PL117292B1 - Agent for protection of crops against aggressive chemicals used in agriculturegressivnykh khimikatov,primenjaemykh v sel'skom khozjastve - Google Patents

Description

The subject of the invention is an agent for the protection of crops against aggressive chemicals used in agriculture, containing new carbamates and carbonates of oximes of the general formula 1. In formula 1, Ar may be: - a phenyl radical of the formula 2 or a naphthyl radical of the formula 3, - a furan or thiophene ring optionally substituted with halogen, NO 2 or a lower alkyl radical, - one of the groups —COOR 4 or —CO — R ", X represents a —CN group, a lower alkanoyl radical, a carboxylic acid ester group, a —COOH group, hydrogen, a carboxylic acid amide group, halogen or lower alkyl radical, R 1 is hydrogen, halogen, lower alkyl, lower alkoxy or phenoxyl in the para position, optionally substituted up to twice with halogen by the CN group. NO2, CFS, Rs and Ra independently represent hydrogen, halogen, NOf group, lower alkyl, haloalkyl or lower alkoxy group, R4 is aliphatic, cycloaliphatic and non-arylaliphatic, the aromatic radical may be substantially substituted as specified for R * and Rs, and additionally the group -CN and R may be optionally: a) the group -NCRsJfRg), in which R5 is hydrogen. 30 or lower alkoxy or Re, and R 6 is aliphatic, cycloaliphatic, arylaliphatic, aromatic or heterocyclic, the aromatic group being substantially substituted as specified for R * and R 3, b) the group - YR7, in which Y is oxygen or sulfur, and R7 is as defined for R6, R8 is optionally: a) the group —N (R ") (R10), in which R9 is hydrogen, a lower alkyl or cycloalkyl radical, and Ri0 is Re or is hydrogen or R9 and Rw together with -N forming a 3- to 7-membered ring which may be substituted with lower alkyl radicals, b) the -NH-CONHR10 group. Compounds of formula I are therefore a) carbamates or b) (thio) carbonate. In formula I, the term halogen is understood to be fluorine, chlorine, bromine or iodine. The carboxylic acid esters are the lower alkyl esters of the carboxylic acids, and the carboxylic acid amides in addition to -CONH2 also denote monoalkylsubstituted or symmetrically or asymmetrically substituted dialkyl amides, the alkyl radicals representing lower alkyl radicals. part of the substituent comprises branched or unbranched alkyl radicals having 1 to 8 carbon atoms. The lower alkyl radical is a C1-C4-alkyl radical. Examples include the radical 117 2923 117 292 4 methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tertiary, butyl, tertiary butyl, as well as higher homologues such as the amyl radical, isoamyl, hexyl, heptyl and octyl together with their isomers. According to their meaning, alkanoyl or cyanoalkyl radicals contain an additional carbon atom. The term aliphatic radical includes saturated (alkyl) as well as unsaturated (alkenyl, alkadienyl, alkynyl) radicals substituted with halogen, substituted with cyano and interrupted with oxygen containing at least 8 carbon atoms. The term aromatic radical in the definition of R 4, B ", R" includes phenyl and naphthyl radicals. The term aryl-aliphatic radical should be interpreted in accordance with both of the above definitions. An aryl-aliphatic radical includes an aryl radical such as, for example, an optionally mono-, di- and triple-substituted phenyl or naphthyl radical which, via a lower alkyl or lower alkenyl radical, it is bound to the rest of the molecule. Examples are basic elements such as benzyl, phenethyl, phenylallyl as well as homologues. The term heterocyclic radical includes ring systems of 5 to 10 members with 1 or 2 rings and at least 3 heteroatoms from the series N, O and S. The C1 - Cf - cycloalkyl radicals are: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cycloheptyl radicals. Cycloaliphatic radicals correspond to this ring chord and, if possible, may also contain one or more double bonds. No. 3,799,757 aryloxylnitrileximes of the general formula where X is H, Cl, Br, NO * have insufficient performance as plant growth inhibitory and regulating agents, and are not permanently and after a short period of time. May is decaying. They are not known to act as antidotes for herbicides, while oximes of formula I are excellent for the protection of crops such as millet, rice, maize, types of grain (wheat, rye, barley, oats), cotton, sugar beet, cane. sugar, soybean, etc., against the attack of agricultural chemicals aggressive to plants, especially herbicides belonging to the most diverse classes of substances, such as triazines, phenylurea derivatives, carbamates, thiolcarbamates, haloacetanilides, esters of halogenated phenoxyacetate esters phenoxy phenoxy acetic acid and phenoxy phenoxy propionic acid, substituted esters of pyridine oxyphenoxy acetic acid and pyridine oxyphenoxy propionic acid, derivatives of benzoic acid etc., as long as these substances do not act selectively or insufficiently selectively, so in addition to the weed control, also in less or more severe damage to crops. Invention to This also applies to compositions containing the above-mentioned oxime ethers of the formula I together with herbicides. Various substances have already been proposed as antidotes or antidotes which are suitable for specifically counteracting the damaging effects of the herbicide on crops, i.e. exerting a discernible effect on the herbicidal activity of the weeds to be controlled; Such a countermeasure, also called Safener, can, depending on its properties, be used for the pretreatment of seed material of a cultivated plant (seed or cuttings dressing) or before sowing into seed furrows, or as a tank mixture alone or with a herbicide before or after plant emergence . Pre-emergence trimming involves not only pre-plant incorporation trimming (PPi ™) but also trimming of sown but not yet cultivated land. British Patent No. 1277557 describes the treatment of seeds or shoots of wheat and sorghum with certain oxamate esters and amides before attack by N-methoxymethyl-2 ', 6'-diethylchloroacetanilide (Alachlor). Other references (German DOS Patents No. 1952910 and No. 2245471, French Description Patent No. 2,021,611 proposes counter-agents for the treatment of seeds of cereals, maize and rice to protect against herbicidal thiolcarbamates. German Patent No. 1,576,676 and U.S. Patent No. 3,131,509 propose hydroxyaminoacetanilides and hydrantoins to protect seeds. cereals against carbamates such as IPC, CIPC etc. In further development all these preparations, however, turned out to be insufficient As antidotes, one should mention especially those compounds of formula I, where Ar is a phenyl or naphthyl radical as defined above, and the other substituents have the following meaning: X represents a cyano group, hydrogen, lower alkanoyl radical, carboxylic acid ester group, an acroxylic acid amide group or a lower alkyl radical, R 1 is hydrogen, halogen or a phenoxyl group located in the position of para and possibly substituted up to twice with halogen, the group CN or CF, Ri and Rj independently of each other mean hydrogen, halogen, lower alkyl radical, haloalkyl radical, lower alkoxy group, while Y, R5, R *, R7 have the meanings given above. This subgroup is called the group of compounds Ia. Among these compounds, the group Ia, one of the most preferred antidotes of the group of compounds is the new group Ib, in which Ar is a phenyl radical, X is a cyano group, hydrogen, acetyl radical, group —COO lower alkyl, COONH, group —COONH lower alkyl, group —COON (lower alkyl, methyl radical, Ri is hydrogen, R * and Rt mean, hydrogen, halogen, lower alkyl radical, CFt group, Metolugr 10 20 29 30 35 40 41 50 55 M117 292 5 6 Iowa, ethoxy group, and R5 is hydrogen, lower alkyl or lower alkoxy, R "is aliphatic or phenyl, optionally substituted with halogen , lower alkyl group, CFS group, methoxy group or ethoxy group, Y is oxygen or sulfur and R7 has the meaning given above for R1. An important group of antidotes are those compounds of formula I in which Ar is an optionally substituted thiophenyl ring halogen or low a lower alkyl radical and in which the X, Y, R5, R6, R7 substituents have the meaning given for the group of compounds Ia and preferably for the group of compounds Ib. Another important group of antidotes for the protection of crops against herbicides is this subgroup of formula 1, where Ar is one of the groups —COOR4 or —COR8, where R4 is a lower aliphatic group of at least 4 carbon atoms or a phenyl radical and in the definition of Re the substituents R * and Rio independently represent hydrogen, lower alkyl radical or the radical fe ¬nyl optionally substituted by halogen, the group CF3, lower alkyl radical, and the substituents X, Y, R5, Re, R7 have the meaning given for the group of compounds Ia and preferably the meaning given for the group of compounds Ib. The compounds No. 62, No. 79 and No. 111 are particularly preferred. The oximes of formula I surprisingly have the property of protecting crops from the effects of agricultural chemicals that are aggressive to plants, especially herbicides of various classes of such substances. such as 1,3,5-triazines, 1,2,4-triazinones, phenylurea derivatives, carbamates, thiolcarbamates, esters of phenoxyacetic acid, esters of phenoxypropionic acid, haloacetanilides, esters of halophenoxyacetic acid, substituted esters of phenoxyphenoxyacetic and phenoxy-phenoxyacetic acid , substituted esters of pyridinoxyphenoxyacetic acid and pyridine oxyphenoxypropionic acid derivatives of benzoic acid, etc., as long as they are intolerant or insufficiently tolerated with respect to crops. Such antidotes or antidotes of formula 1 may be used depending on the purpose for which they are used. for the pretreatment of seed of a cultivated plant (seed treatment n or cuttings) or introduce into the soil before or after sowing or use alone or together with the herbicide before or after emergence of the plants. Therefore, plants or seeds can be treated in principle independently of the application of the phytotoxic chemical. This treatment may, however, also be carried out simultaneously (tank mix). Pre-emergence treatment includes not only the pre-plant incorporation treatment of the cultivated area (PPi "Pre plant incorporation") but also the treatment of sown but not yet covered cultivation areas. to the herbicide depends as much as possible on the type of application. If a field treatment is carried out, the ratio of the amount of antidote of formula I to the phytotoxic chemical is from 1: 100 to 5: 1, preferably from 1: 20 to 1: 1 For seed treatment and the like, however, much less antidotes are needed compared to, for example, the amount of later applied herbicide per hectare of cultivated area (e.g., about 1: 3000 to 1). : 1000). As a rule of thumb, preventive measures such as seed dressing, the antidote of formula 1 is only loosely related to possible later half-treatment. m with chemicals used in agriculture. The pretreated seed or plant material may later come into contact with a variety of chemicals in agriculture, horticulture and forestry. The invention therefore also relates to crop protection agents which as active ingredients contain an antidote of formula I with the usual the media used. Such agents may, if appropriate, also be mixed with an agricultural substance against which the cultivated plant is to be protected, e.g. with a herbicide. As arable crops in the sense of this invention, it is necessary to consider all plants which, in any way, The figures produce income-generating substances (seeds, roots, stems, tubers, leaves, flowers, content such as oils, sugar, starch, protein, etc.) and are cultivated and cared for for this purpose. Such plants include, for example, all kinds of cereals, corn, rice, millet, soybeans, beans, peas, potatoes, vegetables, cotton, sugarcane, sugarcane, peanuts, tobacco, hops and also ornamental plants. , fruit trees as well as banana, cocoa and rubber plants. The above list is not intended to be limiting. In principle, the antidote can be used wherever a crop needs to be protected against the phytotoxicity of a chemical. The compounds of formula I can be prepared from the free oximes by several methods shown in Schemes 1-6, with carbamates being prepared according to in schemes 1-3 a (thio) carbon according to schemes 4-6. (Na represents sodium or another alkali metal in these schemes.) For the preparation of the compounds of the formula I, mainly all solvents which behave inertly under the reaction conditions, such as, for example, hydrocarbons, are suitable, but above all polar solvents such as acetonitrile, dioxane, 2-ethoxyethanol, dimethylformamide, as well as ketones such as methyl ethyl ketone, acetone, etc. However, solvents containing hydroxyl groups are excluded. Reactions are carried out at temperatures from -10 ° C to about 150 ° C, preferably between 20 ° C and 120 ° C. Bases such as tertiary amines (triethylamine, triethylenediamine, piperidine and others) can be used as splitters for hydrogen halide. In some cases it is also sufficient to suspend the soda in an anhydrous reaction medium. Oximes exist in two stereoisomeric forms, the syn variant and the anti-variant, both stereoisomeric forms as such and as mixtures of any ratio varying within the scope of the description. The following examples illustrate the preparation of new oximes of formula 1. The temperature is given in degrees Celsius. Example 1 Preparation of the compound of formula 5 (Compound No. 1). A total of 23.5 g (0.16 moles) is added to 100 ml of acetonitrile. ) benzyl cyanide oxime. After the addition of 25 ml of methyl isocyanate and a small amount of catalytically acting diazabicyclooctane, the reaction mixture is heated to 50 ° C., and the final product is precipitated after a short time. The mixture is left to stand overnight, drained, and washed with acetonitrile. and then dried at 60 ° C. with hexane. The yield was 29.2 g (89.8% of theory) of a product having a melting point of 172-175 ° C. EXAMPLE II. Preparation of the Compound of Formula 6 (Compound No. 34). 14.6 (0.1 mol) of benzyl cyanide oxime are introduced into 100 ml of acetonitrile and then 18.7 g (0.1 mol) of 3-trifluoromethylphenyl isocyanate are added and a catalytically small amount of diazabicyclooctane. The reaction is immediate and the reaction mixture is heated to 50 ° C. The mixture is stirred for another 4 hours in the water bath. The final precipitate is filtered off, washed with acetonitrile and dried in vacuo at 50 ° C. 25.5 g of product are obtained, mp 172-173 ° C. Example III. Preparation of the compound of formula 7. To a mixture of 11.9 g (0.05 mole) of sodium 3,4-dichlorobenzyl cyanide oxime in 50 ml of acetonitrile, 6.3 g (0.05 mole) of the acid S-ethyl ester are added dropwise. The reaction mixture is then heated for 4 hours, refluxed, and concentrated under reduced pressure. The remainder is mixed with methylene chloride, mixed with activated carbon and filtered. After evaporating the slurry, 11.2 g (73.7% of theory) of product are obtained in the form of an oil. Preparation of the Compound of Formula 8 (Compound No. 77). 14.2 g (0.1 mole) of ethyl cyanoacetate oxime in 100 ml of acetonitrile are placed in a stirred flask. While stirring, a solution of 15.3 g of p-chlorophenyl isocyanate in 20 ml of acetonitrile is added dropwise thereto, and the reaction mixture is stirred for 5 hours at 60-70 ° C. The solution is then filtered hot and the filter is cooled in water. with ice. The final crystallized product is filtered off, washed with a mixture of acetonitrile and hexane and then dried. The melting point of the product is 147-148 ° C. Thus, or according to one of the above-mentioned methods, the carbamates listed in Tables 1-7 are prepared, in which the abbreviation r in parentheses denotes decomposition. Table 1 Compounds of formula 9 Compound No. 1 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 Ri 2 HHHHHHHHHHHHH 2 — a 2 — Cl H 2 — Cl H 4-III. C4Hf HHHH Rj 3 HHHHHH 4 -C1 4r-Cl 4 ^ -Cl 4-C1 4 ^ -Cl 4 ^ -Cl 4 ^ -Cl 4 ^ -Cl 4 — Cl 4 ^ -Br 4 ^ -Cl 4 — Cl H 4 — CH, 0 4 ^ -CH, 0 4-CH, 0 3-CF, Hs 4 HHHHHHHHHHHHHH CH, H CH, HHHHH He 5 CHs C, H5 n — C, H7 isoC, H7 n — C4H9 —CH3CH —Cl n — C4H | —CHi — O — CH, Tertiary C4H »isoC | H7 CH, C, H, nC, H7 CH, CH, CH, isoC, HT CH, CH, CH, C, H, isoC, H7 CH, Temperature mp ° C 6 172-175 93-96 89-91 92-94 98-101 138-141 124-126 110-114 102-105 140-144 191-193 105-108 112-113 152-154 124-128 112 —115 92— 93 131 ^ 132 162—165 182—184 ioe — 110 129—131 150—151117 292 * 10 cont. table 1 1 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 1 • »HHHH 3 — Cl 3 — Cl H 'HHHHHHHHH 4-IIIrd C4H, 4-IIIrz .C4H9 4-Tertiary C4H, HH 2-a 2-a 2-a 4-Tertiary C4H, 1 HHH 4-Tertiary C4H9 4 — Cl 4 — Cl HHHHH 4 — Cl 4 — Cl 4 ^ -Cl 4— Cl 4 ^ -Cl HHH 3-CF, 3-CF, 4-Cl 4-C1 4-Cl H 4 HHHHHHHHHH 1 HHHHHHHHHHHHHHH 5 -CcHs -C6H4C1 (4) -C6H4-CH, (4) -C6H5 -C6H8C1, ( 3,4) —C6H8Cl (3) isoC3H7 <4) —C6H4-CF8 (4) —C6H8C1 (3) CF8 (4) -C «H, (CF3) 2 <3.5) -C« H4-F ( 4) —C6H4 — CF8 (3) —C6H4 — CF8 (3) -C6H4C1 (4) -C6H3Cl2 (3,4) —C6H8Cl (3) isoCIH7 (4) -CeH5 —C6H4C1 (4) -C | HiCM3,4 ) —CeHrfCFgktf ^) —C6H5 isoC8H7 -CeHj -C6H8 (CF3) 2 (3.5) and —C6HtCli (2.4) -CeH ^ CF ^ tf) 1 6 132—134 184—186 153 ^ 154 131—133 210—213 172—175 188—190 207—208 196—198 159—161 172—173 187—190 204—205 204—205 150—151 148—150 131—133 68— 71 58— 60 141—143 116— 118 163—164 110—113 152—153 136—140 Table 2 Compounds of formula 10 Compound No. 49 50 51 52 53 54 55 56 57 58 59 60 X CH8 HHHHH CH8 —COCHt HHHH Hi H 2 — Cl HHH 2— Cl HHHHHH Ri H 4 ^ -Cl H 4 ^ -Cl H 6 — Cl HH 4 ^ -Cl 4 — Cl 4 ^ -Cl 4 — Cl Rs HHHHHHHHHHHHR “CHt CH, CH8 CHj -C6H4Cl (4) -CH” C1 < 4) -C6H4C1 (4) -C6H4C1 (4) -C6H4CK4) -CeHs —CsH.-CH ^ S) —CJU-F (4) Melting point ° C 97— 99 137 92— 94 133—136 145—146 142 —144 105—106 297—298 151—152 106—109 119—121 130—132 Table 3 Compounds of formula 11 1 Compound no | 1 1 61 62 63 64 65 66 67 | 68 Ar 2 a-naphthyl a-naphthyl HjN — CO— HjN — CO— HjN — CO— HiN — CO— H2N — CO— HjN — CO— X 3 —CN —CN —CN -CN —CN —CN —CN - CN R5 4 H C2H5 HHHHHH R6 5 CH8 C2H5 —Cs ^ Ci ^) -C6H4C1 (4) -C6H8C12 (2.5) -CeH.CF ^) —CsH.CFjW —C “H8Cl (3) CHt (4) Temperature mp ° C 6 154 ° 158 162-164 203-204 201-203 176-177 179-183 170-180 163-164 1117 292 11 12 cd. table 4 1 1 69 70 71 72 73 74 75 76 77 78 79 80 61 2 HjN — CO— HzN — CO— H2N — CO— H, N — CO— H2N — CO— HjN — CO— HsN — CO— H2N— CO— CH5OOC— C * H5OOC— (5Cl) 2-thienyl (5Cl) 2-thienyl (5Cl) 2-thienyl 3 —CN —CN —CN -CN -CN -CN -CN —CN -CN -CN —CN - CN —CN 4 HHHHHHHHHHHHH 5 CHS C, H5 —CHtCHi — Cl —nC, H7 — isoCjH7 —nC4H, -C.H5 —C * H, CF3 (3) C1 (4) -CflH4Cl (4) CH, -C6H4C1 ( 4) CHi —C ”HtCl (4) CF ^ 3) 6 J 176—177 116—120 141—142 113—116 125—126 92— 96 174—175 182—183 147—148 101—103 186 186 184 Table 4 Compounds of formula 12 Compound # 1 [82 83 84 85 86 87 88 89 90 91 92 93 94 95 96 97 98 99 100 101 102 103 104 105 106 | 107 1 108 109 110 111 112 113 114 115 116 117 118 119 120 | R4. 2 CH, 0 - CH, 0 - CH, 0 - CH, 0 - CH, 0 - CH, 0 - CH, 0 - CH, 0 - CH, 0 - CH.O - 1 CH, 0 - CH, 0 - CH, 0— CH, 0— CH, 0— CH, 0— CH, 0— CH, 0 — CH, 0— CH, 0— CH5 — O CaHs — O CH, —O C2H5 — OC, H, —OC »Hb — O CH, —O CaHs — O CHs — O CaHs — O CiHf — O CHb — O C1H5 — O C1H5—0 CtHj — O C2H5 — O CtHs — O CH, —O (s) C4H9-0 | R «3 HHHH 1 HHHHHHHHHHHHHHHHHHHHH HHHHH 1 HHHHHHHHHH Rt 4 C6HICF, (3) C1 (4 C6H4CF, (3) CH, C, H4NO2 (3) C6H4C1 (3) C.H4CK4) Ce <4H4CK4) C «Hl (OC4H§) i) (4) CACU3.4) 1 C, H, Cl (3) Br (4) CH, Cl2 (2.5) C, H« CH5 (2) C1 (3) CH , CH, <2) C1 (4) C <H3Br (2) CH, (4) CiHs (CH ^ 2.4) CeHrfn (2) NO2 <4) C6H ^ 12 (2.4) —CH, —CHtCHjCl -CH, -CAGW) - —C.H4C1 (3) -C6H4C1 (4) -C «H4CF ^ 3) -CeH4CF, (4) —CHiNCO) -GACHtf4) —C, H4 (0-C4Hf) and X4)« -CtHlCl1 <3,4) -C.H2CW2.5) -CiHlCFs (3) Cl (4) -CiHlCl (2) NOt (4) -C «Hf (CFI), (3,5) -CH, (2 ) C1 (4) -CHtCW2,4,5) —CH, —CHtCl, -CH "C1 (4) \ Melting point ° C 5 162—163 147—148 14 * —150 1 166—167 162—163 157— 158 136—138 127—128 139—140 162—163 (r) 170—171 164—165 118—120 119—120 134—135 115—117 165—166 (r) 143—145 122—123 72—74 130 —132 81—82 139—141 156—157 117—119 136—137 145—147 121—122 127—128 160—161 136—137 141—142 j 133—134 155—157 90—91 137—139 104— 106 73—75 128—130 \ 117 292 13 14 cont. table 4 1 1 121 122 123 124 125 126 127 128 129 130 131 132 133 134 135 136 137 138 139 140 141 142 143 144 145 146 147 148 149 150 2 (s) C4H, -0 1 (s) C4H «—O (s) C4H, -0 (s) C4H9 — O (s) C4H, —O (s) C4H9 — O (s) C4H9 — O CH2 = CH — CH, —O CH2 = CH — CH, —O CH2 = CH — CH, —O CH2 = CH — CH, —O CH2 = CH — CH, —O CH2 = CH — CH, —O CH2 = CH — CH, —O CH2 = CH — CH, —O CH2 = CH— CH, —O formula 13 formula 13 formula 13 formula 13 formula 13 H5C «—CH = CH — CHjO— H5C« —CH = CH — CH, 0— HjCe — CH = CH — CHiO— CHsO— CH, 0 formula Formula 13 CH80— 3 HHHHHHHHHHHHHHHHHHHHH HHHH CH8 HHHH 4 —CeH.CFstf) -C6H4CFs (4) —CHtCKS ^ -C6H4CW2.5) —C6H4CF, (3) C1 (4) —CH, C6H5CH) —CH, C6H5CH) (4) C6H4CF3 (3) CeH.CF ^) C6H3C12 (3.4) C6H3C1, (2.5) C6H, Ci3 {2.4.5) —CH2CH, C1 —C6H4C1 (4) —C6H4CF ^ 3) - C6H4C1 (4) —C6H3CF8 (3) C1 (4) -C6H2C13 (2I4.5) —CH, —CeHlCltf) —C6H, Cl2 (3.4) —C6H, C18 (2.4.5) —CH8 CH, C1, (3.5) C6H, C1, (3.5) C6H, CW3.4) C6H8C1, (3.4) 5 93—95 109—110 140—141 100—101 126—127 80—81 57— 59 103—105 118—120 131—132 106—107 121—123 126—127 130—131 124—126 61—63 141—142 1 94—96 162 —163 131—132 124—126 99—101 136 (r) 138 (r) 161 (r) 105—106 156 (r) i07—108 162—163 162—163 Table 5 Compounds of formula 14 1 Compound No. 1 151 152 153 154 155 156 157 158 159 160 161 162 163 164 165 166 167 168 169 1 170 1 171 172 R * 2 HHHHHHHHHHHHHHHHHHHHH HR «3 C« H8CW3,4) C8H3CF8 (3) C1 (4) C6H5 C6H4C1 (2) C6H4C1 (4) C6H4CF3 <4) C6H8C18 (3.4) CsH.CHjW C6H8CF8 (3) C1 (4) C6H, C1 (2) NO, (4) C6H, C18 {2,4,5) —CH, -C6H5 CeH.CIW) C6H8C1, {3,4) C6H8CF8 (3) C1 (4) —CH8 C8H7 CH (CH5), C, H5 Cl2CH,), CH8 R “4 —CH, —CH, —CH, —CH, —CH, H —CH, .Rio 5 —CH8 —CH, pattern 15 pattern 15 pattern 15 pattern 15 pattern 15 pattern 15 pattern 15 pattern 15 pattern 15 pattern 16 pattern 16 pattern 16 pattern 16 pattern 16 CH, CH, CH, H CH, m.p. ° C 6 '153-154 154-156 143-144 120—123 142-144 160—162 153-154 133-135 140 (r) 165 143-145 113 (r) 124 ^ 125 125—127 155—157 145 (r) 90 (r) 46—50 62—66 90 206—207 72—76 117 292 15 16 cd. table 5 1 1 173 174 175 176 177 178 179 180 181 182 183 184 185 186 187 188 189 190 191 192 193 194 195 196 197 198 199 200 201 202 203 204 205 206 207 208 209 210 211 212 213 214 215 216 217 218 219 220 221 222 223 224 225 226 227 1 2 HHHHHHHHHHHHHHHHHHHHH HHHHH —CH, '—CH, —CH, —CH, —CH, HHHHHHHHHHHHHHHHHHHHH H n H 1 3 CHzCHjC3 (C8H4C5) C3H4C1 (C8H6C1) (4) C6H5 C5H4CK4) C6H3C12 (3,4) C6H3CF, (3) C1 (4) C6H5 C6H4C1 (3) C6H4C1 (4) CeH4CF ^ 3 C6H4CH3 (3) CeH, Cl, <3.4) C6H, C1, (2,5) C6H, CF, (3) C1 (4) C «H, CH3 (2) C1 (4) C, H4CHrf2) Cl (3) C6H, CW2,4) C6H9C1 (3) CeH4Cl (4) C6H4CF, (4) C6H4C1 (4) C6H4CF, (4) C6H3C1, (3,4) C6H3C1 (2) NO2 <4) —CH, —CH, —CH, —CH, —CH, C — H, C1, (2.5) C6H4C1 (3) C6H, CF3 <3) a (4) C6H, C1 (3) CF, (4) C6H4C1 (4) C6H, Cl2 (3.4) —CH, CH (CH3), C3H7 C4H9 C3H7 CH (CH3), C4H, CH, —CH, —Cl C, H4C1 (4) C6H, C] ^ 3.4) C6T-J, C1 (3) CH ^ 4) —CH, CH4CK3) C6H3C1 ^ 3,4) C 1 H 3 Cl (3) CF, (4) C 1 H 4 CF, (4) CH 3 CH, C 1 —CH, [1 4 CH, HHHHHHHHHHHHHHHHHHHHH HHHHHHHHHH HHHHHHHHHHHHHHHHHH 1 5 1 CH, formula 17 formula 17 formula 17 1 —C6H4CF, (3) -GtH &lt; GF <(3) -C6H4CF3 (3) -CeH4CF3 (3) -C, H3CW2,4) -C &lt; H ^ W2 , 4) -C6H, CW2.4) -C, H, C1, <2.4) -C, H, C1, (2.4) -CH ^ W2.4) -CSH, CW2.4) | -C, H3CW2,4) 1 -C, H3C1, (2,4) -CeH, CW2,4) -C8H, C1, (2,4) -CHrfCF,), ^) -C6H, (CF3), ( 3,5) —C6H, —C6H, Cl (2) NO, (4) —C6H3C1 (2) N0, (4) —C6H3Cl (2) NO, (4) —C6H3Cl (2) NO, (4) formula 15 —C, H3CH, (2) C1 (3) -C, H4CF, (3) -CHycisAS) formula 16 —C, H, Br (2.6) CH, (4) CH, CH - CH, CH, CH = CH, CH, CH * = CH, CH, CH- CH, CH, CH = CH2 CH, CH = CH, C, H, C, H5 C, H, CH, CH, CH, CH, nC, H , nC, Hs nC, H5 nC, H5 C12 H, CW3.5) C6H, Cl4.3.5) C6H, CW3.5) CH2Cl2 S) H CH3 1 6 1 99-101 159-161 130-132 176—178 163 (r) 180 (r) 161 {r) 169 (r) 179 (r) 154 (r) 172 165 (r) 152 (r) 176 (r) 185 (r) 162 (r) 154 ( r) 140 (r) 172 (r) 165 (r) 179 (r) 188 (r) 187 (r) 198 (r) 198 (r) 185 (r) 104-105 164 {r) 115-117 162- 164 71—72 120 (r) 154 (r) 175 (r) 139 (r) 170 (r) 164 (r) 111—113 103—105 78—90 70.5—74 67—70 116—118.5 107—109 105—106 177—178 18Ó (r) 166—167 124—126 190 (r) 173 (r) 182 (r) 169 (r) 141—142 167—168 117 292 1T M Table 6 Compounds of formula 18 1 Compound No. 1 228 229 230 231 232 233 234 235 236 237 238 239 240 241 242 243 244 245 246 247 248 249 250 251 252 253 254 255 256 257 258 259 260 261 262 263 264 265 266 267 268 269 270 271 272 273 274 275 276 277 278 279 280 281 282 283 284 285 Re 2 C «H4C1 (3) 1 C6H4C1 (3) C« H4C1 (3) C6H4C1 (3) C « H4C1 (4) 1 C «H4C1 (4) C6H4C1 (4) C« H4C1 (4) C6H3CH, (4) C1 (3) C6H3CH, (4) C1 (3) C6H3CH, (4) C1 (3) CeH3CH, (4) Cl (3) CeH8CH, (4) Cl (3) C6H, Cl2 <3.4) C6H, Clz (3.4) C «H, Cl2 <3.4) GAGM3. 4) C« H, CF, (3) C1 (4) C6H, CF, (3) C1 (4) C6H5CF, (3) C1 (4) C6H8CF, (3) C1 (4) C6H, CF, (3) C1 (4) C , H, C1 (3) CF3 (4) C6HIC1 (3) CF3 (4) CeHICl (3) CF8 (4) C6H, C1 (3) CF, (4) C6H, C1 (3) CFS (4) C6H4CF1 ( 2) C6H4CF, (2) CaH4CF ^ 4) CHCFjtf) CflH4CF, (4) C «H4C1 (3) C6H4C1 (4) C6H4C1 (4) C6HsCl2 <3.5) C§HjCl2 <3.5) C8H8Cl2 {3 , 5) C6H4CF, (3) C «H4CF, (3) C6H5 CaH CeH3CW2, 3) CH, CHjCH, CH, CjHrfn) C« H3C1 (3) CH1 (4) C | H ^ CH | (4) C1 ( 3) 06 ^ 011 (3.4) CH1CF ^ ClW C 'H4C1 (3) C6H, C1 (3) CH, (4) C' H, C1 '(3.5) C6H4CF, (3) C.H5 C6H , Clt (2,3) CH, H, 3 HHH CHj H ¦ HH CH, H CH3 HHHHHHHHHHHH CH, HHHHHHHH CH, HHHHHHH CH, HHHHHHHHHHHHHHHHHH Rio 4 CH, C, H5 H CH, CH, HC, H5 CH, CH, HC CH, C, H5 C4H9 (n) H CH, CtHs C4H9 H CH, CtH, HC, H7 (n) C4H, (n) CH, H CH, CjHs C4H9 (n) H CH, H CH, CH, C, H7 (n) CjHtfn) C4H9 (n) HC, H5 CH , CH, CH, H CH, HHHC, H5 HH CONH, CONH, CONH, CONH, CONH, CONH, CONH, CONH, CONH, CONH, mp. ° C 5 177-178 166-167 203 (r) 125-128 198—200 203 (r) 180 (r) 161—162 180 (r) 144—146 163—163.5 142—145 163—166 195 (r) 175.5 (r) 167.5—170 192—193 198 (r) 185 183 (r) 172 (r) 174—177 156—158 191 (r) 183—185 167—169 149—150 183 (r) | 193 (r) 180 (r) 189 (r) 134—135 155—157 - 170 (r) 170—174 200 (r) 159 (r) 190 (r) 190 (r) 109—110 175 (r) 162 , 5—163.5 156 (r) 177 {r) 116—120 119.5—124 113—116 163—164 197 (r) 205 (r) 200 (r) 206 (r) 197 {r) 197 ( r) 208 (r) 214-215 '203 (r) 216 (r) 19 117 292 20 Table 7 Compounds of formula 19 Compound No. 286 287 288 289 290 Re C4H9 C, H7 (n) CjH-Kizo) —CH, —CH, —Cl CsH-Kizo) Melting point ° C 131 (r) 133 (r) 207 (r) 140—145 (r) | 207 (r) 1 According to example III or one of the above methods, the (thio) carbonates listed in Tables 8 and 9 as well as other compounds listed in Table 10 are produced, where r is the distribution. Table 8 Compounds of formula 20 1 Compound No. 291 292 293 294 295 296 297 298 299 300 301 302 303 304 305 306 YR7 OCeH5 OCH, OCiH-Kizo) OCH | OC4H9 (n) OC »H7 0 (CH,), CH, OCH, OCH, OCH, OCH, SC, H, OC4H9 (n) OCjH-Kizo) SC, H5 SC, H $ Rio HHH CH, H CH, CH , H CH, —CONH, —CONH, H —CONH, —CONH, —CONH, CH, Melting point ° C 1 149 (r) 170 171-173 97-98.5 165-167 109-110 75—76 120—121 73—74 168 (r) 171—172 124 ^ 125 173 (r) 173 (r) 179 (r) 76-78 Table 9 Compounds of Formula 21 Compound No. 307 3C8 1 309 | 310 311 Ri HHHHHR * HHHHHG —O — C, H5 —O — iso C, H7 —O — CH, —O — IIICiH, —S — C, H, Melting point ° C 105-108 108 —110 108—110 85—86 59—62 Table 10 Compound No. 312 313 314 315 - 316 | 317 Structure Formula 22 Formula 23 Formula 24 Formula 25 Formula 26 Formula 27 Melting point ° C 184 (r) 144-146 (r) 83-85 126 (r) 145 (r) 170 {r) | As already mentioned, various methods and techniques are employed in the use of the compounds of the formula I for the protection of crops against chemicals used in agriculture. 1. Dressing the seed a) Dressing the seed The active ingredient, prepared as a wettable powder, is shaken out in a vessel until it is evenly distributed over the seed surface (dry dressing). w Per 100 kg of seed, from about 10 to 500 g of active compound of the formula I (40 g to 2 kg of wettable powder) are used. b) Dressing the seeds with an emulsion concentrate of the active compound of the formula 1 according to method a) (wet dressing). c) Dressing by immersing the seed in a spray liquid containing 50 to 3200 ppm of active compound of the formula I for a period of 1-72 hours and possibly subsequent drying of the seeds (treatment by immersion). Dressing the seed or treating the germinated seedlings is inherently the best method of application, since the treatment with the active ingredient is entirely directed to the crop in question. 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, whereby depending on the methodology allowing for the addition of other active ingredients or micro-supplements, there may be upward or downward deviations. downstream of the indicated limit concentrations (repeatable mortar). 2. Application of the tank mix A liquid mixture of the antidote and the herbicide is used (ratio between the amounts of 1:20 to 5: 1), the dose of the herbicide being 0.1 to 6 kg per hectare. Such a tank mix is preferably applied before or immediately after sowing or incorporated into the soil that has not yet been sown to a depth of 5-10 cm. 40 3. Application to seed furrows The antidote is introduced into the open seed furrow in the form of an emulsion concentrate, wettable powder or granules and then, after covering the furrow, the herbicide is applied as usual before the plants emerge. Basically, the antidote can be applied before, together or after the pesticide and may be used on the seed or in the field before or after sowing, or in some cases also after emergence of the seeds. 4. Controlled release of active ingredient. The active ingredient in solution is applied to mineral carriers in the form of granules or polymerized granules (urine / formaldehyde) and dried. Optionally, a coating (coated granules) can be applied, which makes it possible to dose the active ingredient over a period of time in a metered manner. 60 It goes without saying that all other methods of administering the active substance can also be used. This will be given in the examples below. The compounds of formula I can be used alone or together with suitable carriers and / or other additives. 117 292 21 22 Suitable carriers and additives can be solid or liquid, and are substances normally used in the formulation technique. such as, for example, natural or regenerated minerals, solvents, dispersants, wetting agents, adhesion promoters, thickeners, binders or fertilizers. The active ingredient content in commercial preparations is 0.1 to 90%. Agents containing compounds of formula I can be prepared in the form of the following application preparations (where the percentages by weight in brackets are the preferred amounts of the active ingredient): Solid preparations: dusts and sowing agents (up to 10%), granules, coated granules, impregnated granules and homogeneous granules, tablets (grains) (1 to 80%); Liquid preparations: a) Water-dispersible active ingredient concentrates: wettable powders and pastes (25-80% in the commercial package and 0.01-15% in the ready-to-use solution), emulsion concentrates and soluble (10 to 50%; from 0.01 to 15% in ready-to-use solution), b) Solutions (0.1 to 20%); aerosols. The compositions according to the invention are prepared, for example, as described below: Dusting agent: For the production of a) 5% and b) 2% dusts, the following substances are used: a) 5 parts of active ingredient 95 parts of talcum b) 2 parts of active substance 1 part of silicic acid with a finely divided degree of 97 parts of talc. The active substances are mixed with carriers and ground. The obtained preparation can be used for dusting. Granulate: The following substances are used to produce 5% of the granules: 5 parts of the active substance 0.25 parts of epichlorohydrin 0.25 parts of cetyl ether polyglycol 3.50 parts of polyethylene glycol 91 parts of kaolin (grain size 0 (0.3-0.8 mm). The active substance is mixed with epichlorohydrin and dissolved in 6 parts of acetone, and then added to this polyethylene glycol and polyglycol celyl ether. The solution obtained in this way is dusted on kaolin and then the acetone is evaporated under reduced pressure. Wettable powder: For the preparation of a) 70%, b) 40%, c) and d) 25% and e) 10% of wettable powder, the following ingredients are used: a) 70 parts of active substance 5 parts of sodium dibutylnaphthylsulfonate 3 parts of condensate of naphthalenesulfonic acids, phenolsulfonic acids and formaldehyde (3: 2: 1) 10 parts of kaolin 12 parts of Champagne chalk b) 40 parts of active substance 6 parts of sodium salt of lignosulfonic acid 1 part of sodium dibutylnaphthalenesulfonic acid 54 parts of silicic acid c) 25 parts of active substance 5 4.5 parts of calcium lignin sulphonate 1.9 parts of a mixture of Champagne chalk and hydroxyethyl cellulose (1: 1) 1.5 parts of sodium dibutylnaphthalenesulphonate in 19.5 parts of silicic acid 19.5 parts of chalk 28.1 parts of kaolin d) 25 parts of active substance 2.5 parts of isooctylphenoxy-polyoxyethylene-ethanol 1.7 parts of a mixture of chalk C hampagne and hydroxyethylcellulose (1: 1) 8.3 parts of sodium aluminosilicate 16.5 parts of diatomaceous earth 20 46 parts of kaolin e) 10 parts of active substance 3 parts of a mixture of sodium salts, saturated fatty alcohol sulphates 5 parts of naphthalenesulfon-2 acid condensate * and formaldehyde 82 parts of kaolin. The active substances are thoroughly mixed with additives in suitable mixers and ground on suitable mills and rollers. * A wettable powder with excellent wettability and the ability to form suspensions is obtained, which can be diluted with water to suspensions of the desired concentration. Emulsifiable concentrates: The following substances are used to prepare a 25% emulsifiable concentrate: 25 parts of the active ingredient 2.5 parts of epoxidized vegetable oil 10 parts of a mixture of alkylarylsufonate and ether in fatty alcohol with polyglycol 5 parts Dimethylformamide 57.5 parts xylene. From such concentrates can be diluted ie water to produce emulsions of a given concentration. 45 Antidote and postemergence test on culture medium General methodology: Small plastic pots (upper diameter 6 cm) pierced from the bottom are filled with a granular zonolite and the seeds of the crop are sown. M The pot is then placed in a second transparent pot with plastic (with an upper diameter of 7 cm) containing 50 ml of water. This water rises by capillary action and moistens the seeds. From the fifth day on, the current water loss will be leveled out by Hewitt's nutrient. Beginning on the fifth day, when the crop is at the 1 1/2 to 2 leaf stage, it is again supplemented with 50 ml of food containing 10 ppm of the antidote to be tested and the amount of herbicide indicated below. From the sixteenth day onwards, Hewitt's pure nutrient is again equalized for the loss of liquid. The temperature is 20-23 ° C. and a relative air humidity of 60-70% during the entire test period. Three weeks after adding the herbicide and antidote, the rating is 23 117 292 24 on a linear scale from 1 to 9, with 1 representing complete damage to the plant and 9 being unharmed. Test options: 1) 15 ppm of propaphylthylol acid ester a - [4- - / 3,5-dichloropyridyl-2-phenoxy] -propionic in wheat grade "Zenith", 2) 4ppm 4-ethylamino-6-tertiary-butyl-amino-2-chloro s-triazines in wheat of the "Zenith" grade, 3) 2 ppm of n-btitoxyethyl ester of - (p-trifluoromethylphenoxy) -phenoxy] -propionic acid in maize "Orla" grade, 4) 8 ppm of h-butoxyethyl acid ester - (p- trifluoromethylphenoxy) -phenoxy] -propionic in piglet of the species "Funk G-522", 5) 4 ppm of promethrin, i.e. 2,4-bis- (isopropylamino) -6-methylthio-s-triazine in the piglet of the species "Funk G- 522 ", 6) 8 ppm of chloroplridyloxy-2) -phenoxy] -propionic acid methyl ester in" Zenith "grade wheat. Compounds of Formula 1 showed good detoxifying activity in these tests. Examples are the results given in Table 11. Table U Test variant 1 6 1 6 Compound No. 55 35?) Degree of herbicide effect (without) with antidote 6/8 3/7 2/5 | *) Compound of formula 21, where Ri = * H, Rt ~ H and G = ¦ OCHtCHjCH * Antidote-pre-emergence test ha nutrient. Hewitt's nutrient is prepared, which contains the following amount of herbicide, as well as 10 ppm of the tested antidote. The seeds of cultivated plants are used, which, at the given control concentration of the herbicide used, should be damaged as expected and sown into a granular (expanded vermiculite) in a plastic pot perforated at the bottom (upper diameter 6 cm). The pot is placed in a second transparent plastic pot (upper diameter 7 cm) which contains about 50 ml of nutrient medium, containing herbicides and an antidote. The bulge now rises by capillary action to the filling material of the smaller pot and moistens the seeds and germinating plant. The loss of liquid is replenished daily with pure Hewitt nutrient up to 50 ml. After 3 weeks from the start of the test, an assessment is made on a linear scale from 1 to 9, with 1 representing complete damage to the plant and 9 being in good health. The control solution used in parallel does not contain any additional antidote. The following are used: I) 4 ppm of pro-heretrin, i.e. 2,4-bis- (isopropylamino) -6-methylthiosstriazine in piglet grade "Funk G-532", 2) 4 ppm of 4-ethylamino-6-III-order .-butyl-amino-2-chloro-s-triazine in "Farnese" grade wheat, 3) 4 ppm of o- [4- - (p-trifluoromethylphenoxy) -phenoxy] -propionic acid n-butyloxyethyl ester in barley grade " Mazurka ", 4) 5 ppm of Metolachloride, i.e. N- (1-methyl-2-methoxyethyl) -N-chloroacetyl-2-ethyl-6-methylaniline in piglet grade" Funk G-522 ", 5) lppm 2- methoxy-4,6- (γ-methoxypropylamino) -s-triazinium in sugar beet "Klein-wanzleben". The compounds of formula 1 showed a good detoxifying effect in these tests. The results given in Table 12 may be mentioned as examples. Test variant 2 4 4 4 4 5 5 3 5 4 4 Compound No. 49 57 312 4 *) *) 23 60 62 33 32 Degree of herbicide effect (without) with antidote 2/5 2/5 2/5 3/7 2 / 6 (at an antidote concentration of 1 ppm) [2/5 1/5 f 2/5 1/7 (at an antidote concentration of 1 ppm) 2/5 2/5 *) Compound of formula 9, in which m Ri = 3-Cl, Ri-4-Cl, R5 * "H, Rt" Ill-r. C "Hi. Antidote test for swelling of seeds. Rice grains of the IR8 species are saturated within 48 hours with solutions of the test substances containing 10 or 100 ppm. The grains are then dried for about 2 hours until they are no longer sticky. Rectangular plastic pots (8 x 8 cm, height 10 cm) are filled with sandy loam to a height of 2 inches below the rim. 4g of seeds are sown in each pot and the cover is quite poor (about the diameter of the seed). The soil is kept moist (not marshy). Then either N * (1-methyl-2-methoxy-yetyl) -N-chlor-: roacetyl-2-ethyl-6-methylaniline or N- herbicide is applied as an option. propoxy-ethyl-N-chloroacetyl-2,6-dimethylaniline in dilute solution and in an amount which corresponds exactly to 1.5 kg of active ingredient per hectare. 18 days after planting the plants, an evaluation is made according to a linear scale of 1 to 9, with 1 representing complete damage to the plant and 9 being unharmed. The compounds of formula 1 showed good detoxification activity in this test. As an example, the results given in Table 13, Pre-emergence antidote test (Basic Test) may be mentioned. l 10 15 20 29 80 35 40 45 90 95 60 117 292 25 26 Table 13 Dose 100 ppm 10 ppm Compound No. 312 313 54 77 Degree of herbicide effect (without) with antidote 2/5 1 2/5. 1/4 | 2/5 i General method: Small pots with an upper diameter of 6 cm are filled with garden soil, in which the plant cultivation is placed, covered and slightly kneaded. Subsequently, the test substances as an antidote in the form of a diluted solution (obtained from the powder) The amount of active ingredient is 4 kg per hectare. The herbicide is sprayed in a suitable manner immediately afterwards. After 18 days of storage at 20-23 ° C and 60-70% relative air humidity, an evaluation is made on a linear scale from 1 to 9, with 1 representing complete damage to the plant and 9 being unharmed. As a control, plants serve without the addition of an antidote. The following are used: 1) 1.5 kg of active substance / ha of α- [4- (p-trifluoromethylphenoxy) -phenoxy] -propionic acid n-butyloxyethyl ester in "Orla" maize 264 ", 2) 1.5 kg of active substance / ha of Metolachlor, i.e. N- (1-methyl-2-methoxyethyl) -N-chloroacetyl-2-ethyl-6-methylaniline in" Funk G-522 "piglet 3) 2.0 kg active ingredient / ha promethrin, i.e. 2,4-bis {isopropylamino) -6-methylthio-s-triazine in soybeans, 4) 2.0 kg active ingredient / ha 4-ethylamino-6- III-pre-butylamino-2-chloro-s-triazine in wheat grade 4, Farnese ", 5) 4.0 kg of active substance / ha of promethrin, i.e. 2,4-bis- (isopropylamino) -6-methylthio- s-triazines in "Funk G-522" millet, 6) 2.0 kg of active ingredient / ha of n-butoxyethyl ester a- [4- (p-trifluoromethylphenoxy) -phenoxy] -propyrium in barley species "Mazurka", 7) 1.0 kg of active ingredient / ha N-methoxyethyl * -N-chloroacetyl-2,6-dimethylaniline in maize of the "Anjou 196" grade. The compounds of formula I showed a good detoxifying effect in these tests. Examples are the results given in Table 14. Table 14 Test variant 6 5 4 and 7 f 3 Compound No. 77 •) 22 32 311 Herbicide effect degree (without) with antidote 4/7 1/4 2/4 2/5 2/5 '*) Compound of formula HjC * —C (Cl) = NO — CO— —NHCHj. Detoxifying effect on replanted rice when applied separately (antidote * applied pre-emergence; herbicide post-East). Pots with of plastic material (8Xfccm, height 10 cm), the soil of a swampy-wet consistency is filled up to 2 cm below the edge of the wedge. The substances in the form of a diluted solution as an antidote are sprayed onto the earth's surface in an amount corresponding to 4 kg of active substance per hectare. The pots prepared in this way are transplanted and the rice plants of the "IR-8" species, which are at the 11/2 stage to 2 leaves. The next day the water level is increased by about 1.5 cm. 4 days after settling, 2-ethylamino-4 (1,2-dimethyl-n-propylamino) -6 is added to the water. -methylthio-s-triazine in the form of granules at the rate of exactly 0.75 kg of active substance / ha. During the test, the temperature is 26 ° -28 ° C. and the relative air humidity is 60-80%. After 20 days. from the time of treatment with the herbicide, a rating is made on a linear scale of 1 to 9, with 1 representing complete damage to the plant and 9 being unharmed. The control serves the plant without protection of the detoxifier. 1 show a good detoxifying effect in this test The results are given in Table 15. TABLE 15 Compound No. 312 24 Herbicide Effect Level (Without) With Antidote 3/6 1 5/7 | Claims 1. A product for the protection of crops against aggressive chemicals used in agriculture, characterized in that it contains a compound of formula I as detoxifying active ingredient, in which Ar is optionally: a phenyl radical of the formula 2 or naphthyl of formula 3; a furan or thiophene ring optionally substituted with halogen, an NO * group or a lower alkyl radical, or one of the "COOR 4 or" CO 4 R "groups; X represents a -CN group, a lower alkanoyl group, a carboxylic acid ester group, a -COOH group, hydrogen, a carboxylic acid amide group, a halogen or a lower alkyl radical, R 1. is hydrogen, halogen, lower alkyl, lower alkoxy or phenoxy in the position of para, optionally substituted by up to 60 times with halogen, the group —CN, NO *, CFj, Ra and R * independently of one another are hydrogen , halogen, NO, lower alkyl, haloalkyl or lower alkoxy group, R4 is aliphatic, cycloaliphatic or arylaliphatic, the aromatic radical may be substantially substituted as specified for Rt and R $ and additionally the group —CN, and R — selectable from: a) the group —N (RsXR ”) and wherein R§ is hydrogen or a lower alkoxy group or R #, and R * represents an aliphatic, cycloaliphatic, ary - loaliphatic, aromatic or heterocyclic, the aromatic group may be substantially substituted as indicated for R * and Rt, b) the group -YR7, where Y is oxygen or sulfur and R7 is as defined for R *, Ra stands for: a) the group —N lower alkyl radical b cycloalkyl and Ri0 is R # or is hydrogen or R # and Rit together with -N forms an a-7 membered ring which may be substituted with lower alkyl radicals, b) the -NH-CONHRie group. 2. The measure according to claim A compound according to claim 1, characterized in that the detoxifying active ingredient is a compound of formula I in which X is an acetyl radical, the group —COO lower alkyl, —COONH, —COONH — lower alkyl, —COON (lower alkyl) " , methyl radical, R * and R * represent CF, methoxy group, ethoxy group, and R "represents lower alkyl radical, R * represents phenyl radical optionally substituted with halogen, lower alkyl radical, CH * methoxy group or ethoxy, and the other symbols have the meanings given in claim 1 1. 1S 3. Measure according to claim A compound according to claim 1 or 2, characterized in that the detoxifying active substance is a compound of formula I, in which Ar is one of the groups —COOR * or —CORs, where R4 is a lower aliphatic group of at most 4 carbon atoms or a phenyl radical and by definition Ra, Rf and R10, independently of each other, represent a phenyl radical optionally substituted with halogen, CF * or a lower alkyl radical, and the substituents X, Y, R5, R1, Rt have the meaning given in the preceding claims. 2. 4. The measure according to claim A compound according to claim 1, characterized in that the detoxifying active ingredient is the compound of formula 11, in which Ar is α-naphthyl, X is CN, and R1 and R <are ethyl radicals. 5. The measure according to claim The compound of claim 1, wherein the detoxifying active ingredient is the compound of formula 11, in which Ar is 2-thienyl substituted with 5 chlorine, X is CN, Ra is hydrogen and R * is methyl. 6. The measure according to claim A compound according to claim 1, characterized in that the detoxifying active ingredient is a compound of formula 12, wherein R 4 is ethoxyl, R 5 is hydrogen and R 1 is phenyl substituted with chlorine in positions 3 and 4 R. kc-n-oh Xn ON Formula 3 Yiz6r4 @ -C-CN NO-CO-NHCH3 Nzór5 W ft-0-CO-NH- Formula 6 o ^ cVc-cn mn ft NO-CO-S-CzH * 117 292 H5C200C -C-CN no-co-nh ^ C ^ ci Ri Nzcr8 N-0-CO-1 ^ -Rj Rb Formula 9 Rz Ri CX N-0-CO-fJJ-Rs Model 10 ^ 6 Ar-CX N-0 -CO-N-Rs Formula Re117 292 R4-0-CC-CN O NOCN; R Pattern 12 N Pattern n Pattern 15 9 / CN Rio-nc-cx from R9 NOCN ^ Pattern 14 Pattern 16 Pattern 17 R9, CN ¦NCC R 0 10 N0-C-NHR6 Pattern 18 117 292 H2N-C0-NH-C0- C-CN Formula 19 N-0-CO-NH-R6 Rio-NH-CC-CN N-0-C-YR7 Formula 20 O C-CN NO-CO-G Formula 21 HaN-CO-NH-CO-C -CN N0-CChN-0-CH3 Formula 22 CH = 117 292 NH, -CO-C-CN £ ii NO-CO-NO-CH, 1 ° Formula 23 CH, Hfip-CO-C = N0-C0-NHCH3 3 Formula 24 CF »s Iflzór 25 Qh (CJ-NH- CO- CH = NO -CONHCH3 CF3 Yitór 26 H3C ^ C ^ NH-CO-CH-NO-CONHCH3 INzOR 27 Ar Ar. ^: C-NOH + 0- C = N-R6— * ^ C = NO-CO-NHR6 Scheme / Ar. Ar. C = NO-Nq + Cl-C0-N-R6— * C = NO-CO-NR6 X Rs X Rs Scheme 2 Ar Ar C = NO-CO-Cl + NH-Re—- C = N0-C0-NHR6 Scheme 3117 292 Ar ONO-Na + Q- CO-YR? - Scheme 4 Arv C = NO-CO-Cl + HO-R7 - ^ Scheme 5 ^ ON0-C0-Cl + Na-S-R7- Scheme 6 Ar ^ C = NO-CO-YR7 Ar. ^ C = NO-CO-OR7 Ar - C = NO-CO-SR7 PL

Claims (4)

Claims 1. A product for the protection of crops against aggressive chemicals used in agriculture, characterized in that it contains a compound of formula I as detoxifying active ingredient, in which Ar is optionally: a phenyl radical of the formula 2 or naphthyl of formula 3; a furan or thiophene ring optionally substituted with halogen, an NO * group or a lower alkyl radical, or one of the "COOR 4 or" CO 4 R "groups; X represents a -CN group, a lower alkanoyl group, a carboxylic acid ester group, a -COOH group, hydrogen, a carboxylic acid amide group, a halogen or a lower alkyl radical, R 1. is hydrogen, halogen, lower alkyl, lower alkoxy or phenoxy in the position of para, optionally substituted by up to 60 times with halogen, the group —CN, NO *, CFj, Ra and R * independently of one another are hydrogen , halogen, NO, lower alkyl, haloalkyl or lower alkoxy group, R4 is aliphatic, cycloaliphatic or arylaliphatic, the aromatic radical may be substantially substituted as specified for Rt and R $ and additionally the group —CN, and R — selectable from: a) the group —N (RsXR ”) and wherein R§ is hydrogen or a lower alkoxy group or R #, and R * represents an aliphatic, cycloaliphatic, ary - loaliphatic, aromatic or heterocyclic, the aromatic group may be substantially substituted as indicated for R * and Rt, b) the group -YR7, where Y is oxygen or sulfur and R7 is as defined for R *, Ra stands for: a) the group —N lower alkyl radical b cycloalkyl and Ri0 is R # or is hydrogen or R # and Rit together with -N forms an a-7 membered ring which may be substituted with lower alkyl radicals, b) the -NH-CONHRie group. 2. The measure according to claim A compound according to claim 1, characterized in that the detoxifying active ingredient is a compound of formula I in which X is an acetyl radical, the group —COO lower alkyl, —COONH, —COONH — lower alkyl, —COON (lower alkyl) " , methyl radical, R * and R * represent CF, methoxy group, ethoxy group, and R "represents lower alkyl radical, R * represents phenyl radical optionally substituted with halogen, lower alkyl radical, CH * methoxy group or ethoxy, and the other symbols have the meanings given in claim 1 1. 1S 3. The measure according to claim A compound according to claim 1 or 2, characterized in that the detoxifying active substance is a compound of formula I, in which Ar is one of the groups —COOR * or —CORs, where R4 is a lower aliphatic group of at most 4 carbon atoms or a phenyl radical and by definition Ra, Rf and R10, independently of each other, represent a phenyl radical optionally substituted with halogen, CF * or a lower alkyl radical, and the substituents X, Y, R5, R1, Rt have the meaning given in the preceding claims. 2. 4. The measure according to claim A compound according to claim 1, characterized in that the detoxifying active ingredient is the compound of formula 11, in which Ar is α-naphthyl, X is CN, and R1 and R <are ethyl radicals. 5. The measure according to claim The compound of claim 1, wherein the detoxifying active ingredient is the compound of formula 11, in which Ar is 2-thienyl substituted with 5 chlorine, X is CN, Ra is hydrogen and R * is methyl. 6. The measure according to claim A compound according to claim 1, characterized in that the detoxifying active ingredient is a compound of formula 12, wherein R 4 is ethoxyl, R 5 is hydrogen and R 1 is phenyl substituted with chlorine in positions 3 and 4. R. Nzór2 £) kc-n-oh Xn ON Formula 3 Yiz6r4 @ -C-CN NO-CO-NHCH3 Nzór5 W ft-0-CO-NH- Formula 6 o ^ cVc-cn mn ft NO-CO- S-CzH * 117 292 H5C200C-C-CN no-co-nh ^ C ^ ci Ri Nzcr8 N-0-CO-l ^ -Rj Rb Formula 9 Rz Ri CX N-0-CO-fJJ-Rs Model 10 ^ 6 Ar-CX N-O-CO-N-Rs Formula Re117 292 R4-0-CC-CN O NOCN; R. Formula 12 Nzor n Formula 15 9 / CN Rio-nc-cx from R9 NOCN ^ Formula 14 Formula 16 Formula 17 R9, CN ¦NCC R 0 10 N0-C-NHR6 Formula 18 117 292 H2N-C0-NH-C0- C-CN Formula 19 N-0-CO-NH-R6 Rio-NH-CC-CN N-0-C-YR7 Formula 20 O C-CN NO-CO-G Formula 21 HaN-CO-NH-CO-C -CN N0-CChN-0-CH3 Formula 22 CH = 117 292 NH, -CO-C-CN £ ii NO-CO-NO-CH, 1 ° Formula 23 CH, Hfip-CO-C = N0-C0-NHCH3 3 Formula 24 CF »s Iflzór 25 Qh (CJ-NH- CO- CH = NO -CONHCH3 CF3 Yitór 26 H3C ^ C ^ NH-CO-CH-NO-CONHCH3 INzOR 27 Ar Ar. ^: C-NOH + 0- C = N-R6— * ^ C = NO-CO-NHR6 Scheme / Ar. Ar. C = NO-Nq + Cl-C0-N-R6— * C = NO-CO-NR6 X Rs X Rs Scheme 2 Ar Ar C = NO-CO-Cl + NH-Re—- C = N0-C0-NHR6 Scheme 3117 292 Ar ONO-Na + Q- CO-YR? - Scheme 4 Arv C = NO-CO-Cl + HO-R7 - ^ Scheme 5 ^ ON0-C0-Cl + Na-S-R7- Scheme 6 Ar ^ C = NO-CO-YR7 Ar. ^ C = NO-CO-OR7 Ar - C = NO-CO-SR7 PL