GB2028797A

GB2028797A - Oxime carbamates and oxime carbonates for the protection of cultivated crops

Info

Publication number: GB2028797A
Application number: GB7835200A
Authority: GB
Original assignee: Ciba Geigy AG
Current assignee: Novartis AG
Priority date: 1978-08-31
Filing date: 1978-08-31
Publication date: 1980-03-12
Also published as: SE7808906L; ATA601378A; CA1159071A; AT365410B; SE446926B; DE2837204A1; LU80165A1; JPS5535002A; GB2028797B; FR2434802A1; NL7808962A; BE870066A; AU530210B2; AU3938078A; FR2434802B1

Abstract

Oxime carbamates and oxime carbonates of the formula Ar-CX= N-O-CO-R, wherein Ar is a phenyl, naphthyl, fury or thienyl group, which may carry certain substituents, or Ar is a carboxylic ester or carbamyl group, X is cyano, lower alkanoyl, carboxylic ester, -COOH, hydrogen, carboxylic amide, halogen or lower alkyl, and -COR is one of certain carboxylic amide, ester or thioester groups, are suitable as antidotes for the protection of cultivated plants against harmful agricultural chemicals, in particular against herbicides which are insufficiently compatible with the cultivated plants. These compounds of the formula I can be used either on their own or together with the agricultural chemicals. One of the possibilities offered is the dressing or immersion treatment of seed or of seedlings, of the crop to be protected, with solutions or dispersions of compounds of the formula I.

Description

SPECIFICATION Oxime carbamates and oxime carbonates for the protection of cultivated crops The present invention relates to oxime carbamates and oxime carbonates of the general formula I

to novel compositions based on these compounds, and to the application of these compositions or compounds for the protection of cultivated plants against harmful agricultural chemicals.

The symbols in the formula I have the following meanings: Ar is a phenyl group of the formula

a naphthyl group which is substituted by R2 and R3, a furan or thiophene ring which is unsubstituted or substituted by halogen, NO2 or lower alkyl, or Ar is one of the radicals -COOR4 or -CO-R8, X is -CN, lower alkanoyl, a carboxylic acid ester group, -COOH, hydrogen, a carboxylic acid amide group, halogen or lower alkyl, R1 is hydrogen, halogen, lower alkyl, lower alkoxy, or a phenoxy group which is in the para-position and which is unsubstituted or substituted a maximum of twice by halogen, -CN, NO2 or CF3, R2 and R3 independently of one another are hydrogen, halogen, NO2, lower alkyl, haloalkyl, lower alkoxy or di(lower alkyl) amino, R4 is an aliphatic, cycloaliphatic or araliphatic group, and an aromatic radical can be substituted as defined under R2 and R3 and can be additionally substituted by -CN, R is either a) a radical -N(R5)(R6), in which R5 is lower alkoxy or is the same as R8, R6 is hydrogen or an aliphatic, cycloaliphatic, araliphatic, aromatic or heterocyclic group, and an aromatic radical can be substituted as given under R2 and R3, or b) a radical -YR7, in which Y is oxygen or sulfur, and R7 is one of the 5 groups given for R6, R8 is either a) a radical -N(Rg)(R10), in which Rg is hydrogen, lower alkyl or cyclaolkyl, and R10 has the meaning of R6 or is hydrogen, or Rg and R10 together with the -N atom form a 3-7 membered ring which can be substituted by lower alkyl groups, or b) a radical -NH-CONHR10.

Compounds of the formula I are accordingly a) carbamates orb) (thio) carbonates.

Halogen in the formula I is fluorine, chlorine, bromine or iodine.

Carboxylic acid esters are carboxylic acid lower alkyl esters. Carboxylic acid am ides denote, besides -CONH2, also monoalkyl-substituted or symmetrically or unsymmetrically dialkyl-substituted amides, with the alkyl groups being lower alkyl.

The term 'alkyl' on its own or as part of a substituent includes branched and unbranched C1 to C8 alkyl groups; lower alkyl denotes C1-C4 alkyl. Examples are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl and tert-butyl, and also the higher homologues amyl, isoamyl, hexyl, heptyl or octyl, together with isomers thereof. Correspondingly, alkanoyls or cyanalkyls contain an additional C atom.

The term 'aliphatic group' includes radicals which are saturated (alkyls) and also unsaturated (alkenyls, alkadienyls or alkynyls), which are halogen-substituted, cyano-substituted and interrupted by oxygen, and which contain a maximum of 8 carbon atoms. The term 'aromatic group' in the definition of the substitutents R4, R5 and R8 embraces phenyl and naphthyl. The term 'araliphatic radical' is to be interpreted in accordance with the two preceding definitions. An araliphatic radical includes an aryl group such as unsubstituted or mono- to tri-substituted phenyl, or naphthyl, which is bound by way of lower alkyl or lower alkenyl to the radical of the molecule. Examples are benzyl, phenethyl or phenylallyl and also homologues.

The term 'heterocylic radical' includes 5-to 1 0-membered ring systems having 1 or 2 rings and a maximum of 3 heteroatoms from the series N, O or S. C3-C7 cycloalkyl groups are cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cycloheptyl. Cycloaliphatic radicals correspond to these ring systems, but in addition they may contain, if structurally possible, one or more double bonds.

The arylglyoxylnitrile oximes of the general formula

(X = H, Cl, Br, NO2), suggested in the U.S. Patent Specification No. 3,799,757, are insufficiently effective as growth inhibitors and plant-growth regulators; furthermore, they are not stable and decompose after a fairly short space of time.

No herbicidal-antidote action has become known.

In comparison with the above compounds, oximes of the formula I are excellently suitable for protecting cultivated plants, such as cultivated millet, rise, maize, varieties of cereals (wheat, rye, barley or oats), cotton, sugar beet, sugar cane, soya bean, etc., from being attacked by agricultural chemicals harmful to plants, particularly by herbicides of the most varied classes of substances, such as triazines, phenylurea derivatives, carbam ates, thiolcarbamates, haloacetanilides, halophenoxyacetic acid esters, substituted phenoxyphenoxyacetates and phenoxyphenoxypropionates, substituted pyridineoxyphenoxyacetates and pyridineoxyphenoxypropionates, benzoic acid derivatives, and so forth, in cases where these chemicals do not act selectively or do not act sufficiently selectively, that is to say, damage to a greater or lesser extent the cultivated plants in addition to destroying the weeds to be controlled. The invention relates also to compositions which contain these oxime derivatives of the formula I, together with herbicides.

There have already been suggested as antidotes various substances able to specifically antagonise the harmful action of a herbicide on the cultivated plant, that is to say, able to protect the cultivated plant without noticeably affecting the herbicidal action against the weeds to be controlled. Depending on its properties, an antidote of this kind (also called a safener) can be used for the preliminary treatment of the seed of the cultivated plant (dressing of the seed or of the seedlings); or it can be applied into the seed furrows before sowing; or it can be applied as a tank mixture, on its own or together with the herbicide, before or after emergence of the plants.The pre-emergence treatment includes both the treatment of the cultivated area before sowing (ppi = pre plant incorporation) and the treatment of the sown cultivated area before emergence of the plants.

Thus, the British Patent Specification No. 1,277,557 describes the treatment of seed and seadlings of wheat and sorghum with certain esters and am ides of oxamic acid before the attack by N-methoxymethyl-2', 6'-diethyl-chloroacetanilide (Alachlor). Other publications (German Offenlegungsschriften Nos. 1,952,910 and 2,245,471, and French Patent Specification No. 2,021,61 1) suggest antidotes for the treatment of cereals, maize seed and rice seed to protect them against attack from herbicidal thiolcarbamates. In the German Patent Specification No. 1,576,676 and U.S. Patent Specification No. 3,131,509, hydroxyaminoacetanilides and hydantoins are suggested for the potection of cereal seeds against carbamates, such as IPC, CIPC, and so forth. In further development, however, all these preparations have proved to be inadequate.

To be emphasised an antidotes are in particular those compounds of the formula I in which Ar is a phenyl or naphthyl radical as defined in the foregoing, X is cyano, hydrogen, lower alkanoyl, a carboxylic acid ester group, a carboxylic acid amide group or lower alkyl, R1 is hydrogen, halogen, or a phenoxy group which is in the para-position and which is unsubstituted or substituted a maximum of twice by halogen, -CN or CF3, R2 and R3 independently of one another are hydrogen, halogen, lower alkyl, haloalkyl or lower alkoxy, and R is defined above. This subgroup is to be called compound group la.

Amongst these compounds ofthe group la, the group Ib constitutes one of the compound groups preferred as antidotes. Compounds of the group Ib are those of the formula I in which Ar is phenyl group as defined in the foregoing, Xis cyano, hydrogen, acetyl, -COO-lower alkyl, -COONH2, -COONH-lower alkyl, -COON (lower alkyl)2 or methyl, R1 is hydrogen, R2 and R2 are hydrogen, halogen, lower alkyl, CF3, methoxy or ethoxy, R8 is hydrogen, lower alkyl or lower alkoxy, R6 is an aliphatic group, or a phenyl group which is unsubstituted or substituted by halogen, lower alkyl, CF2, methoxy or ethoxy, Y is oxygen or sulfur, and R7 has the meaning given above for R8.

An important group of antidotes is formed by those compounds of the formula I in which Ar is a thiophene ring unsubstituted or substituted by halogen or lower alkyl, and in which the substituents X, Y, R5, R6 and R7 have the meanings given for the compound group la, but preferably the meanings given for the compound group Ib.

A further important group of antidotes for the protection of cultivated plants against herbicides is the subgroup of the formula I in which Ar is one of the radicals -COOR4 or -COR8, wherein R4 is a lower aliphatic group having a maximum of 4 C atoms or is phenyl, and in the definition of R8 the substituents Rg and R10 independently of one another are hydrogen or lower alkyl, or phenyl unsubstituted or substituted by halogen, CF3 or lower alkyl, whilst the substituents X, Y, R5 and R7 have the meanings given for the compound group la, but preferably have the meanings given for the coupound group Ib.

Surprisingly, oximes of the formula I have the property of being able to protect cultivated plants against attack from agricultural chemicals harmful to plants, particularly against herbicides of the most varied classes of substances, including 1,3, 5-triazines, 1,2, 4-triazinones, phenylurea derivatives, carbamates, thiolcarbamates, phenoxyacetates, phenoxypropionates, haloacetanilides, halophenoxyacetates, substituted phenoxyphenoxyacetates and phenoxyphenoxypropionates, substituted pyridinephenoxyacetates and pyridinephenoxypropionates, benzoic acid derivatives, and so forth, in cases where these chemicals are not compatible, or not sufficiently compatible, with the cultivated plants.

Depending on the purpose of application, such an antidote of the formula I can be used for pretreatment of the seed of the cultivated plant (dressing of the seed or of the seediings), or can be applied to the soil before or after sowing, or can be applied on its own or together with the herbicide before or after emergence of the plants. The treatment of the plant or of the seed with the antidote can therefore be carried out essentially independently of the point of time of application of the phytotoxic chemicals. It can however be carried out also simultaneously (tank mixture). Pre-emergence treatment includes both the treatment of the cultivated area before the sowing (ppi = pre plant incorporation) and the treatment of the sown area before emergence of the plants.

The applied amounts of the antidote in proportion to the amounts of herbicide depend largely on the type of application. If a field treatment is undertaken, the amounts of antidote of the formula I with respect to amounts of the phytotoxic chemical are in the ratio of 1:100 to 5:1. preferably 1:20 to 1:1. In the case of seed dressing and similar specific protective measures, much smaller amounts of antidote are required however compared with the amounts of herbicide employed for example later per hectare of cultivated area (for example about 1:3000 to 1:1000). There is a rule only a loose connection between protective measures, such as seed dressing with an antidote of the formula I, and a possible subsequent field treatment with agricultural chemicals.Pretreated seed and plant material can later come into contact, in agriculture, horticulture and forestry, with a variety of chemicals.

The invention relates therefore also to compositions for protecting cultivated plants, which compositions contain as active substance an antidote of the formula I together with customary carriers. Compositions of this type can optionally be additionally mixed with those agricultural chemicals having an effect from which the cultivated plant is to be protected, for example they can be mixed with a herbicide.

Within the scope of the present invention, cultivated plants are all plants which produce in some form useful materials (seeds, roots, stalks, tubers, leaves, blossom, and components such as oils, sugar, starch, protein, and so forth), and which are cultivated and attended to for this purpose. These plants include for example all varieties of cereals, maize, rice, cultivated millet, soya bean, beans, peas, potatoes, vegetables, cotton, sugar beat, sugar cane, peanuts, tobacco and hops, and also ornamental plants, fruit trees as well as banana, cocoa and natural rubber plants. This list of planttupes does not constitute any limitation. An antidote can as a rule be used everywhere where a cultivated plant has to be protected against the phytotoxicity of a chemical.

Compounds of the formula can be produced from the free oximes by several processes, which are shown in schematic form in the following: a) Carbamates

b) {This carbonates

(In the preceding diagrams, Na represents sodium or another alkali metal).

Suitable for obtaining compounds of the formula I are essentially all solvents which behave inertly under the conditions of the reaction. For example, hydrocarbons, particularly however polar solvents such as acetonitrile, dioxane, celiosolve or DMF, and also ketones such as methyl ethyl ketone, acetone, and so forth.

Solvents containing hydroxyl groups are excluded.

The temperatures are within the range of -10"C to about 1500C, preferably between 200 and 1200C.

As agents splitting off hydrogen halide, it is possible to use bases, such as tert. amines (triethylamine, triethylenediamine, piperidine, and so forth). Also a suspension of sodium carbonate in an anhydrous reactjion medium suffices in some cases. Oximes are present in two stereoisomeric forms, the syn and anti form. By 'compounds of the formula I' are accordingly meant, within the scope of the present specification, both stereoisomeric forms, on their own or as mixtures with each other in any reciprocal mixture ratio.

The Examples which follow illustrate the production of the novel oximes of the formula I. Temperature values are given in degrees Centrigrade.

Example 1 Production of

23.5 g (0.16 mol) of benzyl cyanide oxime is placed into 100 ml of acetonitrile. After 25 ml of methylisocyanate and a small, catalytically acting, amount of diazabicyclooctane have been added, the reaction mixture is heated to 50"C, and the final product precipitates after a short period of time. It is allowed to stand overnight, and is then filtered off with suction, washed with acetonitrile, and subsequently dried at 600 with hexane to yield 29.2 g (=89.8% of theory) of final product having a melting point of 172-1 750C.

Example 2 Production of

14.6 g (0.1 mol) of benzyl cyanide oxime is placed into 100 ml of acetonitrile; there are then added 18.7 g (0.1 mol) of 3-trifluoromethylphenylisocyanate and a, catalytically acting, small amount of diazabicyclooctane. The reaction commences immediately, whereupon the reaction mixture heats up to about 50". It is stirred on a water bath for a further 4 hours; the final product which has precipitated is then filtered off with suction, washed with acetonitrile, and dried in vacuo at 50 to yield 25.5 g of final product having a melting pointof172-1734 Example 3 Production of

6.3 g (0.05 mole) ofchlorothioformic acid-S-ethyl ester is added dropwise to a mixture of 11.9 g (0.05 mole) of the sodium salt of 3,4-dichlorobenzyl cyanide oxime in 50 ml of acetonitrile. The reaction mixture is then heated, refluxed for 4 hours and concentrated in vacuo. Methylene chloride is added to the residue, and the mixture is stirred with active charcoal and filtered. The filtrate is concentrated by evaporation to yield 11.2 g (= 73. 7% of theory) of the final product in the form of oil.

Example 4 Production of

14.2 g (0.1 mol) of cyanoacetic acid ethyl ester oxime is placed into 100 ml of acetonitrile in a flask fitted with stirrer. A solution of 15.3 g of p-chlorophenyl-isocyanate in 20 ml of acetonitrile is added dropwise with stirring, and the reaction mixture is stirred for 5 hours at 60-70 . The solution is afterwards filtered hot and the filtrate is cooled in ice water. The final product which has crystaliized out is filtered off, washed with acetonitrile/hexane and dried; it has a melting point of 147-148"C.

In this manner or by one of the aforementioned methods, there can be produced the following carbamates of the formula:

Comp. Rt R2 R5 R6 Physical No. constants 1 H H H CH3 m.p. 172-175" 2 H H H C2H5 m.p. 93- 96" 3 H H H n-C3H7 m.p. 89- 91" 4 H H H isoC3H7 m.p. 92- 94"

Comp. R1 R2 R5 R6 Physical No. constants 5 H H H n-C4Hg m.p. 98-101" 6 H H H tert.C4Hg solid 7 H H H -CH2CH2-CI m.p.138-141 8 H H H -CH2-O-CH3 9 H H H 10 H 4-CI H n-C4Hg m.p.124-126 11 H 4-Cl H -CH2-O-CH3 m.p.110-114 12 H 4-CI H tert.C4Hg m.p. 102-105" 13 H 4-Cl H isoC3H7 m.p. 140.1440 14 H 4-CI H CH3 m.p.191-193 15 H 4-Cl H C2H8 m.p.105-108 16 H 4-CI H nC3H7 m.p.112-113 17 2-CI 4-CI H CH3 m.p. 152-154" 18 2-Cl 4-CI H CH2 m.p. 124.1280 19 3-Cl 4-Cl H tert.C4Hg solid 20 H 4-Br CH3 CH3 m.p.113-115 21 2-Cl 4-CI H isoC3H7 m.p. 92- 93" 22 H 4-Cl CH3 CH3 m.p. 131-132" 23 2-Cl 4-CI CH3 CH3 solid 24 4-t.C4H9 H H CH3 m.p. 162-165" 25 4-t.C4Hg H H C2H8 solid 26 4-t.C4H9 H H nC3H7 solid 27 4-t.C4Hg H H tert.C4Hg oil 28 H 4-CH30 H H 29 H 4-CH30 H CH3 m.p.182-184 30 H 4-CH30 H C2H5 m.p.106-110 31 H 4-CH30 H isoC3H7 m.p. 129-131" 32 H 4-(CH3)2N- H CH3 33 H 4-C2H5O H CH3 34 H 4-C2H5O H isoC3H7 35 H 4-NO2 H CH3 36 H 3-CF3 H CH3 m.p. 150.1510 37 H 3-CF3 H C2H5 38 H 3-CF3 H H 39 H 3-CF3 CH3 CH3 40 H H C2H5 C2H5 oil 41 H 3-CF3 H nC4Hg 42 H H H -CeHe m.p.132-134 43 H H H -C6H4Cl(4) m.p. 184.1860 44 H H H -C6H4-CH3(4) m.p. 153-154" 45 H 4-t.C1/2H9 H -C6H5 m.p. 131-133" 46 3-Cl 4-CI H -C6H4Cl(4) 47 3-CI 4-CI H -C6H3C12(3,4) m.p.210-213 48 3-Cl 4-CI H -C6H3CI(3)isoC3H7(4) m.p. 172-175" 49 H H H -C6H4-CF3(4) m.p. 188-190" 50 H H H -C6H3Cl(3)CF3(4) m.p. 207-208" 51 H H H -C6H3(CF3)2(3,5) m.p. 196-198" 52 H H H -C6H4-F(4) m.p.159-161 53 H H H -C6H4-CF3(3) m.p. 172-173" 54 H 4-Cl H -C6H4-CF3(3) m.p. 187-190" 55 H 4-CI H -C6H4CI(4) m.p.204-205 56 H 4-Cl H -C6H3C12(3,4) m.p. 204-205" 57 H 4-CI H -C6H3Cl(3)isoC3H7(4) m.p. 150.1510 58 H 4-Cl H -C6H5 m.p. 148.1500 59 2-Cl 4-Cl H -C6H3C12(3,5) solid 60 4t.C4H9 H H -C6H4CI(4) m.p. 131-133" 61 4-t.C4Hg H H -C6H3Ci2(3,4) m.p. 68- 71" 62 4-t.C4H9 H H -C6H3(CF3)2(3,5) m.p. 58- 60 63 H 3-CF3 H -C6H4(CF3)(3) 64 H 3-CF3 H -C6H4(CF3)(4) 65 H 4-CH30 H -C6H3Cl2(3,4) Comp.R1 R2 R5 R6 Physical No. constants 66 H 4-C2H5O H -C6H4-CF3(3) 67 H 3-CF3 H -C6H5 m.p.141-143 68 H 3-CF3 H -isoC3H7 m.p. 116-118 69 2-Cl 4-Cl H -C6H5 m.p. 163-164 70 2-Cl 4-Cl H -C6H3(CF3)(3,5) m.p. 110-113 71 2-Cl 4-Cl H -C6H3Cl2(2,4) m.p. 152-153 72 4-t.C4H9 H H -C6H4(F3)(3) m.p. 136-140 and also following carbamates of the formula:

Comp.X R R2 R5 R6 Physical No. constants 73 CH3 H H H CH3 m.p. 97- 99 74 COCH3 H H H CH3 75 H 2-Cl 4-Cl H CH3 m.p. 137 76 H H H H CH3 m.p. 92- 94 77 H H 4-Cl H CH3 m.p.133-136 78 H H 4-(CH3)2N H CH3 79 CH3 H 4-(C2H5)2N H CH3 80 CH3 3-NO2 H H CH3 81 H 3-CF3 H H CH3 82 -COOC2H5 3-CF3 H H CH3 83 H 4-CH3O H H CH3 84 CH3 4-CH3O H H CH3 85 H 3-NO2 H H CH3 86 H 2-NO2 H H CH3 87 -COCH3H H H -C6H3C12(3,4) 88 -COCH3 H H H -C6H3(CH3)2(2,4) 89 H H H H -C6H4Cl(4) m.p.145-146 90 H 2-Cl 6-Cl H -C5H4Cl(4) m.p.142-144 91 CH3 H H H -C6H4Cl(4) m.p.105-106 92 -COCH3 H H H -C6H4Cl(4) m.p.297-298 93 H H 4-Cl H -C6H5Cl(4) m.p.151-152 94 H H 4-Cl H -C6H5 m.p.106-109 95 H H 4-Cl H -C6H4-CH3(3) m.p.119-121 96 H H 4-Cl H -C6H4-F(4) m.p.130-132 97 H H 4-Cl H -C6H4NO2(4) 98 -COOC2H5 H H H CH2 99 -COOCH3 H H H CH3 100 -COOtC4H9 H H H CH2 101 -COOCH3 H 4-Br H CH3 102 -COOC2H5 H 3-CF3 H CH3 103 -COOCH3 H 4-Cl H -C6H5 104 -CONHCH2 H H H CH3 105 -CONH2 H H H CH3 106 -CONHisoC3H, H H H CH3 107 -CONHCH3 H 4-CH2O H CH3 108 -CONHCH3 H 4-Cl CH3 CH3 109 -CONHisoC4Hg H H H CH3 110 -CONHt.C4Hg H 4-Cl H CH3 and also following carbamates of the formula

Comp.Ar X R5 R6 Physical No. constants 111 a-naphthyl -CN H CH3 m.p.154-158 112 a-naphthyl -CN C2H5 C2H5 m.p.162-164 113 ss-naphthyl -CN H tert.C4Hg 114 t3-naphthyl -CN H isoC3H7 115 ss-naphthyl -CN H -C6H4Cl(4) 116 2-furanyl -CN H CH3 117 2-furanyl -CN H -CH2-C=CH 118 2-furanyl -CN H -C6H3C12(3,4) 119 2-thienyl -CN H CH2 120 2-thienyl -CN H C2H5 121 2-thienyl -CH3 H CH3 122 (p)C6H5-O-CeH4- NO2 H CH3 123 (p)C6H5-O-C6H4 -COCH3 H -C6H4CF3(4) 124 H2N-CO- -CN H -C6H4Cl(3) m.p.203-204 125 H2N-CO- -CN H -C6H4Cl(4) m.p.201-203 126 H2N-CO- -CN H -C6H3CI2(2,5) m.p.176-177 127 H2N-CO- -CN H -C6H4CF3(2) m.p.179-183 128 H2N-CO- -CN H -C6H4CF3(4) m.p.170-180 129 H2N-CO- -CN H -C6H3CI(3)CH3(4) m.p.163-164 130 H2N-CO- -CN H CH2 m.p.176-177 131 H2N-CO- -CN H C2H m.p.116-120 132 H2N-CO- -CN H -CH2CH2-CI m.p. 141-142 133 H2N-CO- -CN H -nC3H7 m.p.113-116 134 H2N-CO- -CN H -isoC3H7 m.p.125-126 135 H2N-CO- -CN H -nC4Hg m.p. 92- 96 136 H2N-CO- -CN H -C6H5 m.p. 174-174 137 H2N-CO- -CN H -C6H3CF3(3)CI m.p. 182-183 138 C2H5OOC. -CN H -C6H4Cl(4) m.p.147-148 139 C2H5OOC- -CN H CH3 m.p. 101-103 140 2-thienyl -CN H -C6H3C12(3,4) oil 141 (5Cl)2-thienyl -CN H CH3 m.p.186 142 (5Cl)2-thienyl -CN H -C6H4Cl(4) m.p.186é 143 (5Cl)2-thienyl -CN H -C6H3Cl(4)CF3 m.p. 184 ; and also following carbamates of the formula:

Comp. R4 R5 R6 Physical No. constants 144 CH3- H C6H3CF3(3)Cl(4) m.p. 162-163 145 CH3- H C6H4CF3(3) m.p. 147-148 148 CH3- H C8H5 m.p. 148-150 147 CH3- H C6H4NO2(3) m.p. 166-167 148 CH3- H C6H4Cl(3) m.p. 162-163 149 CH2- H C6H4Cl(4) m.p. 157-158 150 CH3- H C6H4Cl(2) m.p. 136-138 151 CH3- H C6H4CF3(4) m.p. 127-128 152 CH3- H C6H4(OC4Hg(i))(4) m.p. 138-140 153 CH2- H C6H3Cl2(3,4) m.p. 162-163 decomp.

154 CH2- H C6H3Cl(3)Br(4) m.p. 170-171

Comp. R4 R5 R6 Physical No. constants 155 CH3- H C6H3Cl2(2,5) m.p. 164.1650 156 CH2- H C6H3CH3(2)CI(3) m.p. 118-120" 157 CH2- H C6H3CH3(2)c1(4) m.p. 1 19-1 20" 158 CH3- H C6H3Br(2)CH3(4) m.p. 134.1350 159 CH3- H C6H3(CH3)2(2,4) m.p. 115-117" 160 CH2- H C6H3C1(2)NO2(4) m.p. 165-l660decomp. 161 CH2- H C6H3Cl2(2,4) m.p. 143.1450 162 CH3- H -CH3 m.p. 122-123" 163 CH3- H -CH2CH2CI m.p. 72- 74" 164 C2H5- H -C6H5 m.p.130-132 165 C2H H -C6H4Cl(2) m.p. 81- 82" 166 C2H5- H -CeH4Cl(3) m.p. 139-141" 167 C2H5- H -C6H4Cl(4) m.p. 156-157" 168 C2H5- H -C6H4CF3(3) m.p.117-119 169 C2H5- H -C6H4CF3(4) m.p. 136-137" 170 C2H5- H -C6H4NO2(3) m.p. 145.1470 171 C2H H -C6H4CH3)4) m.p. 121-122" 172 C2H5- H -C6H4(O-C4Hg(i))(4) m.p. 127-128" 173 C2H H -C6H3C12(3,4) m.p. 160.1610 174 C2H5- H -C6H3C12(2,5) m.p. 136-137" 175 C2H5- H -C6H3CF2(3)Cl(4) m.p. 141-142" 176 C2H5- H -C6H3C1(2)NO2(4) m.p. 133-134" 177 C2H5- H -C6H3(CF3)2(3,5) m.p. 155-157" 178 C2H5- H -C6H3CH3(2)CI(4) m.p. 90- 91" 179 C2H5- H -C6H2Cl3(2,4,5) m.p. 137-139" 180 C2H5- H -CH3 m.p.104-106 181 C2H5- H -CH2Cl2 m.p. 73- 75" 182 (s)C4H9- H -C6H4Cl(4) m.p. 1280.1300 183 (s)C4H9- H -C6H4CF3(3) m.p. 93- 95" 184 (s)C4H9- H -C6H4CF3(4) m.p. 109-110" 185 (s)C4Hg- H -C6H3C12(3,4) m.p. 140.1410 186 (s)C4H9- H -C6H3C12(2,5) m.p. 100-101" 187 (s)C4H9- H -C6H3CF3(3)CI(4) m.p. 126-127" 188 (s)C4Hg- H -CH3 m.p. 80- 81" 189 (s)C4H9- H -CH2CH2CI m.p. 57- 59" 190 CH2=CH-CH2- H C6H5 m.p. 103-105" 191 CH2=CH-CH2- H C6H4Cl(3) m.p. 118-120" 192 CH2=CH-CH2- H C6H4Cl)4) m.p. 131-132" 193 CH2=CH-CH2- H C6H4CF3(3) m.p. 106-107" 194 CH2=CH-CH2- H C6H4CF3(4) m.p. 121-123" 195 CH2=CH-CH2- H C6H3C12(3,4) m.p. 126-127" 196 CH2=CH-CH2- H C6H3Cl2(2,5) m.p. 130.1310 197 CH2=CH-CH2 H C6H2C13(2,4,5) m.p. 124.1260 198 CH2=CH-CH2- H -CH2CH2CI m.p. 61- 63" 199 C} H -C6H4CI(4) m.p.141-142 200 Q H -C6H4CF3(3) m.p. 94- 96" 201 H -C6H4CI(4) m.p.162-163 202 H -C6H3CF3(3)CI(4) m.p. 131-132" 203 H -C6H2Cl3(2,4,5) m.p.124-126 204 Q H -CH3 m.p. 99-101"

Comp. R4 R5 R6 Physical No. constants 205 C6H5 CH=CH-CH2- H -C6H4Cl(3) m.p. 136"(decomp.) 206 CeH5 CH=CH-CH2- H -C6H3C12(3,4) m.p. 138"(decomp.) 207 C6H5 CH=CH-CHr H -C6H2Cl3(2,4,5) m.p. 16l"(decomp.) 207a CH3- CH3 -CH3 m.p. 105-106" 208 CH3 H C6H3C12(3,5) m.p. 156"(decomp.) 209 H C6H3C12(3,5) m.p. 107-108" 210 Q H C6H3C12(3,4) m.p. 162-163" 211 CH3- H C6H3C12(3,4) m.p. 162-163";

and also following carbamates of the formula

Comp. R5 R6 R9 Rlo Physical No. constants 212 H C6H3C12(3,4) -CH3 -CH3 m.p. 153-154" 213 H C6H3CF3(3)CI(4) -CH3 -CH3 m.p. 154.1560 214 H CeH5 m.p. 143.1440 215 H C5H4Cl(2) m.p.120-123 216 H C6H4Cl(4) m.p: 142.1440 217 H C6H4CF3(4) 9 m.p.160-162 218 H C6H3C12(3,4) 3 m.p.153-154 219 H C6H4CH3(4) 3 m.p. 133.1350 220 H C6H3CF3(3)Cl(4) t3 m.p. 1400(decomp.) 221 H C6H3Cl(2)NO2(4) X m.p.165 (decomp.) 222 H C6H2CI3(2,4,5) X m.p.143-145 223 H -CH3 t3 m.p. 113"(decomp.) 224 H C6H5 m.p. 124.1250 225 H C6H4CI(4) \r m.p. 125-127" 226 H C6H3C12(3,4) m.p. 155.1570

Comp. R5 R6 R9 R70 Physical No. sL, constants 227 H C6H3CF3(3)CI(4) m.p. 145"(decomp.) 228 H -CH3 m.p. m.p.90 (decomp.) 229 H C3H7 CH3 CH3 m.p. 46- 50 230 H CH(CH3)2 CH3 CH3 m.p. 62- 66" 231 H C4H9 CH3 CH3 oil 232 H C2H5 CH3 CH3 m.p. 90" 233 H CH(CH3)2 H H m.p. 206-207" 234 H CH3 CH3 CH3 m.p. 72- 76" 235 H CH2CH2CI CH3 CH3 m.p. 99-101" Th 236 H C6H4Cl(3) m/ m.p. 159-161" /m 237 H C6H4CF3(3) m.p. 130.1320 /m 238 H C6H3CF3(3)CI(4) m.p. 176-178" 239 H C6H5 H -C6H4CF3(3) m.p. 1630(decomp.) 240 H C6H4Cl(4) H -C6H4CF3(3) m.p. 180"(decomp.) 241 H C6H3C12(3,4) H -CsH4CF3(3) m.p. 16l"(decomp.) 242 H C6H3CF3(3)Cl(4) H -CeH4CF3(3) m.p. 169"(decomp.) 243 H C6H5 H -C6H3Cl2(2,4) m.p. 179"(decomp.) 244 H C6H4Cl(3) H -C6H3CI2(2,4) m.p. 154"(decomp.) 245 H C6H4C1(4) H -C6H3CI2(2,4) m.p. 172"(decomp.) 246 H C6H4CF3(3) H -C6H3Cl2(2,4) m.p. 165"(decomp.) 247 H C6H4CH3(3) H -C6H3Cl2(2,4) m.p. 152"(decomp.) 248 H C6H3C12(3,4) H -C6H3Cl2(2,4) m.p.176 (decomp.) 249 H C6H3Cl2(2,5) H -C6H3Cl2(2,4) m.p. 1 85"(decom p.) 250 H C6H3CF3(3)CI(4) H -C6H3Cl2(2,4) m.p. 162"(decomp.) 251 H C6H3CH3(2)CI(4) H -C6H3Cl2(2,4) m.p. 154"(decomp.) 252 H C6H3CH3(2)CI(3) H -C6H3Cl2(2,4) m.p. 140"(decomp.) 253 H C6H3Cl2(2,4) H -C6H3Cl2(2,4) m.p. 172"(decomp.) 254 H C6H9Cl(3) H -C6H3(CF3)2(3,5) m.p. 1650(decomp.) 255 H C6H4Cl(4) H -C6H3(CF3)2(3,5) m.p. 179"(decomp.) 256 H C6H4CF3(4) H -C6H3(CF3)2(3,5) m.p. 1880(decomp.) 257 H C6H4CI(4) H -C6H3Cl)2)NO2(4) m.p. 187"(decomp.) 258 H C6H4CF3(4) H -C6H3Cl(2)NO2(4) m.p. 198"(decomp.) 259 H C6H3C12(3,4) H -CeH3Cl(2)NO2(4) m.p. 198"(decomp.) 260 H CeH3Cl(2)NO2(4) H -C6H3CI(2)NO2(4) m.p. 185"(decomp.) 261 -CH3 -CH3 X m.p. 104.1050 262 -CH3 -CH3 H -C6H3CH3(2)CI(3) m.p. 164"(decomp.) 263 -CH3 -CH3 H -C6H4CF3(3) m.p. 115-117" 264 -CH3 -CH3 H -CeH3C12(2,5) m.p. 162-164 Am 265 -CH3 -CH3 \r ) m.p. 71- 71" 266 H C6H3Cl2(2,5) H m.p. 1200(decomp.) 267 H C6H4Cl(3) H CH2CH=CH2 m.p. 154"(decom p.) 268 H C6H3CF3(3)Cl(4) H CH2CH=CH2 m.p. 175"(decomp.) 269 H C6H3Cl(3)CF3(4) H CH2CH=CH2 m.p. 1390(decomp.) 270 H C6H4Cl(4) H CH2CH=CH2 m.p. 1700(decomp.) 271 H C6H3C12(3,4) H CH2CH=CH2 m.p. 164"(decomp.) 272 H -CH3 H CH2CH=CH2 m.p. 111-113" 273 H CH(CG3)2 H C2H5 m.p. 103-105" 274 H C3H? H C2H m.p. 78- 90" 275 H C4H9 H C2H5 m.p.70,5-74

Comp. R5 R6 Rg Rto Physical No. constants 276 H C3H7 H CH3 m.p. 67- 70" 277 H CH(CH3)2 H CH3 m.p. 116-118,5" 278 H C4H9 H CH3 m.p. 107-109" 279 H CH2-CH2CI H CH3 m.p. 105-106" 280 H C6H4Cl(4) H -a m.p. 177-178 281 H C6H3C12(3,4) H m.p. 1800(decomp.) 282 H CeH3Cl(3)CH3(4) H -a m.p. 166-167" 283 H -CH3 H < m.p.124-126 284 H C6H4Cl(3) H C6H3C12(3,5) m.p. 1900(decomp.) 285 H C6H3CF3(3)Cl(4) H C6H3Cl2(3,5) oil 286 H C6H3C12(3,4) H C6H3C12)3,5) m.p. 173"(decomp.) 287 H C6H3CI(3)CF3(4) H CeH3Cl2(3,5) m.p. 182"(decomp.) 288 H C6H4CF3(4) H C6H3C12(3,5) m.p. 1 69"(decom p.) 289 H CH2CH2C I H H m.p.141-142 290 H -CH3 H CH3 m.p. 167-168"; and also the following carbamates of the for

Comp.R6 R9 R10 Physical No. constants 291 C6H4Cl(3) H CH3 m.p. 177-178 292 C6H4Cl(3) H C2H5 m.p. 166-167 293 C6H4Cl(3) H H m.p. 203 (decomp.) 294 C6H4Cl(3) CH3 CH3 m.p. 125-128 295 C6H4Cl(4) H CH3 m.p. 198-200 296 C6H4Cl(4) H H m.p. 203 (decomp.) 297 C6H4Cl(4) H C2H5 m.p. 180(decomp.) 298 C6H4CI(4) CH3 CH3 m.p. 161-162 299 C6H3CH3(4)CI(3) H CH3 m.p. 180(decomp.) 300 C6H3CH3(4)Cl(3) CH3 CH3 m.p. 144-146 301 C6H3CH3(4)Cl(3) H C2H5 m.p. 163-163,5 302 C6H3CH3(4)Cl(3) H C4H9(n) m.p. 142-145 303 C6H3CH3(4)Cl(3) H H m.p. 163-166 304 C6H3Cl2(3,4) H CH3 m.p. 195 (decomp.) 305 C6H3Cl2(3,4) H C2H5 m.p. 175,5 (decomp.) 306 C6H3Cl2(3,4) H C4H9 m.p. 167,5-170 307 C6H3C12(3,4) H H m.p. 192-193 C6H3CF3(3)Cl(4) H CH3 m.p. 198 (decomp.) 308 C6H3CF3(3)Cl(4) H C2H5 m.p. 185 (decomp.) 309 C6H3CF3(3)Cl(4) H H m.p. 183 (decomp.) 310 C6H3CF3(3)Cl(4) H C3H7(n) m.p. 172 (decomp.) 311 C6H3CF3(3)Cl(4) H C4H9(n) m.p. 174-177 312 C6H3CF3(3)Cl(4) H CH3 m.p.156-158 313 C6H3CF3(3)Cl(4) CH3 H m.p.191 (decomp.) 314 C6H3CF3(3)Cl(4) H 315 C6H3CI(3)CF3(4) H CH3 m.p. 183-185 316 C6H3CF3(3)Cl(4) H C2H5 m.p.167-169 317 C6H3CF3(3)Cl(4) H C4H9(n) m.p.149-150 318 C6H4CF3(2) H H m.p. 183 (decomp.) 319 C6H4CF3(2) H CH3 m.p. 193 (decomp.) 320 CeH4CF3(4) H H m.p. 180 (decomp.) 321 C6H4CF3(4) H CH3 m.p.189 (decomp.) 322 C6H4CF3(4) CH3 CH3 m.p. 134-135 323 C6H4CI(3) H C3H7(n) m.p. 155-157 Comp.R6 R9 R10 Phvsical No. constants 324 C6H4CI(4) H C3H7(n) m.p.170 (decomp.) 325 C6H4Ci(4) H C4H9(n) m.p. 170-174 326 C6H3Cl2(3,5) H H m.p. 200 (decomp.) 327 C6H3Cl2(3,5) H C2H5 m.p. 159 (decomp.) 328 C6H3Cl2(3,5) H CH3 m.p. 194 (decomp.) 329 C6H4CF3(3) H CH3 m.p. 190 (decomp.) 330 C6H4CF3(3) CH3 CH3 m.p. 109-110 331 C5H5 H H m.p. 175 (decomp.) 332 C6H5 H CH3 m.p. 162-163,5 333 C6H3Cl2(2,3) H H m.p. 156 (dcomp.) 334 CH3 H H m.p. 177 (decomp.) 335 CH2CH2 H H m.p. 116-120 336 CH3 H C2H m.p.119,5-124 337 C3H7(n) H H m.p.113-116 338 C6H3CI(3)CH3(4) H H m.p.163-174 339 C6H3CH3(4)Cl(3) H CONH2 m.p. 197 (decomp.) 340 C5H3Cl2(3,4) H CONH2 m.p. 205 (decomp.) 341 C6H3CF3(3)Cl(4) H CONH2 m.p. 200 (decomp.) 342 C6H4Cl(3) H CONH2 m.p. 206 (decomp.) 343 C6H3Cl(3)CH3(4) H CONH2 m.p. 197 (decomp.) 344 C6H3C12(3,5) H CONH2 m.p. 197 (decomp.) 345 C6H4CF3(3) H CONH2 m.p. 208 (decomp.) 346 C6H5 H CONH2 m.p.214-215 347 C6H3Cl2(2,3) H CONH2 m.p.203 (decomp.) 348 CH3 H CONH2 m.p.216 (decomp.); and also following carbamates of the formula:

Comp. R6 Physical No. constants 349 C4H9(n) m.p.131 (decomp.) 350 C3H7(n) m.p.133 (decomp.) 351 C3H7(iso) m.p. 207 (decomp.) 352 -CH2-CH2-Cl m.p.140-145 (decomp.) 353 C3H7(iso) m.p.207 (decomp.) The following (thio) carbonates are produced according to Example 3 or by one of the methods given in the foregoing: Comp.YR7 R10 Physical No. constants 354 OC6H5 H m.p.149 (decomp.) 355 OCH3 H m.p. 170 (decomp.) 356 OC3H7(iso) H m.p.171-173 357 OCH3 CH3 m.p. 97-98,5 358 OC4H9(n) H m.p. 165-167 359 OC3H7(iso) CH3 m.p.109-110 360 O(CH2)3CH3 CH3 m.p. 75- 76 361 OCH3 H m.p. 120-121 362 OCH3 CH3 m.p. 73- 74 363 OC6H5 -CONH2 m.p. 168 (decomp.) 364 OCH3 -CONH2 m.p. 171-172 Comp.YR7 R70 Physical No. constants 365 SC2H5 H m.p.124-125 366 OC4Hg(n) -CONH2 m.p. 173 (decomp.) 367 OC3H7(iso) -CONH2 m.p.173 (decomp.) 368 SC2H5 -CONH2 m.p.179 (decomp.) 369 SC2H5 CH3 m.p. 76- 78 In the manner described in Example 3 or by one of the methods described in the foregoing, there can be produced following carbonates of the formula: :

Comp. R, R2 G Physical No. constants 370 H H -O-C6H5 m.p.105-108 371 H H o-isoC3H7 m.p. 108-110 372 H | H -O-CH2CH20CH3 oil 373 H H -O-CH3 m.p. 108-110 374 H H -O-CH2-CCl3 solid 375 H H -O-C6H4NO2(4) solid 376 H H -S-nC4Hg 377 H H -O-tert.C4Hg m.p. 85- 86 378 H H -S-C2H5 m.p. 59- 62 379 3-Cl 4-Cl -S-C2H5 oil 380 H 4-Cl -S-C2H5 oil 381 2-Cl 4-Cl -S-C2H5 oil 382 H 4-CH3 -S-C2H5 oil 383 H H -O-C6H4C1(4) 384 H 4-Cl -O-sec.C4Hg 385 H 3-CF3 -O-CH3 386 H C-CF3 -O-C6H5 387 H 3-CF3 -S-C2H5 388 H 3-CF3 -S-CH3 389 H 4-Br -S-C2H5 390 H 4-CH3O -O-C6H4-OCH3(4) oil 391 H 4-CH3O -O-C6H4CI(4) viscous 392 H 4-C2H5O -O-isoC3H7 oil and also the following carbonates of the formula::

Comp. R1 R2 X G Physical No. constants 393 H 4-(CH3)2N H -OC2H5 oil 394 H 4-CH30 H -S-C2H5 oil 395 H 4-CI -COOCH3 -OCH3 oil and the following compounds: No. 396

m.p. 184"(decomp.) No. 397

m.p. 144-146"(decomp.) No 398 H5C6-C(CI)=NO-CO-NHCH3 oil No 399 H5C2O-CO-C(CN)=NO-CO-SC2H5 oil No.400 H5C2O-CO-C(CH3)=NO-CO-NHCH3 m.p. 83- 85" No.401

m.p. 126"(decomp.) No. 402

m.p. 145"(decomp.) No. 403

m.p. 1700(decomp.) As already mentioned, various methods and techniques are suitable for application of the compounds of the formula I for the protection of cultivated plants against agricultural chemicals: 1.) Seed dressing a) Dressing of the seed with an active substance formulated as a wettable powder by shaking in a vessel until there exists a uniform distribution over the surface of the seeds (dry dressing). The amount of active substance of the formula I used for this purpose is about 10 to 500 g (40 g to 20 kg of wettable powder) per 100 kg of seed.

b) Dressing of the seed with an emulsion concentrate of the active substance of the formula I using method a) (wet dressing).

c) Dressing by immersion of the seed in a liquor containing 50-3200 ppm of active substance of the formula I for 1-72 hours and, optionally, subsequent drying of the seed (immersion dressing).

The dressing of the seed or the treatment of the germinated seedlings are naturally the preferred methods of application because the treatment with the active substance is directed completely at the target crop.

There is used as a rule 10 g to 500 g, preferably 50 to 250 g, of active substance per 100 kg of seed, it being possible, depending on the method used, which method enables also the addition of other active substances or micronutrients to be made, to deviate either upwards or downwards from the given limiting concentrations (repeat dressings).

2) Applicationasatankmixture A liquid preparation of a mixture of antidote and herbicide (reciprocal quantitative ratio between 1:20 and 5:1 is used, the applied amount of herbicide being 0.1 to 6 kg per hectare. A tank mixture of this type is preferably applied before or immediately after sowing, or is worked into the unsown soil to a depth of 5-10 cm.

3) Application into the seed furrow The antidote is introduced, as an emulsion concentrate, wettable powder or granulate, into the open sown seed furrow and, after covering of the seed furrow in the normal manner, the herbicide is applied using the pre-emergence process.

Essentially, the antidote can therefore be applied before, together with, or after the herbicide, and its application to the seeds or to the field can be effected either before or after sowing, or in certain cases also after germination of the seed.

4) Controlled release of active substance The active substance in solution is absorbed onto mineral granulate carriers or onto polymerised granules (urea/formaldehyde), and the material is allowed to dry. It is possible if desired to apply a coating (coated granules), which enables the active substance to be released in controlled amounts over a specific period of time.

The term "seed" within the meaning of the foregoing is not limited to kernels (of cereals, etc.) but encompasses all propagative organs of cultivated plants. By the team "propagative organs" are meant all generative plant parts which can be used for the propagation of the cultivated plants. These parts include kernels, roots, fruits, tubers, rhizomes and stalks, and also emerged plants and seedlings which are intended for transplanting.

It is naturally possible to employ also all other known methods of applying active substances. Examples in this connection are given later in the text.

The compounds of the formula I can be used on their own or together with suitable carriers and/or other additives. Suitable carriers and additives can be solid or liquid and they correspond to the substances common in formulation practice, such as natural or regenerated mineral substances, solvents, dispersing agents, wetting agents, adhesives, thickeners, binders and/or fertilisers.

The content of active substance in commercial compositions is between 0.1 and 90%.

The compounds of the formula I can be in the following forms for application (the weight-percentage figures in brackets signify advantageous amounts of active substance): Solid preparations: dusts and scattering agents (up to 10%), and granulates [coated granules, impregnated granules and homogeneous granules] (1 to 80%); Liquid preparations: a) water-dispersible concentrates of active substance: wettable powders and pastes (25 to 90% in the commercial packing, 0.01 to 15% in ready-for-use solutions); emulsion concentrates and solution concentrates (10 to 50%; 0.01 to 15% in ready-for-use solutions); b) solutions (0.1 to 20%) and aerosols.

The active substances of the formula I of the present invention can be formulated for example as follows Dust: The following substances are used to produce a) a 5% dust and b) a 2% dust: a) 5 parts of active substance, and 95 partsoftalcum, b) 2 parts of active substance, 1 part of highly dispersed silicic acid, and 97 partsoftalcum.

The active substances are mixed and ground with the carriers, and in this form they can be applied by dusting.

Granulate: The following substances are used to produce a 5% granulate: 5 parts of active substance, 0.25 part of epichlorohydrin, 0.25 part of cetyl polyglycol ether, 3.50 parts of polyethylene glycol, and 91 parts of kaolin (particle size 0.3 - 0.8 mm).

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

Wettable power: The following constituents are used to produce a) a 70% wettable powder, b) a 40% wettable powder, c) and d) a 25% wettable powder, and e) a 10% wettable powder: a) 70 parts of active substance, 5 parts of sodium dibutylnaphthylsulfonate, 3 parts of naphthalenesulfonic acid/phenolsulfonic acid/formaldehyde condensate 3:2:1, 10 parts of kaolin, and 12 parts of Champagne chalk; b) 40 parts of active substance, 5 parts of sodium lignin sulfonate, 1 part of sodium dibutyinaphthalenesulfonate, 54 parts of silicic acid; c) 25 parts of active substance, 4.5 parts of calcium lignin sulfonate, 1.9 parts of Champagne cha Ik/hydroxyethyl cellulose mixture (1:1).

1.5 parts of sodium dibutyinaphthalenesulfonate, 19.5 parts of silicic acid, 19.5 parts of Champagne chalk, and 28.1 parts of kaolin; d) 25 parts of active substance, 2.5 parts of isooctylphenoxy-polyoxyethyleneethanol, 1.7 parts of Champagne chalk/hydroxyethylcellulose mixture (1:1), 8.3 parts of sodium aluminium silicate, 16.5 parts of kieselgur, and 46 parts of kaolin, and e) 10 parts of active substance, 3 parts of a mixture of the sodium salts of saturated fatty alcohol sulfates, 5 parts of haphthalenesulfonic acid/formaldehyde condensate, and 82 parts of kaolin.

The active substances are intimately mixed in suitable mixers with the additives, and the mixture is then ground in the appropriate mills and rollers. There are obtained wettable powders which have excellent wetting and suspension properties, and which can be diluted with water to give suspensions of the desired concentration.

Emulsifiable concentrate: The following substances are used to produce a 25% emulsificable concentrate: 25 parts of active substance, 2.5 parts of epoxidised vegetable oil.

10 parts of an alkylarylsulfonate/fatty alcohol polyglycol ether mixture, 5 parts of dimethylformamide, and 57.5 parts of xylene.

Emulsions of the desired concentration can be prepared from these concentrates by dilution with water.

Post-emergence antidote test in nutrient solution General procedure Plastic flower pots (upper diameter 6 cm), which have a pierced bottom, are filled with Zonolite and the cultivated seeds are sown therein. The pot is placed into a second transparent plastic flower pot (upper diameter 7 cm) in which there is 50 ml of water, which rises by capillary attraction and wets the seeds. From the 5th day the continuous loss of water is compensated with Hewitt nutrient solution. From the 15th day, when the cultivated plants are in the 11/2. to 2-leaf stage, there is added to the nutrient solution, made up again to 50 ml, 10 ppm of the antidote to be tested + the amount of herbicide given below.

From the 16th day, the loss of liquid is again made up with pure Hewitt nutrient solution. During the entire duratior of the test, the temperature is 20-23"C with a relative humidity of 60-70%. Three weeks after addition of the herbicide and antidote, an evaluation is made on the basis of a linea scale from 1 to 9, with 1 signifying total plant destruction, and 9 an unimpaired condition of health of the cultivated plants.

Test variants 1) 15 ppm of ct-[4-(3,5-dichloropyridyl-2-oxy)-phenoxy]-propionic acid propargyl thiol ester in wheat of the "Zenith" variety; 2) 4 ppm of 4-ethylamino-6-tert-butylamino-2-chloro-s4riazine in wheat of the "Zenith" variety; 3) 2 ppm of a-[4-(p-trifluoromethyl phenoxy)-phenoxy]-propionic acid-n-butoxyethyl-ester in maize of the "Orla" variety; 4) 8 ppm of a-[4-(p-trifluoromethylphenoxy)-phenoxy]-propionic acid-n-butoxyethyl ester in sorghummillet of the "Funk G-522"variety; 5) 4 ppm of Prometryne = 2,4-bis-(isopropylamino)-6-methylthio-s-triazine in sorghum-millet of the "Funk G-522" variety; and 6) 8 ppm of a-[4-(3,5-dichloropyridyl-2-oxy)-phenoxyl-propionic acid methyl ester in wheat of the "Zenith" variety.

Compounds of the formula I have a good antidote action in these tests. The following results are given as examples: Test variant Compound No. Rating ofthe herbicidal effect (without/with antidote) 1 91 6/8 6 54 3/7 6 372 2/5 Pre-emergence antidote test in nutrient solution A Hewitt nutrient solution is prepared, which contains the amount of herbicide given below and 10 ppm of the antidote to be tested.

There is used cultivated seed which could be expected to suffer damage from the employed herbicide at the given test concentration, and the seed is sown in granulated Zonolite (= expanded vermiculite) which is contained in a plastic flower pot having a pierced bottom (upper diameter 6 cm). This pot is placed into a second transparent plastic flower pot (upper diameter 7 cm), in which there is about 50 ml of the nutrient solution that has been prepared with herbicide and antidote; this solution then rises by capillary attraction in the filler material of the smaller pot and wets the seed and germinating plants. The loss of liquid is made up daily with pure Hewitt nutrient solution to 50 ml.Three weeks after commencement of the test, evaluation is made on the basis of a linear scale from 1 to 9, with the rating 1 signifying total plant destruction, and the rating 9 signifying an unimpaired condition of health ofthe plants. The control solution used in a parallel test contains no antidote addition.

There are used the following: 1) 4 ppm of Prometryne = 2,4-bis-(isopropylamino)-6-methylthio-s-triazine in sorghum-millet of the "Funk G-522" variety; 2) 4 ppm of 4-ethyl am ino-6-tert-butylamino-2-chloro-s-triazine in wheat of the "Farnese" variety; 3) 4 ppm of a-[4-(p-trifluoromethyl phenoxy)-phenoxy]-propionic acid-n-butoxyethyl ester in barley of the "Mazurka" variety; 4) 5 ppm of Metolachor = N.(1-methyl.2-methoxy-ethyl)-N-chloroacetyl-2-ethyl-6-methylaniline in sorgum-milletofthe "Funk G-522" variety; and 5) 1 ppm of 2-methoxy-4,6-bis-(y-methoxy-propylamino )-s-triazine in sugar beet of the "Kleinwanzleben" variety.

Compounds of the formula I exhibited in these tests a good antidote action. The following results may be given as examples: Test variant Compound No. Rating ofthe herbicidal effect (without/with antidote) 2 73 2/5 4 93 2/5 4 396 2/5 4 4 3/7 4 19 2/6 (with 1 ppm antidote concentration) 5 19 2/5 5 36 1/5 3 96 2/5 5 112 1/7 (with 1 ppm antidote concentration) 4 52 2/5 4 51 2/5 Antidote test with seed soaking Rice seeds of the IF 8 variety are saturated during 48 hours with solutions of the test substances of 10 or 100 ppm concentration. The seeds are subsequently allowed to dry for about 2 hours, until they no longer stick together. Rectangular plastic pots (8 x 8cm, cm in height) are filled up to within 2 cm of the edge with sandly loam. In each pot is sowed 4 g of seed, and the seed is only very slightly covered (about the diameter of a seed). The soil is maintained in a moist (not boggy condition). There is then applied either the herbicide N-(1 -methyl-2methoxyethyl).N-chloroacetyl-2-ethyl-6-methylaniline or N-propoxyethyl-Nchloroacetyl-2,6-diethylaniline in dilute solution and in an amount which converted corresponds to 1.5 kg of active substance per hectare. An evaluation is made 18 days after planting on the basis of a linear scale from 1 to 9, according to which the rating 1 signifies total plant destruction, and the rating 9 an unimpaired condition of health of the plants.

Compounds of the formula I exhibit in this test a good antidote action. The following results may be given as examples: Compound No. Rating of the herbicidal effect lwithoutlwith antidote) 100 ppm 396 2/5 397 2/5 10 ppm 90 1/4 138 2/5 Pre-emergence antidote test (basic test) General procedure: Smali flower pots (upper diameter 6 cm) are filled with garden soil, into which the cultivated plants are sown, covered over and lightly pressed down. The substance to be tested as antidote is then sprayed on as a diluted solution (obtained from a wettable powder) in an amount corresponding to 4 kg of active substance per hectare. The herbicide is afterwards sprayed on in a similar manner.After a standing time of 18 days at about 20-23"C with 60-70% relative humidity, an evaluation is made on the basis of a linear scale from 1 to 9, according to which the rating 1 signifies total plant destruction, and the rating 9 an unimpaired condition of health of the cultivated plants. Plants without antidote protection are used in control tests.

The following are used: 1) 1.5 kg of active substance per hectare of a-[4-(p-trifluoromethylphenoxy)-phenoxy]-propionic acid-n-butoxy-ethyl ester in maize of the "Orla 264" variety; 2) 1.5 kg of active substance per hectare of Metolachlor = N-(l -methyl-2-methoxyethyl )-N-chloroacetyl- 2-ethyl-6-methylaniline in sorghum-millet of the Funk G-522"variety; 3) 2.0 kg of active substance per hectare Prometryne = 2,4-bis-(isopropylamino)-6-methylthio-s-triazine in soya bean; 4) 2.0 kg of active substance per hectare of 4-ethylamino-6-tert-butylamino-2-chloro-s-traizine in wheat of the "Farnese" variety; 5) 4.0 kg of active substance per hectare of Prometryne = 2,4-bis-(isopropylamino)-6-methylthio-striazine in sorghum-rnllletofthe "Funk G-522" variety;; 6) 2.0 kg of active substance per hectare of ct-[4-(p-trifluoromethylphonoxy)-phenoxy]-propionic acid-n-butoxyethyl ester in barley of the "Mazurka" variety; and 7) 1.0 kg of active substance per hectare of N-methoxy-ethyl-N-chloroacetyl-2,6-dimethylaniline in maize of the "Anjou 196" variety.

Compounds of the formula I exhibit in these tests a good antidote action. The following results are given as examples.

Test variant Comp. No. Rating of the herbicidal effect lwithoutlwith antidote 6 138 4/7 5 398 1/4 4 31 2/4 7 51 2/5 3 378 2/5 Antidote action on transplanted rice with separate application (antidote pre-emergence + herbicide post-emergence) Plastic pots (8 x 8cm, cm in height) are filled to within 2 cm of the edge with soil in the boggy-wet condition. The substance to be tested as antidote is sprayed in dilute solution, onto the surface, in an amount corresponding to 4 kg of active substance per hectare. Rice plants of the "IR-8" variety in the 11/2. to 2-leaf stage are transplanted into the pots prepared in this manner. The water level is raised to about 1.5 cm on the next day.Four days after transplanting, there is added to the water 2-othylamino-4-(1 ,2-dimethyl-n- propylamino)-6-methylthio-s-triazine in granular form in an amount which, when converted, corresponds to 0.75 kg of active substance per hectare. The temperature during the duration of the test is 26-28"C, and the relative humidity is 60-80%. Twenty days after treatment with the herbicide, an evaluation is made based on a linear scale from 1 to 9, the rating 1 signifying total plant destruction, and the rating 9 unimpaired condition of health of the cultivated plants. Plants without antidote protection are used in control tests.

Compounds of the formula I exhibit in this test a good antidote action. The results below are given as examples.

Comp. No. Rating of the herbicidal effect (without/with antidote) 396 3/6 42 5/7

Claims

1. A process for protecting cultivated plantsfrnm being damaged by harmfulagricultural chemicals, which process comprises applying to sald plants or parts thereof or to their growth, a compound of the formula I

in which AR - is a phenyl group of the formula

a naphthyl group which is substituted by R2 and R3, a furan or thiophene ring whio @ sunsubstituted or substituted by halogen, NO2 or lower alkyl, or Ar is one of the radicals COOR4 or -CO-R8, X is -CN, lower alkanoyl, a carboxylic acid ester group, -COOH, hydrogen, a carboxylic acid amide.

group; halogen or lower alkyl, R1 is hydrogen, halogen, lower alkyl, lower alkoxy, or a phenoxy group which is in the para-position and which i unsubstituted or substituted a maximum of twice by halogen, -CN, NO2 or CF3, R2 and independently of one another are hydrogen, halogen, NO21 lower alkyl, haloalkyl, lower alkoxy or di (lower alkyl) amino, R4 is an aliphatic, cycloaliphatic or araliphatic group, and an aromatic radical can substituted as defined under R2 and::R3 and can be additionally substituted by -CN, R is either a) a radical -N(R5)(R6), in which R5 is lower alkoxy or is the same as Re, Re is hydrogen or an aliphatic, cycloaliphatic, araliphatic, aromatic or heterocyclic group, and an aromatic radical can basubstituted as givenunder.

R2 and R3, or b) a radical -YR1, in which Y is oxygen or sulfur, and R7 is one of the 5 groups given or R6; R8 is either a) a radical -N(Rs)(Rio), in which Rg is hydrogen, lower alkyl or cycloalkyl, and R10 has the meaning of R8 or is hydrogen or R9 and R10 togsther with the -N atom for a 3-7- membered ring whichcan.be substituted by lower alkyl groups, or b) aradical -NH-CONHR10.

2. A process according to Claim 1 wherein there is applied a compound of the formula lin which Ar is a phenyl or naphthyl group as defined in Claim 1, Xis cyano, hydrogen, lower alkanoyl,.a carboxylic acid ester "group, a carboxylic acid amide group or lower alkyl, R1 is hydrogen, halogen, or a phenoxy group which is in the para-position and which is unsubstituted or substituted a maximum of twice by halogen, -CN or CF3R2 and R3 independently of one another are hydrogen, halogen, lower alkyl, haloalkyl or lower alkoxy, and R is as defined in Claim 1.

3. A process according to Claim 1 wherein there is applied a compound of the formula I in which Ar is a phenyl group as defined in Claim 1, Xis cyano, hydrogen, acetyl, -COO-lower alkyl, -COONH2, -COON H-lower alkyl, -COON (lower alkyl)2 or methyl, R1 is hydrogen, R2 and R3 are hydrogen, halogen, lower alkyl, CF3, methoxy or ethoxy, R5 is hydrogen, lower alkyl or lower alkoxy, R6 is an aliphatic group, or a phenyl group which is unsubstituted or substituted by halogen, lower alkyl, CF3, methoxy or ethoxy, Y is oxygen or sulfur, and R7 has the meanings given above for R6.

4. A process according to Claim 1 wherein there is applied a compound of the formula I in which Ar is a thiophene ring unsubstituted or substituted by halogen or lower alkyl, and Xis as defined in Claim 2 and R is as defined in Claim 1.

5. A process according to Claim 1 wherein there is applied a compound of the formula I in which Ar is a thiophene ring unsubstituted or substituted by halogen or lower alkyl, and X, Y, R5, R6 and R7 are as defined in Claim 3.

6. A process according to Claim 1 wherein there is applied a compound of the formula I in which Ar is one of the radicals -COOR4 or -COR8, wherein R4 is a lower aliphatic group having a maximum of 4 carbon atoms or is phenyl, and in the definition of R8 the substituents Rg and R1O independently of one another are hydrogen, lower alkyl, or phenyl which is unsubstitute or substituted by halogen, CF3 or lower alkyl, and Xis as defined in Claim 2 and R is as defined in Claim 1.

7. A process according to Claim 6 wherein there is applied a compound of the formula I in which X, Y, R5, R6 and R7 have the meanings given in Claim 3.

8. A process according to Claim 1 wherein there is applied a compound of the formula I specifically identified herein.

9. A process according to any one of Claims 1 to 8, wherein the crop area of cultivated plants is treated with the compound of the formula I either before or after application of an agricultural chemical.

10. A process according to any one of Claims 1 to 8, wherein the crop area of cultivated plants is treated simultaneously with an agricultural chemical and the compound of the formula I.

11. A process according to any one of Claims 1 to 8, wherein the cultivated plants or parts thereof are treated with the compound of the formula I before cultivation.

12. A process according to Claim 11, wherein the generative parts of the plant are treated.

13. A composition for the protection of cultivated plants against harmful agricultural chemicals, which composition contains, as an antidote active substance, a compound of the formula I as defined in Claim 1.

14. A composition according to Claim 13, which contains, as an antidote active substance, a compound of the formula las defined in Claim 2.

15. A composition according to Claim 13, which contains, as an antidote active substance, a compound of the formula las defined in Claim 3.

16. A composition according to Claim 13, which contains, as an antidote active substance, a compound of the formula I as defined in Claim 4.

17. A composition according to Claim 13, which contains as an antidote active substance, a compound of the formula I as defined in Claim 5.

18. A composition according to Claim 13, which contains, as an antidote active substance, a compound of the formula las defined in Claim 6.

19. A composition according to Claim 13, which contains as an antidote active substance, a compound of the formula I as defined in Claim 7.

20. A composition according to Claim 13, which contains, as an antidote active substance, a compound of the formula I specifically identified herein.

21. An agricultural composition which composition comprises an agricultural chemical and, as antidote therefor, a compound as defined in any one of Claims 1 to 8.

22. A composition according to Claim 21 wherein the agricultural chemical is a herbicide.

23. A composition according to any one of Claims 13 to 22 which also contains as solid extender and, optionally, a surface active agent or a liquid diluent and a surface active agent.

24. A compound of the formula las defined in Claim 1.

25. A compound of the formula I as defined in Claim 2.

26. A compound of the formula las defined in Claim 3.

27. A compound of the formula I as defined in Claim 4.

28. A compound of the formula las defined in Claim 5.

29. A compound of the formula I as defined in Claim 6.

30. A compound of the formula I as defined in Claim 7.

31. Any one of the compounds of the formula I according to Claim 24 specifically identified herein.

32. A generative part of the cultivated plant, which part has been treated with a compound of the formula I as defined in Claim 1.

33. A generative part according to Claim 32 wherein the compound of the formula I used is as defined in any one of Claims 2 to 7.

34. A generative part according to Claim 32 wheren the compound of the formula I used is a compound specifically identified herein.