenly distributed on the seed surface (dry pickling). About 10 to 500 g of active compound of the formula I (40 g to 2 kg of wettable powder) per 100 kg of seed are used.

(b) Seed pickling of the active ingredient of the formula I in the form of an emulsion concentrate according to method (a) (wet pickling).

c) Pickling by dipping the seed in a suspension containing 50 to 3200 ppm of the active compound of the formula I for 1 to 72 hours and, optionally, subsequent drying of the seeds (dipping).

Seed pickling or the treatment of germinated plants are naturally preferred methods of application, since the treatment of the active ingredient is entirely concentrated on the intended crop plant. As a rule, from 10 g to 500 g, preferably from 50 to 250 g of active ingredient per 100 kg of seed are used, and depending on the methodology used, which also allows the addition of other active substances or trace nutrients, it is possible to deviate up or down (repeated pickling).

2) Application in tank form

A liquid preparation of a mixture of antibody (antidote) and herbicide (ratio between 1:20 and 5: 1) is used, the amount of herbicide used being 0.1 to 6 kg per ha. Such a mixture prepared in a tank is preferably applied before or immediately after sowing or is worked 5 to 10 cm deep into the still unsown soil.

3] Application in sown grooves

The antibody is applied in the form of an emulsion concentrate, wettable powder, or granulate into the still uncovered sown grooves, and after covering the sown grooves, the herbicide is normally applied preemergently.

Thus, in principle, the antibody can be administered before, together or after application of the pesticide, either to the seed or to the field before sowing or after sowing or, in certain cases, also after seed has emerged.

4) Controlled delivery of active substance

The active ingredient is applied as a solution to a mineral granular carrier or polymerized granulate (a mixture of urea and formaldehyde) and the solvent is allowed to evaporate.

Of course, all other methods of application of the active compounds can also be used. The following examples are given to illustrate them.

The compounds of formula I can be used alone or together with suitable carriers and / or other additives. Suitable carriers and additives may be solid or liquid and correspond to those commonly used in the preparation of such compositions, such as natural or regenerated minerals, solvents, dispersants, wetting agents, adhesives, thickeners, binders or fertilizers.

The active substance content of the products in the market is between 0.1 and 90%.

For application, the compounds of formula (I) may be present in the following processing forms (wherein the percentages by weight in brackets represent the preferred amount of active ingredient):

solid processing forms: dusting and spreading (up to 10%), granules, coated granules, impregnated granules and homogeneous granules, pellets (grains) (1 to 80%);

Liquid processing:

(a) water-dispersible concentrates of the active substance:

wettable powders and pastes (25 to 90% in the case of commercial packaging, 0.01 to 15 why in ready-to-use solution);

emulsion concentrates and concentrated solutions (10 to 50%; 0.01 to 15% in ready-to-use solution);

b) solutions (0.01 to 20%); aerosols.

The active compounds of the formula I according to the invention can be processed, for example, in the following combinations:

Dust:

The following substances shall be used to prepare (a) 5% and (b) 2% dusts:

(a) 5 parts active substance 95 parts talc;

(b) 2 parts of active substance: part of highly dispersed silicic acid, parts of talc.

The active compounds are mixed with the carriers and the mixture is ground and in this form can be applied by dusting.

Granuplát:

The following substances are used to prepare the 5% granulate:

parts of the active substance

0.25 parts of epichlorohydrin

0.25 parts of cetyl polyglycol ether

3.50 parts of polyethylene glycol 91 parts of kaolin (particle size 0.3-0.8 mm).

The active ingredient is mixed with epichlorohydrin and dissolved in 6 parts of acetone. Polyethylene glycol and cetyl polyglycol ether are then added. The solution thus obtained is sprayed onto kaolin and then the acetone is evaporated in vacuo.

Wettable powder:

The following ingredients are used to prepare a) 70%, b) 40%, c) and d) 25% and e) 10% wettable powder:

(a) 70 parts of active substance, parts of sodium dibutylnaphthylsulfonate, parts of the condensation product of naphthalenesulfonic acids, phenolsulfonic acids and formaldehyde 3: 2: 1, parts of kaolin, parts of chalk (Prov. Champagne); (b) 40 parts of active ingredient, parts of sodium ligninsulfonic acid, parts of dibutylnaphthalenesulfonic acid sodium, parts of silicic acid; cj 25 parts of the active substance,

4.5 parts by weight of lignin sulphotic acid calcium salt,

1.0 parts of a mixture of chalk (prov. Champagne) and hydroxyethylcellulose (1: 1),

1.5 parts by weight of dibutylnaphthalenesulfonic acid sodium,

19.5 parts of silicic acid,

19.5 Chalk (Champagne),

28.1 parts of kaolin;

(d) 25 parts of active substance;

2.5 parts of isooctylphenoxypolyoxyethylenethanol,

1.7 parts of a mixture of chalk (prov. Champagne) and hydroxyethylcellulose (1: 1),

8.3 parts of sodium aluminum silicate,

16.5 parts of diatomaceous earth, parts of kaolin;

(e) 10 parts of active substance, parts of a mixture of sodium salts of saturated sulphated fatty alcohols, parts of the condensation product of naphthalenesulphonic acid and formaldehyde, parts of kaolin.

The active ingredients are thoroughly mixed with the ingredients in suitable mixing media and ground in appropriate mills and rollers. A wettable powder of excellent wettability and suspensibility is obtained, which is diluted with water to suspensions of any desired concentration and can be used in particular for application to plant leaves.

Emulsifiable concentrate:

The following substances are used to prepare the 25% emulsifiable concentrate:

parts of the active substance,

2.5 parts of epoxidized vegetable oil, parts of a mixture of alkylarylsulphonates and a fatty alcohol polyglycol ether, parts of dimethylformamide,

57.5 parts xylene.

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

Test in nutrient solution for post-emergence administration of antibody (antidote)

General methodology:

The small plastic pots (6 cm upper diameter), which are provided with holes at the bottom, are filled with granular zono207722 lithium and seed of crop plants is sown in this substrate. The pots are then placed in a second transparent plastic pot (7 cm upper diameter) in which there are 50 ml of water which rises and capillaries the seeds. From day 5, Hewitt's nutrient solution is gradually increasing. From day 15, when the crop plant is in the 1 to 2-leaf stage, it is added to the nutrient solution replenished to 50 ml ppm of test antibody (antidote) + amount of herbicide below

From day 16, the loss of liquid is rebalanced by the addition of Hewitt's nutrient solution. For the duration of the test, the temperature is 20 to 23 ° C and the relative humidity is 60 to 70 why. 3 weeks after the addition of the herbicide and the antibody (antidote), a linear scale of 1 to 9 is performed, with 1 representing total plant damage and 9 representing healthy plants without adverse effects; influence.

Test variants:

1) 15 ppm of α- [4- (3,5-dichloro-pyridyl-2-oxy-phenoxy) -propionic acid propargylthiol ester in wheat of the species "Zenith"

2) 4 ppm 4-ethylamino-6-tert-butylamino-2-chloro-s-trlazine in 'Zenith' wheat

3) 2 ppm of N- [4- (p-trifluoromethylphenoxy] phenoxy] propionic acid n-butoxyethyl ester in maize of the type "Orla"

4) 8 ppm of .alpha .- [4- (p-trifluoromethylphenoxy) phenoxy] propionic acid n-butoxyethyl ester in sorghum (Sorghum) of &quot; Funk G-522 &quot;

5) 4 ppm of prometryne = 2,4-bis- (isopropylamino) -6-methyl-thio-s-triazine in sorghum sorghum of the species "Funk G-522"

6} 8 ppm of α- [4- (3,5-dichloropyridyl-2-oxy) -phenoxy] propionic acid methyl ester in wheat of the species "Zenith"

The compounds of formula (I) have a good effect as antidotes (antibodies) in these experiments. Examples include:

test variant compound number effect herbicide (without / with antibody)

91 6/8

54 3/7

372 2/5

Test in nutrient solution for pre-emergence application of antibody (antidote):

Hewitt's nutrient solution was prepared, containing the amount of herbicide listed below, as well as 10 ppm of test antibody (antidote).

Seeds of crop plants are used which, at the test concentration indicated, are expected to be damaged by the herbicide used and are sown in a granular "zonolith" (expanded verrnikulitj, found in a plastic pot whose bottom is perforated (top diameter 6 cm) The pot is placed in a second plastic pot which is transparent and has an upper diameter of 7 centimeters and contains about 50 ml of a pre-prepared nutrient solution with the herbicide and the antibody, which solution rises in small drops by the filler material and wets seeds of germinating plants.

The loss of liquid is replenished daily with 50 ml pure Hewitt nutrient solution. Three weeks after the start of the test, the experiment is evaluated on a linear scale of 1 to 9, with 1 representing total plant damage and 9 representing healthy intact plants. The control solution used in parallel does not contain an antibody (antidote). The test used:

1) 4 ppm of prometryne = 2,4-bis- (isopropylamino) -6-m, ethylthio-s-triazine in sorghum (Sorghum) of the type "Funk G-522"

2) 4 ppm 4-ethylamino-6-tert-butylamino-2-chloro-s-triazine in 'Farnese' wheat

3) 4 ppm of α- (4- (p-trifluoromethylphenoxy) phenoxy) propionic acid n-butoxyethyl ester in barley "mazurka"

4) 5 ppm; of metolachlor, ie N- (1-methyl-2-methoxyethyl) -N-chloroacetyl-2-ethyl-6-methylaniline in sorghum (Sorghum) of 'Funk G-522'

5) 1 ppm of 2-methoxy-4,6 - (t-methoxypropylamino) -s-triazine in "Kleinwanzleben" beet.

The compounds of formula I achieve good antibody performance in these experiments. As; Examples include the following results:

test variant Compound No. herbicide impact assessment (without / with antibody) 2 73 2/5 4 93 2/5 4 396 2/5 4 4 3/7 4 19 Dec 2/6 (at concentration 1 ppm) 5 19 Dec 2/5 5 36 1/5 3 96 2/5 5 112 1/7 (at concentration antibodies 1 ppm ') 4 52 2/5 4 51 2/5 4 141 3/6 4 143 3/6 1 112 1/7 1 173 1/7 1 140 2/7 1 135 1/6 1 275 2/6 1 349 2/6 Test in which antidote (antidote) but not in the muddy state. Then applied during the swelling of the seed) applies the herbicide N- (1-methyl-2-methoxy- Soaking) ethyl) -N-chloroacetyl-2-ethyl-5-methylaniline or N-propoxyethyl-N-chloroacetyl-2,6-di- Rice seeds of the kind "IR 8" with <time ethylaniline in dilute solution and in quantity Impregnate for 48 hours solutions tested which, after conversion, corresponds to 1,5 kg 10 or 100 ppm. After- active substances per ha. 18 days after planting the seeds are left for about 2 hours o- the experiment is evaluated on a linear scale to prevent it from sticking. Rectangular May- from 1 to 9, where 1 is the total state plastic boxes (8 x 8 cm, height and 9 means condition 10 cm) is filled up to 2 cm under the clay edge- unaffected healthy plants. it-sandy soil. On even one flower pot with The compounds of formula I exhibit in this sow 4 g seeds and these seeds overlap test as an antibody (pro- only a very thin layer (about tijedy). The following are examples grain diameter). Soil up keeps in damp, results: compound number effect herbicide (without / with antibody) 100 ppm 396 2/5 397 2/5 46 2/7 326 2/5 331 2/5 352 2/5 10 ppm 90 1/4 138 2/5 313 2/5 302 2/5 303 2/5 311 2/5 171 2/5 1 2/6 53 2/6 55 2/5 56 2/5 61 2/6 26 2/5 35 2/6 3 379 2/5

compound number effect of herbicide (without / with antibody)

68 2/6 144 2/5 166 2/6 232 2/5 245 2/5 259 2/5 275 2/5 328 2/5 344 2/5 345 2/5 346 2/5

Pre-emergence antibody test (basic test):

General methodology:

The small pots (6 cm in diameter) are filled with horticultural soil into which the crop plants are sown, the seeds are covered with soil and they are slightly pressed. Subsequently, the substance to be tested as an antibody (prepared from a wettable powder) in an amount corresponding to 4 kg of active substance per ha is sprayed in the form of a dilute solution. Immediately thereafter, the herbicide is sprayed appropriately. After standing for 18 days at about 20-23 ° C and 60-70% relative air humidity, the experiment is evaluated on a linear scale of 1 to 9, with 1 indicating the state of total plant destruction and 9 indicating the state of healthy and not affected plants. Plants without antibody are used as controls.

This test uses:

1) 1.5 kg of α- [4- (p-trifluoromethylphenoxy) phenoxy] propionic acid n-butoxyethyl ester per hectare in "Orla 264" maize *

2) 1.5 kg of Metolachlor, ie N- (1-methyl-2-methoxyethyl) -N-chloroacetyl-2-ethyl-6-methylaniline per hectare in sorghum (Sorghum) of the species "Funk G — 522" »

3) 2.0 g of Prometryn, ie 2,4-bis- (isoipropylamino) -6-methylthio-s-triazine in soybean per ha

4) 2.0 kg of 4-ethylamino-6-tert-butylamino-2-chloro-s-triazine per ha in 'Farnese' wheat

5) 4,0 kg of Prometryn, ie 2,4-bis- (isoproipylamino) -6-methylthio-s-triazine per ha in sorghum (Sorghum) of the species 'Funk G-522'

6) 2,0 kg of N- [4- (p-trifluoromethylphenoxy) phenoxy] propionic acid n-butoxyethyl ester per hectare in 'Mazurka' barley

7) 1,0 kg of N-methoxyethyl-N-chloroacetyl-2,6-dimethylaniline per ha in 'Anjou 196' maize

The compounds of formula (I) give a good effect (as an antidote) in these experiments. Examples include:

test variant compound number evaluation of herbicide effect (without / with antibody)

6 138 4/7 5 398 1/4 4 31 2/4 7 51 2/5 3 378 2/5 3 291 2/5 3 306 2/5 3 226 2/5 3 179 2/5

Effect of antibody (antidote) on transplanted rice plants in separate application (application of antibody preemergence, application of herbicide postemergence).

Plastic pots (8x8 cm, height 10 cm) are filled up to 2 cm below the edge with soil moistened to muddy state. The substance to be tested as an antidote is applied by spraying as a dilute solution onto the soil surface in an amount corresponding to 4 kg of active substance per ha. The 'IR — 8' rice plants are transplanted into pre-prepared flower pots at a stage of 1 1/2 to 2 leaves. The next day the water level rises to about

1.5 cm ;. 4 days after transplanting, 0.75 kg of 2-ethylamino-4- (1,2-dimethyl-n-propylamino) -6-methylthio-s-triazine is applied to the water in the granulate form after 1 ha. The temperature for the duration of the experiment is 26-28 ° C, the relative humidity 60-80%. 20 days after the herbicide treatment, the experiment is evaluated on a linear scale of 1 to 9, with 1 indicating the state of total plant damage and 9 indicating the state of healthy unaffected plants. Plants without antibody protection serve as controls.

The compounds of formula I show good activity in this experiment as antibodies (antidotes).

compound number herbicide effect evaluation (without / with antibody)

396 3/6

5/7

5/8

Claims (7)

SUBJECT Composition for the protection of crop plants against aggressive agrochemicals, characterized in that they contain, as an active antidote, at least one compound of the general formula I Ar — C — X (I) N — O — CO — R wherein Ar is arbitrary - a phenyl or naphthyl radical of the formula - optionally a halogen, nitro or C 1 -C 4 alkyl group substituted with a furan or thiophene ring, - one of -COOR 4 or -CO-Re, X is cyano, alkanoyl of 2 to 4 5 carbon atoms, C 2 -C 5 carboxylic acid ester residue, -COOH group, hydrogen, C 1 -C 9 carboxylic acid arnide residue, halogen or C 1 -C 4 alkyl, R1 is hydrogen, halogen, C1-C4alkyl, C1-C4alkoxy or, optionally, at most twice, para, phenoxy substituted by halogen, cyano, nitro or trifluoromethyl, R 2 and R 5 are each independently hydrogen, halogen, nitro, C 1 -C 4 alkyl, C 1 -C 8 haloalkyl, C 1 -C 4 alkoxy, Rd represents an aliphatic group of up to 8 carbon atoms, a cycloaliphatic group of 3 to 7 carbon atoms, an araliphatic group of 7 to 18 carbon atoms, wherein the aromatic radical may be substantially substituted as indicated: for the radicals R 2 and R 3 and additionally substituted with cyano , and R is arbitrary a) a residue of N - (R 5) (Re), wherein R 8 is hydrogen or C 1 -C 4 alkoxy or the radical R 6, R 6 represents an aliphatic group having 1 to 8 carbon atoms, a cycloaliphatic group having 3 to 7 carbon atoms, an araliphatic group having 7 to 18 carbon atoms, an aromatic group having 6 or 10 carbon atoms or. a 5- to 10-membered beterocyclic ring system with 1 or 2 rings and at most 3 heteroatoms from the group consisting of nitrogen, oxygen or sulfur, the aromatic radical may be substantially substituted as indicated; for Rz and R3, (b) a residue - YR7 in which: Y is oxygen or sulfur; and R7 has the meaning given for R6, Re means arbitrarily (a) —N (Rg) (Rio) in which: R 9 is hydrogen, C 1 -C 4 alkyl or C 3 -C 7 cycloalkyl; and R 10 has the same meaning as R e or - represents hydrogen, or R 9 and R 10 together with the nitrogen form a 3- to 7-membered ring which may be substituted with C 1 -C 4 alkyl groups, (b) the radical —NH — CONHR10, wherein R 10 is as defined above. 2. A composition according to claim 1, wherein the antidote comprises at least one compound of formula (I) wherein: Ar represents a phenyl or naphthyl radical as defined in point 1, X represents cyano, hydrogen of C2 -C5 alkanoyl, C2 -C5 carboxylic acid ester residue, C1 -C9 carboxylic acid amide residue or C1 -C4 alkyl group, R 1 represents hydrogen, halogen or, optionally, at most twice halogen, cyano or trifluoromethyl substituted phenoxy in the para position, R 2 and R 3 are each independently hydrogen, halogen, C 1 -C 4 alkyl, C 1 -C 8 haloalkyl, C 1 -C 4 alkoxy, and Y, R 5, R 6 and R 7 have the meaning given in point 1. 3. Compositions as claimed in claim 1, characterized in that they contain at least one compound of the formula I as an active antidote in which: Ar represents a phenyl radical as defined in point 1, X is cyano, hydrogen, acetyloxy, -COO (alkyl) of 1 to 4 carbon atoms in alkyl, -COONH2, COONH (alkyl) of 1 to 4 carbon atoms in alkyl, -CON (alkyl) 2 of 1 to 4 carbon atoms alkyl carbon atoms, methyl group, R 1 is hydrogen, R2 and R3 are hydrogen, halogen, C1-C4alkyl, trifluoromethyl, methoxy, ethoxy, R 5 is hydrogen, C 1 -C 4 alkyl or C 1 -C 4 alkoxy, R e represents an aliphatic group of up to 8 carbon atoms or optionally a halogen, an alkyl group of 1 to 4 carbon atoms, a trifluoromethyl group, a methoxy group or an ethoxy substituted phenyl group, Y is oxygen or sulfur; and R 7 is as defined above for R e. 4. The composition of claim 1, wherein the antidote comprises at least one compound of formula (I) wherein: Ar is optionally a halogen or C 1 -C 4 alkyl group substituted with a thiophene ring, Y, X, R 5, R 6 and R 7 are as defined in point 2. 5. A composition according to claim 1, wherein the antidote comprises at least one compound of formula I wherein: Ar is optionally a halogen or C 1 -C 4 alkyl group substituted with a thiophene ring and X, Y, R 5, R 6 and R 7 are as defined in point 3. 6. A composition according to claim 1, wherein said antidote comprises at least one compound of formula (I) wherein: Ar represents a group - COOR 4 or * —CORe, wherein Rd represents an aliphatic group of up to 4 carbon atoms or a phenyl group and R5 denotes R 8 and R 10 independently of one another are hydrogen, alkyl of 1 to 4 carbon atoms or optionally halogen, trifluoromethyl or alkyl of 1 to 4 carbon atoms substituted by phenyl, and X, Y, R 5, R 6 and R 7 are as defined in roll 2. 7. A composition according to claim 6, wherein the antidote comprises at least one compound of formula I wherein X, Y, R5, R6 and R7 are as defined in point 3.