FR2488781A1 - HERBICIDAL COMPOSITIONS CONTAINING ANTIDOTE AND METHODS USING THE SAME - Google Patents

Abstract

HERBICIDE COMPOSITION CONSISTING OF AT LEAST ONE ACTIVE HERBICIDE COMPOUND AND AN ANTIDOTE TO THIS COMPONENT CORRESPONDING TO GENERAL FORMULA I (CF DRAWING IN BOPI) OR X REPRESENTS OXYGEN OR NITROGEN, N VALUE ZERO OR 1, Y IS A HYDROGEN, A POTASSIUM, A POTASSIUM. A HALOGEN, A HYDROXYL OR AN ALCOYL HAVING 1 TO 4 CARBON ATOMS, POSSIBLY SUBSTITUTED BY A HYDROXYL OR A HALOGEN, Z IS AN ALCOYLENE, A CYCLOHEXYLENE, A CYCLOHEXYLIDENE OR PHENYLENE PARTICULARLY SUBSTITUTED BY A NICOLOHEXYLIDENE OR PHENYLENE SUBSTITUTE SUBSTITUTE WITH A PAROGENON OR PHENYLIDENE SUBSTITUTE SUBSTITUTE IF X REPRESENTS AN OXYGEN, NZERO.

Description

-1 -

  The present invention relates to composi-

  herbicides containing an antidote. More particularly

  The invention provides a herbicidal composition

  comprising an active herbicidal compound as defined above

  below, and an antidote to this compound corresponding to the general formula I It

Z X - (Y) (

  X represents an oxygen or a nitrogen, n is zero or 1, Y is a hydrogen, a potassium, a halogen, a hydroxyl or an alkyl having from 1 to 4 carbon atoms, optionally substituted by a hydroxyl or a halogen,

  Z is an alkylene, cyclohexylene, cyclohexyl,

  diene or phenylene optionally substituted with

  halogen or nitro with the precision that if X represents

feels oxygen, n = zero.

  The use of agricultural chemicals is

  including herbicides is essential for agriculture.

  modern culture. Of the many herbicide compounds that have been developed in recent decades,

  for example triazines, ureas, chloroacethanes

  lides and recently thiolcarbamates as well as several

  their blends have reached a high degree of

2488581 -

  commercial success. However, it has proved to be

  However, the use of these herbicides, apart from their weeding effect, can also cause serious damage to the crop plants, ie their selectivity is not satisfactory. The importance of phytotoxic side effects depends mainly on the dose of the active ingredient, but is also influenced by weather conditions, soil type, etc. Some active compounds as herbicides, for example ureas, are selective at low doses,

  but these doses are not always sufficient, however,

  to obtain the desired herbicidal effect.

  The phytotoxic side effect of thiol-

  carbamates active as herbicides is particularly

  pronounced. Among the N, N-dialkyl homologues

  S-alkyl-thiolcarbamates alone the Sutan has a lower toxicity, while by the example the EPTO which is

  a much stronger herbicidal agent also causes

  damage to crop plants when it is

  used in an amount where it is effective as herbicide

cide.

  Previous attempts to solve this problem

  bleme involve a treatment of the plant

  with a certain antagonist. So it was established by O.L. Hoffmann et al. that the undesirable phytotoxic effect of some herbicides can be reduced

  by treating the cultivated plant with 1,8-

  naphthalic acid or an ester salt thereof, (United States Patents

  Nos. 3,131,509, 3,702,759 and German No. 952,910).

  Recently carboxylic amide derivatives

  NR, I-disubstituted, preferably N, N-diallyl-dichloro

  acetamlide have been shown to be potently active compounds as antidotes, particularly in combination with thiolcarbamate herbicides (Hungarian patent).

No. 165,736).

-3-

  The two classes of compounds mentioned above

  However, they are not enough to solve all the practical problems related to the phytotoxic effects of the numerous and various known herbicide compounds. There is an urgent need to continue research to find new classes

  compounds capable of alleviating or eliminating

  harmful effects of various herbicides on cultivated plants

véese

  It has now been found that the derivatives of

  The cyclic dicarboxylic acids of general formula I as defined above have excellent properties.

  antidotes in combination with various herbicides

in commerce.

  In the description above the various

  substituent groups must be translated in the way

  following: for Y, halogen includes fluorine, chlorine

  bromine or iodine, preferably chlorine or bromine; and the term alkyl having from 1 to 4 carbon atoms

  carbon "applies to aliphatic hydrocarbon groups.

  saturated straight or branched chain ticks having from 1 to 4 carbon atoms, for example methyl, ethyl,

  n- and isopropyl, n-butyl, etc .; for Z the ter-

  "alkylene" includes the bi-hydrocarbon groups

  saturated valencies with straight or branched chain,

  preferably from 1 to 6, or more preferably from 1 to 4, carbon atoms.

  bone, for example methylene groups; ethylene, pro-

  pylene, etc., while the term "halogen" is used

  in the same sense as defined above.

  The following are listed in Table I below

  characteristic representatives of the compounds of

General mule I.

TABLE I

  Cm o S u b s t i t u t s t s Compounds of formula (I)

vompose, m ,,,, ....

  nO n Y X. Z chemical name pF OC - - O phenylene

- - O tetrachloro-

  phenylene - - O0 tetrabromophenyl -H 1 -IH

1 -IM

1 -H

1 -K

1 -OH

1 -Cl

1 -H

1 -H

1 -C 1 OH

  1 -CM1 '1C4HI8Br 1 -Cl 1 -Br 1 -OH 0 cyclohexylene 0 ethylene 0 propylene N ethylene N cyclohexylene N cyclohexylydene N phenylene N phenylene N phenylene N phenylene N 3 -nitro-phenylene N 4-nitro-phenylene N phenylene N phenylene N phenylene N ethylene N ethylene N ethylene anhydride phthalic acid

tetrachloroacid anhydride

phthalic

anhydride of tetrabromo-

phthalic

1,2-anhydride of cyclic acid

  hexane dicarboxylic anhydride succinic acid anhydride glutaric acid imide succinic acid imide cis-hexahydrophthalic

dicyclohexène- (4) -dicarbox-

  imide (1,2) imide phthalic imide phthalic-potassium imide N-hydroxyphthalic imide N-chloro-phthalic imide 3-nitro-phthalic imide 4-nitrophthalic imide N-hydroxyethyl-phthalic imide N-chloromethyl-phthalic imide N-bromobutyl-phthalic imide of N-chlorosuccinic acid imide of N-bromo-succinic acid

imide of N-hydroxy-acid

succinic

131-133

255-256

- 31 - 53

126-127

233.5

235-237

129.5

134-135

77-78

  oo Co Co TABLE I (Continued) Compound S u b s t i t u t n s s Compounds of formula (I) n n Y X Z chemical name pF 0 N 4-nitro-phenylene

1 -CH 2 OH N 4-cyclohexen-1,2-

ylene

I -C 2 H 4 OH N 4 -cyclohexen-1,2-

ylene

I -CH20H N 4-chloro

phenylene

I -C 2 H 4 OH N 4-chloro

phenylene

1 -C H60H N 4-chloro

  3 6phenylene - - O 4 -nitrophenylene - - O 3 -nitrophenylene

- - 0 2-cyclohexene

1,2-ylene

- - O 4 -cyclohexen-1,2-

ylene

I -H N tetrachloro-

  phenylene 1 -CH 2 OH N 3 -nitro-phenylene I -H N maleinyl

imide 4-nitro- (N-hydroxymethyl) -

phthalic

(N-hydroxymethyl) -cyclopropanecarboxylic

hexene (4) dicarboximide (1,2)

(N-hydroxyethyl) -cyclopropanecarboxylic

hexen-dicarboximide (1,2)

imide (N-hydroxynmethyl) -4-chloro

phtali ue

imide (N- (2'-hydroxyethyl) -4-

chloro-phthalic

imide (N-3'-hydroxypropyl) -4-

chloro-phthalic

anhydride of 4-nitro-

phthalic

anhydride of 3-nitro-

phthalic

2-cyclohexenic acid anhydride

1,2-dicarboxylic

anhydride of 4-cyclohexenic acid

  1,2-dicarboxylic imide tetrachlorophthalic

156-157

93-94 69-70

126-129

127-129

101-103

-121.5

163-164

78-79

103-104

imide N-hydroxymethyl-3-nitro-

phthalic imide maleic

1 -CH20H

ro oo -o Cc I I -6-

  The compounds of the general formula I are

  specialists and can be prepared by many conventional chemical reactions [Beilstein: Handbuch der Org. Chem. IX. 811; Buc. S.R. J. Am. Chem. Soc. 254-256 (1947); Kissinger, W. W. Nugade, H. E., Jo Org. Chem. 23, 815 (1958); Nefkens H. L., Nature 193, 974 (1962); and German Patent Nos. I 086 704 and

I 125,415].

  The present invention provides herbicidal compositions comprising an active compound as a herbicide and an antidote to this compound. As used herein the term "active compound as a herbicide" relates to thiolcarbamates alone, triazines alone, chloroacetanilides.

  alone and urea alone and any mixtures

  two or more compounds of this kind.

  The amount of the antidote compound present

  in the compositions according to the invention may vary from

  0.1 to 50% by weight relative to the weight of the com-

  posing as active herbicide. The exact amount of the antidote compound is usually determined on economic criteria so that the most effective amount can be taken. We must understand that we

  employs a non-phytotoxic amount of anti-

  endowed with the herbicidal compositions described here.

  The compositions according to the invention can be used in any convenient form. They can be presented in solid formulations or

  liquids, for example wettable powders, in particular

  emulsifiable concentrates, in powder mixtures, in aqueous suspensions, etc. A characteristic pulverulent mixture may for example have the following composition: Active herbicidal compound, for example

  2-chloro-2'-methyl-6'-tert-butyl

  (Butoxymethyl) -acetanilide Antidote, eg Compound No. 28 Wetting agent, for example alkylphenolpolyglycol ether Dispersing agent, for example acid%% 3% alkylaryl sulfonic acid-Ca 2% Active silicic acid 10% Kaolin 25%

  A typical aqueous suspension

  takes the following ingredients: Active herbicide compound, for example

3-methyl-4-amino-6-phenyl-d1,2,4-

  triazine-5- (4H) -one 20% Antidote, for example compound n 22 20% Alkoylaryl sulfonate 1% Sodium lignosulfonate 3% Polyoxyethylenealcoylaryl ether 4% Protective colloid, for example lecithin 2% Water 50% The compositions according to the invention can

  also contain several active compounds as herpes

  bicides. The composition of the

  characteristic powdered nappes, containing a

  combination of a urea and an acetanidic herbicide

  lide: Active herbicidal compound I, for example

  IN- (4-bromophenyl) -1'-methoxy-NT '-

  methyl urea 10% active herbicidal compound II, for example

2-chloro-2'-methyl-6'-ethylbenzylamine

  (ethoxymethyl) -acetanilide 40% Antidote, for example compound n 5% Fatty alcohol sulphonate 3% Sodium lignosulfonate 2% Amorphous silicic acid 10% Kaolin 30%, It should be noted that antidote compounds of general formula I can also be formulated alone. For example, a wettable powder

  characteristic, containing a compound of general formula

  I mix with appropriate media and other ad-

  conventional compounds, may have the following composition: Antidote, for example compound n 8 70.0% Kaolin 17.0% Active silicic acid 5.0% Fatty alcohol sulphonate 2.5% Ligninsulfonic acid-Na 2.5% A emulsifiable concentrate containing an antidote, for example the following composition: Antidote, for example compound n 18 50% Solvent, for example xylene 45% emulsifying agent, for example polyoxyethylenealcoylaryl agent 5%

  Plants can be treated with herbicides

  cides and antidotes simultaneously but also

  sively. According to a preferred embodiment, the seeds of the cultivated plant are treated with a

  non-phytotoxic amount of the antidote of general formula

  and planted in soil that has been treated with

  herbicides, or plant them in soil that does not

  not treated with the herbicide and that

  later with the herbicide. We can also mix

  manage a non-phytotoxic amount of a herbicide antidote compound with a selected herbicide and incorporate

  in the soil before or after planting the seeds.

  The invention comprises a method for protecting the

  plants against damage due to an active compound as a herbicide,

  habitat an effective antidotal

  of general formula I. The invention also comprises

  process of destroying plant pests involving the application to their habitat of an

  as a herbicide of a herbicidal composition containing

an antidote according to the invention.

  The examples below detail the invention in more detail without limiting it in any way.

way.

  The herbicides used in the experiments below are:

  Afalon: herbicide containing N- (5,4-dichloro-

  phenyl) -N'-methoxy-N'-methylurea as an ingredient

  asset, produced by Hoeschst, Federal Republic of Germany;

  Eptam: herbicide containing S-ethyl-N, N-dipropyl

  thiolcarbamate as an active ingredient,

  produced by Stauffer Chemical Co., USA;

  Sencor: herbicide containing 4-amino-5- (tert.-

  butyl) -5-methylthio-4,5-dihydro-1,2,3-Trianon

  zine-5-one as an active ingredient, produced by the Bayer Company, Federal Republic

- from Germany.

  In order to examine how the compounds of the general formula I attenuate or eliminate the harmful effects of various herbicides on the cultivated plants, experiments are carried out with the herbicidal compositions (Afalon, Eptam, Sencor), alone and with combinations of said herbicides and various compounds of general formula I active as antidotes and certain antidotes, respectively. We use for the purposes

  comparing plants that are weeded mechanically

  is lying. The living weight of the harvested plants in the treated plots is compared with that of the

  harvested plants in the control plots.

Example 1

Cultivated plant: sunflower.

  Herbicide: Afalon. Antidotesconnus used for comparison: 1,8-naphthalic anhydride,

  N, 1-diallyl-2,2-dichloroacetamide.

  Four experiments are carried out on

  these on plots of 10 m2. Afalon is used at

  a dose of 5 kg of active ingredient per hectare, while-

  antidotes are used at doses of 0.5; 1.0 and

  2.0 kg per ha, respectively. the results of the experi-

  when the herbicide and antidotes are applied

  to the plants simultaneously by spraying are given in Table 2 below:

TABLE 2

  Live Weight Treatment (%)

when applying the

endowed with a dose of

0.5 1.0 2.0

  kg / ha kg / ha kg / ha Afalon 41 41 41 Afalon + anhydride 1,8- 58 69 75 naphthalic Afalon + N, N-Diallyl-48 51 67 2,2-dichloroacetamide Afalon + Compound No. 2 70 102 106 Afalon + Compound No. 8 85 98 133 Afalon + Compound No. 13 67 83 98 Afalon + Compound No. 16 78 100 105

Witness (mechanical tearing

  The data in the table above clearly shows that the compounds of the general formula I tested attenuate the phytotoxicity of Afalon a great deal.

  more effectively than the two known antidotes used

  its for comparison purposes, and that in addition in three

  case they provide better results than the

mechanical grassland.

  In another series of field trials, sunflower seeds are disinfected with 0.5; 1.0 and 2.0 kg per 100 kg of seed, respectively, and the doses of antidotes and Afalon are

  5 kg of active ingredient per ha after seeding.

  In addition, the conditions of the experiment are as described above. The experiments are carried out

four times.

  The results obtained are given in Table

* 3 below.

  2> 0 Treatment Seed disinfection

TABLE 3

  Live weight (%) When applying the antidote Pulverium at a dose of 0.5 kg 1.0 kg 2.0 kg per 100 kg of Afalon 41 41 41 Anhydride 1.8- Afalon 57 69 75 naphthalic acid N, N-diallyl-2,2-Afalon 62 71 75 dichloroacetamide Compound n 2 Afalon 100 100 105 Compound n 8 Afaion 100 105 118 Compound n 13 Afalon 87 1100 110 Compound n 16 Afalon 100 117 125 3c) -12-

  Comparing the results listed in

  In Table 3, it can be concluded that the antidote effect, ie the

  reduction of the phytotoxicity of Afalon on the rotator

  soil, is considerably more pronounced when the

  antidotes are used by seed disinfection.

  The living weight of the harvested plants (except

  in one case) is superior or at least

  he of the witness weeded mechanically.

Example 2

  Cultivated plant: but Herbicide: Eptam Known antidotes used for comparison: 1,8-naphthalic anhydride N, N-diallyl-2,2-dichloroacetamide

  Experiments are being carried out on

  those of 20 m2 four times. Eptam is used at a dose of 13 liters of active ingredient per hectare, while antidotes are used at doses of 0.5;

1.0 and 2.0 kg / ha, respectively.

  A combination of Eptam is incorporated into the soil

  and antidotes tested before planting the seeds.

  The results obtained are given in Table 4 below.

below. Treatment -13-

TABLE 4

  Live weight (C%) by applying the antidote to a dose of

0.5 1.0 2.0

kg / ha kg / ha kg / ha Eptam 48 48 48

Eptam + Anhydride 1,8-

naphthalic 60 64 70

Eptam + N, N-diallyl-2,2-

  dichloroacetamide 69 84 92 -. iiiiiii Eptam + Compound No. 10 64 79 95 Eptam + Compound No. 12 57 87 90 Eptam + Compound No. 16 51 83 87 Eptam + Compound No. 19 86 87 98 Eptam + Compound No. 20 82 85 102 Control (Mechanical Weed Removal) 100 100 100

  Compounds N 10, 19 and 20 are no longer

  to reduce the phytotoxicity of Eptam as the known antidotes used for comparison, while the antidote activity of compound 12 is

  substantially identical to that of N, N-diallyl-2,2-

  dichloroacetamide. In another series of field trials, maize seeds are disinfected with doses of 0.25; 0.50 and 1.0 kg of antidote per 100 kg of seed,

  respectively, and the seeds are planted in

  those previously sprayed with a dose of Eptam of 13 liters of active ingredient / ha. Moreover, the conditions of the experiment are as described above. The experiments are carried out fourteen-

  times. The results are given in Table 5 below.

  below. Seed disinfection treatment

TABLE 5

  Live weight (Q /) by applying the antidote Pulveri - at a non-1 nv dosage rate) c kg / 100 kg of semen seed kg / 100 kg of seed kg / 100 kg of seed - 3Eptam 48 48 48 Anhydride 1,8-Eptam 68 7 72 Eptam 68 70 72 naphthalic N, NT-diallyl-2,2-Eptam dichloroacetamide 65 75 80 Compound No. 3 Eptam 68 78 85 Compound No. 7 Eptam 65 76 83 Compound No. 8 Sptam 70 79 90 Compound No. 19 Eptam 72 85 96 Compound No. 20 Eptam 71 80 88 Control (mechanical pulling out of 100 100 100 weeds) The above results clearly demonstrate that all experimental compounds of general formula I (compounds No. 3, 7, 8, 19, 20) are more effective than N, N-diallyl-2,2-dichloroacetamide or 1,8-naphthalic anhydride.

Example 3

  Cultivated plant: soybean Herbicide: Sencor Known herbicides used for comparison: 1,8-naphthalic anhydride, I, N-diallyl-2,2-dich. loroacetamide The experiments are carried out on plots of 10 m2 on four occasions. Sencor is used on a

  1.5 kg of active ingredient / ha, while

  fold antidotes at doses of 0.50; 1.0 and 2.0

  kg / ha, respectively. We combine Sencor and anti-

  in the form of a mixture in the tank and applied to the plants by spraying. The results

  obtained are given in Table 6 below.

TABLE 6

  Live weight (%) treatment by applying the antidote to a dose of

0.5 1.0 2.0

kg / ha kg / ha kg / ha Sencor 17 17 17

Sencor + Anhydride 1,8-

naphthalic 30 41 52

Sencor + N, N-diallyl-2,2-

  dichloroacetamide 20 21 26 Sencor + Compound No. 2 53 71 85 Sencor + Compound No. 12 39 58 73 Sencor + Compound No. 16 46 62 76 Sencor + Compound No. 17 50 64 97

Witness (mechanical weeding

100 100 100

  The results above show that the N, IN-

  diallyl-2,2-dichloroacetamide hardly reduces the phyto-

  toxicity of the triazine herbicide tested (Sencor) and also that the antidote activity of the anhydride

  1,8-naphthyl is also far from satisfactory.

  On the other hand, the compounds tested according to the invention

  are much more powerful than the best anti-

  known endowments used for comparison purposes.

  In another series of tests, soya is disinfected with doses of 0.25; 0.5 and 1.0 kg of antidote per 100 g of seed and spray Sencor & reason

  1.5 kg of active ingredient per ha after sowing

  is lying. Moreover, the conditions of the experiment are as described above. The experiments are done four times. The results obtained are

given in Table 7 below.

TABLE 7

  Seed disinfection treatment

sprayed

  Weight in the live state (%) by applying the antidote at a dose of 0, 25 kg 0.50 kg 1.00 per 100 kg of kg seed Sencor 17 17 17 Anhydride 1, 8- Sencor 51 64 70 naphthalic

N, N-diallyl-2,2-

  dichloro-acetamide Sencor 26 28 31 Compound n - 2 Sencor 58 75 92 Compound n0 12 Sencor 52 69 79 Compound n 16 Sencor 49 67 80 Compound n 17 Sencor 56 71 88 Indicator (mechanical weed control) 100 100 100

  The results obtained show that the activity

  antidote of 1,8-naphthalic anhydride was

  improved by this mode of application but that

  poses of general formula I tested are still very

  more effective shots as antidotes "

  In summary, the results given in

  Tables 2 to 7 clearly show that the compounds of general formula I, where the substituents are as defined above, are antidotes considerably.

-1 7 -

  more powerful than the trade antidotes used

  for comparison purposes. It can also be established that

  they can be used advantageously so

  multi-active with the active compound as an antidote, either formulated with the herbicide or in the form of separate formulations. The results are even better when disinfecting the seeds of a crop plant

  with the antidotes and then apply the herbicide.

  Another advantage of the compounds of general formula

  neral I holds at their reasonable price and ease

  with which one can get them.

  The following experience illustrates the activity

  antidotes according to the invention combined with herbs

chloroacetanilide bicides.

Example 4

  Phytotoxicity of various herbicides is tested

  chloroacetanilide compounds alone and combined with

  to antidotes of general formula I. The greenhouse experiments are carried out 5 times. The herbicides tested are used in the form of the formulations of the

  trade, which has been diluted before application to

  the desired doses of active ingredient per hao

  Antidotes are used at doses given

  in Table 8 below, and were obtained by dilution of the following powder mixture: antidote 70% kaolin 17% active silicic acid 8% fatty alcohol sulfate 2.5% ligninsulfonic acid-INa 2.5% Filled pots 15 cm in diameter from one

  sandy soil up to 5 cm from the top of the pot. In each

  that pot has 10 seeds of corn. We cover

  Seeds with a 5 cm thick layer of untreated or treated soil. The treated soil is prepared in -18-

  incorporating the desired dose of the herbicide and

  tidote in the soil by spraying while stirring the soil for good efficiency. For the purposes of

  comparison untreated control plants are used.

  We keep the pots in a greenhouse and we water them at will.

  The evaluation is carried out four weeks after treatment.

  is lying. Plants are cut immediately above the soil surface and their green weight (in the living state) is compared. The weight is compared to the live weight of the untreated control (100%). The results are

given in Table 8 below.

TABLE 8

  Combined dose Rate kg / ha kg / ha n 0.005 0, 5 1.0 2.0 Weight in the live state as a% of the control ii i i i i, i _J ,,, i

2-chloro-2'-methyl-6'-ethyl-T-

(Ethoxymethyl) acetanilide

  2-chloro-2-ethyl-6-methyl-IN- (i-

  methyl-2-methoxyethyl) -acetanilide 1i0

52 52

72 85

89,100

81 98

85

69 80

83 96

79 90

  9o! ## EQU1 ## ## EQU1 ## ## where ## STR1 ## the compound dose of compound is as follows: ## EQU1 ## 0 2.0 Weight at ('s, tat sivanL en 5, dlu temo n

  c-ch! loro-2 ', O' -di.thth-I-(l.3-di-

  ox-ol .alpha., 1-methyl-tanilide

  2'-chloro-6'-diethyl-NT- (ethoyl)

  carbonyl (tntl ', il) -activated tanililde) o 2'1 o -tc-G 7c 6c, r 7c 0.98 7U o. 9 4S I1CC) 0C0 "1CI 1C, 1C, 1C, 95Co, oo CoCt TABLE 8 (Continued) A ntidote Dose Compound Dose kg / ha kg / ha n 0.005 0.5 1.0 2, 0 H erbicide Live weight in% of the control 2-chloro-2'-methyl-6'-tert-butyl-6-45 45 45 45 N- (butoxymethyl) -acetanilide 6 14 69 80 89 95

6 15 76 91 95 98

6 22 82 101 103 104

6 28 65 89 91 96

6 29 75 86 88 92

6 33 79 98 101 100

  2-chloro-N-isopropylacetanilide 10 - 72 72 72 72

4 85 97 98 98

8 88 98 100 99

9 90 99 99 100

23 92 101 101 102

24 94 102 104 104

30 89 96 95 95

31 87 96 96 97

  2-chloro-1N- (1-methyl-2-propynyl) -6- 62 62 62 62 acetanilide 6 5 75 80 83 89

6 6 73 79 84 86

6 7 72 80 89 92

6 19 78 89 95 98

6 20 80 91 96 96

6 21 89 100 105 100

6 34 85 98 100 101

I IN ru 4c Co -4 Co 00.to -22 -

Example 5

Emulsifiable concentrate

  Herbicide: 2-chloro-2'-methyl-6 '-

ethyl-N- (ethoxymethyl) -

  acetanilide 40% Antidote: Compound n 6 4.0%

Emulsifying Agent: Alkoylarylpoly-

  glycol-ether 6.0% Isophorone 50.0%

Example 6

  Oily suspension Herbicide: I: N-phenyl-N ', N'-dimethylurea 10.0%

  Herbicide II: S-ethyl-NN-dipropyl-thiol

  carbamate 55.0% Antidote: Compound No. 22 5%

  Emulsifying Agent: Alkylphenol Alkoxa-

late + ethylenoxide -

propylene polymerizate

  oxide 5% Vaseline oil 25% -25 -

- R it: IiGATIOKS -

  1 - A herbicidal composition comprising at least one active herbicide compound and an antidote for this compound corresponding to the general formula I

'

  we l! Where X represents oxygen or nitrogen, is zero or 1, Y is hydrogen, potassium, halogen, hydroxyl or alkyl having from 1 to 4 carbon atoms; carbon, optionally substituted by a hydroxyl or a halogen,

  Z is an alkylene, cyclohexylene, cyclohexyl,

  diene or phenylene optionally substituted with

  halogen or a nitro with the precision that if X

has an oxygen, n = zero.

  2 - Composition according to claim 1, comprising said antidote in an amount of 0.1 to 50%

  by weight relative to the active herbicidal compound.

  - Composition according to claim 1,

  o the active herbicide compound is iT, 7-dipropyl-S-

  ethyl-thiolcarbamate, N, I-diisobutyl-S-ethyl-thiol-

  carbamate, iT, -hexamethylene-S-ethyl-thiolcarbamate

  or -diisoprol-S- (2, 5-tricoroallyl-ti)

carbamate or a mixture thereof.

  4 - Comoosition according to claim 1,

  the active herbicidal compound is N-isopropyl-2-

  chloroacetanilide, 2-chloro-T-ethoxym-ethyl-2'-methyl-

-24-

  6'-ethyl-acetanilide or a mixture thereof.

  - Composition according to claim I o

  the active herbicidal compound is IT- (3-chlorophenyl) -

  Methoxyurea, N- (3,4-dichlorophenyl) -N'-methyl-

  methoxyurea or a mixture thereof. 6 - Composition according to claim 1 o

  the active herbicidal compound is 2-chloro-4-ethylamino-

  6-isopropylamino-1,3,5-triazine, 2-butylamino-4-

  chloro-6-ethylamino-1,3,5-triazine, 2- (4-chloro-6-

  1-O-ethylamino) -1,3,5-triazin-2-yl-amino-2-methylpropionic acid

  nitrile, 2-butylamino-4-ethylamino-6-methylthio-

  1,3,5-triazine, 2-ethylamino-4-methylthio-6-iso

  propylamino-1,3,5-triazine or 2,4-bis-isopropylamino-

  6-methylthio-1,3,5-triazine or a mixture of two or

several of these compounds.

  7 - Composition according to claim I o

  the active herbicidal compound is 4-amino-6-tert.-butyl-

  4,5-dihydro-3-methylthio-1,2,4-triazin-5-one. 8 - Composition according to claim I which

  comprises as an antidote compound tetrachlorohydride

  phthalic acid, cis-hexahydro-phthalimide, ET-hydroxy-

  ethyl phthalimide or N-bromosuccinic imide.

  9 - Composition according to any one of

  Claims 1 to 8 also comprising a support or

inert diluent.

  - Control method against parasites

  applying to their habitat an effective herbicidal amount of a composition in accordance with

claim 1.

  11 - Method for protecting a crop against damage due to an active herbicidal compound, involving applying to the plant or to the seed of the plant a non-phytotoxic quantity, effective as an antidote, of a compound of general formula I, o X, n, Y

  and Z are as defined in claim 1.

  12. A method according to claim 11 which involves applying to the seed of the plant before planting a non-phytotoxic quantity, effective as an antidote, of a compound of general formula I, where X, n, Y and Z are such The process according to claim 11, which involves applying the antidote of general formula I,

  o X, n, Y and Z are as defined in the claim

  cation 1, parallel to or prior to treatment

with an active herbicidal compound.