CA1130312A - Oxime derivatives for the protection of cultivated crops - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
There is described a process for the protection of cultivated plants against harmful agricultural chemicals, which process comprises the use of oxime derivatives of the formula (wherein R1 is (a) a radical -OR2, wherein R2 is C1 to C4 alkyl or cyclopropyl, lb) a radical -NH - CO - NH - R4 or (c) 3 radical - N(R3) (R4), wherein R3 and R4 each independently hydrogen or C1 to C4 alkyl, and Q is hydrogen, - CH2 - CN
or a quaternized ammonium salt) as antidotes. The cultivated area or the cultivated plants themselves, or parts of the plants (seed, tubers, sections of stalk, etc.), can be treated with these oxime derivatives.

Description

1~30312 The present invention relates to the use of oxime derivatives of the general formula I
Rl-CO-C-CN (I) N-O-Q
; for the protection of cultivated plants against harmful agricultural chemicals.
In formula I Rl is (a) a radical -OR2, wherein R2 is Cl to C4 alkyl or cyclopropyl, (b) a radical -NH - CO - NH - R4 or (c) a radical -N~R3) (R4), wherein R3 and R4 each independently hydrogen or Cl to C4 alkyl, and Q is hydrogen, - CH2 - CN or a quaternized ammonium salt.
Quaternary ammonium salts contain, as identical or different substitu-ents, hydrogen, Cl-C12 alkyl, lower hydroxyalkyl, benzyl, amino or di-lower-alkylamino, or form from two valencies and the N atom a 5- or 6-membered heterocyclic ring having optionally a further hetero atom, namely N, O or S.
Oximes of the formula I are excellently suitable for protecting cultivated plants, such as rice, maize and varieties of cereals (cultivated millet, wheat, rye, barley or oats) from being attacked by agricultural chemicals harmful to cultivated plants, particularly by herbicides of the most varied classes of substances, in cases where these chemicals do not act selectively or not sufficiently selectively, that is to say, damage to a greater or lesser extent the cultivated plants in addition to destroying the weeds to be con-trolled.
There have already been suggested as antidotes various substances ableto 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 type (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 decribes the treatment of seed and seedlings of wheat and sorghum with cetain esters and amides 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. 2,021,611) 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 United States Patent Specification No.
3,131,509, hydroxyaminoacetanilides and hydantoins are suggested for the pro-tection of cereal seeds against carbamates, such as IPC, CIPC, and so forth.
In further development, however, none of these products has proved adequate.
Surprisingly, oximes of the formula I have the property of being able to protect cultivated plants against attack from agricultural chemicals which -~ are harmful i~3~3:~2 ,~

to such plants, particularly against attack from herbicides of the most diverse classes of substances, including 1,3,5-triazines, 1,2,4-triazinones, phenyl-urea derivatives, carbamates, thiolcarbamates, phenoxy-acetates, phenoxypropionates, haloacetanilides, halo-phenoxyacetates, substituted phenoxyphenoxyacetates and -propionates, substituted pyridinephenoxyacetates and -propionates, benzoic acid derivatives, and so forth, in cases where these chemicals are not compatible, or not suffiently 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 seedlings); or it can be applied to the soil before or after sowing; or it can be applied on its own or together with the herbicide before or after emergence of the plants. The treatment of the plants 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 sowing (ppi = pre plant -incorporation) and the treatmen~
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 thP type of application. If a field treatment is undertaken, the amounts of antidote of the formula I with respect to the 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 ` ~L3~3~Z

with the amounts of herbicide employed for example subsequently per hectare of cultivated area (for example about 1:3000 to 1:1000). There exists as 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 merely an antidote of the formula I
together with customary inert carriers. Compositions ofthis 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 beet, sugar cane~ peanuts, tobac~o and hops, and also ornamental plants, fruit trees as well as banana, cocoa and natural rubber plants. This list of plant types 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.
- The invention relates to a process for the protection , ~ . :

of cultivated plants against harmful (phytotoxic) agricultural chemicals, in which process an oxime derivative of the formula I, which has an antidote action, is employed either before or after application of the agricultural chemical, or simultaneously with the agricultural chemical.
The invention relates also to the propagative organs of cultivated plants, which organs have been protected by treatment with an oxime derivative of the formula I. By the term "propagative organs" are meant all generative plant parts which can be used for the propagation of the cultivated plants.
These parts include seeds ~seed in the narrower sense~, roots, fruits, tubers, rhizomes, parts of stems, cuttings and other parts of plants Also included however are germinated plants and seedlings which, after germination or emergence, are to be transplanted. Young plants of this kind can be specifically protected, by a complete or partial immersion treatment, before being trans-planted.
Compounds of the formula I can be produced by known methods of oxima-tion of compounds of the formula II
R -CO-CH -CN (II) ~with the meanings given under the formula I) by reacting with nitrous acid (HN02) or with an organic or inorganic nitrite; and then converting the result-ing free oximes with bases into the salts, or acylating the free oximes with acids or acid halides, or converting them, with radicals splitting off halogen, into other oxime ethers mentioned under Q. The following may be cited as relevant literature: German Offenlegungsschriften Nos. 2,312,956 and 2,350,910;
and also "Berichte der deutschen chem. Gesellschaft" 42, p. 738 ff. [1909].
Of compound of formula I, the compound of formula ,; ' N-OCH2CN

is novel and forms part of this invention.

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~3~33~

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 ratio.
The Exa~ple which follows illustrates the production of oximes of the formula I. Temperature values are given in degrees Centigrade.
Example 1 10 Production of ll N-OH
~-cyano-~-hydroxyimino-acetyl-urea 50 g of cyanacetylurea is added at 80C in the course of 5 minutes, with vigorous stirring, to 50 g of sodium nitrite in 250 ml of water, and the temperature is then raised to 100. After the addition is completed, the reaction mixture is stirred at room temperature for a further hour, and is sub-sequently cooled to 10. The formed sodium salt of the final product is filtered off, and dissolved, wi~h heating, in 200 ml of water. To the solution is then added 70 ml of concentrated hydrochloric acid, and the mixture is finally cooled and filtered to yield ~-cyano-~-hydroxyiminoacetyl-urea having a melting point of 210 to 212~ ~with decomposition).
In this manner or by one of the aforementioned methods, there can be produced the following compounds of the formula:

N-O-Q

~.~

,~ ~ - 6 -~3~31Z

Comp. Q Physical No. constants 1 H m.p. 185-187

2 -C}I2CN m.p. 165-167 ~ NH(CH3)2-cl2~l25( ) m.p. 74-75,5 4 ~ NH3-CI13 m.p. 136-138 ~ H2N~,0 m.p. 153 6 ~ NH3-N(C~I3)2 m.p. 133-134 7 ~ HIN~C12H25(n) oil 8 ~ NH3-sec.C4Hg m.p. 91-97 9 ~ NH2(CH3)2 m.p. 145-147 ~ ~ 2 ~ 2 ~ m.p. 240(decomp.) 11 C H CH -N-C H (n) wax 12 ~ H2N~CH2CH2-OH)2 oil 13 ~ IIN(C~13)3 m.p. 138-142 and also following compounds of the formula:

N-O-Q
Comp. R Q Physical No. 4 constants 14 H2N-Co 2 oil f --~3(~3:12 Comp- 4 Q Physical No. constants H5C2NH-C0 - 2 oil 16 H N~C0- ~3ll3NCH3 m.p. 176 (decomp.) 17 H N-C0- ~3 NH4 m.p. 209 (decomp.) 18 H N-C0- ~3 ( 3)2 2 m.p. 125-126 19 H N-C0- ~ H2N~_~0 m.p. 160-165 H N-C0- 63NH(CH3)2-C12H25(n) m.p. 110-113 21 H N-C0- ~3 NH3-sec.C4Hg m.p. 149 22 H N-C0- ~3NH(CH3)2-CH2CH20H m.p. 125-128 23 H N-C0- ~NH2(CH2CH2 OH)2 m.p. 136-138 24 H N-C0- ~3NH2(CH3)2 m.p. 171-172 H2N-CO- ~3 NH(CH3)3 m.p. 160 (decomp.) 26 H5C2NH-C0 H m.p. 166-168 27 cyclohexyl H m.p. 202 28 CH3 ~3 H2N~_~0 m.p. 121-123 29 CH3 ~3H3N-N(CH3)2 solid nC4Hg H m.p. 125-126.5 31 CH3 2 m.p. 91-93 32 cyclopropyl H m.p. 181 33 CH3 ~3 7 12 25( ) oil 34 CH3 ~ NH~CH3)2C12H25(n) m-p- 92-93 . ~ - 8 -j.,~

', ~.

~1~()31Z

Comp- 4 Q Physical No. constants CH3 ~3NH3-sec.C4Hg m.p. 146-148 36 CH3 ~3 NH -CH m.p. 175 37 CH3 63 NH2(CH3)2 m.p. 75-78 and also following compounds of the formula:
(CH3)2N-CO-C-CN
N-O-Q
Comp. Q Physical No. constants 38 H m.p. 225 (decomp.) 39 ~3 NH3-sec.C4Hg m.p. 112 G3 NH2(CH2CH20H)2 oil 41 6~NH2(CH3)2 oil 42 ~3 NH(cH3)2-cl2H25( ) oil - ~ and also following compounds of the formula:

N-O-Q
Comp. R Physical No. 2 Q constants 43 C2H5 H m.p. 133-136 44 CH3 -CH2CN oil cyclopropyl -CH2CN oil ", .. _ ~ _ g ':

3~3~Z

~c 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 dressin~ ~
a) Dressing of the seed with an active substance formu-lated 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 2 kg of wettable powder) per 100 kg of seed.
b) Dressing of the seed with an emulsion concentrate of ~he active substance of the formula I using method a) (wet dressing).
c) Dressing by immersion of the seed in a liquor con-taining 50-3200 ppm of active substance of the formula I
or 1-72 hours and, optionally, subsequent drying of the 8eed (immersion dressing).
The dressing of the seed or the treatment of the germin~ted 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) Application as a tank mixtur_ -~ liquid prepaFation of a mixture of antidote and , ' . 10 ;3~31 2 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 kind 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.
It is naturally possible to ëmploy also all other known methods of applying active substances. Examples ln this connection are given later in ~he text~

, , _ . _ _ .. ... . . . .. . ., .. .. .. , .. .. . . . , .. , _ _ _ . _ _ _ _ _ _ _ _ _, , _ _,, ~ _ ~ _ .

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The compounds of the formula I can be used on their own or together with suitabie 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, wet~ing agents, adhesives, thickeners, binders and/or ~ertilisers.
The content of active substance in commercial compo-sitions is between 0.1 and 90 %.
The compounds of the formula I can b~e in the ollowing 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 lcoated granules, impregnated granules and homogeneous granules] (l to 80%);
liquid preparations:
a) water-dispersible concentrates of active substance:
wettable powders and pastes (25 to 90~/O in the commercial packing, 0.01 to 15% in ready-for-use solutions);
emulsion concentrates and solution - concentra~es (10 to 50%; 0.01 to 15%
in raady-for-use solutions), b) solutions (O.L to 20%) and aerosols.
The active substances of the formula I of the present invention can be formulated f~r ex-mple as follows.

, -, ~V3 ~3 ~ranulate: The following substances are used to producea 5% granulate:
parts of active substance, 0.25 part of epichlorohydrin, 0.25 part of cetyl polyglycol ether, 3.50 parts of pol~ ethylene glycol, and 91 parts of kao in (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 powder: The following constituents are used to produce a) a 70% wettable powder and b) a 10% wettable powder:
a) 70 parts of active substance, 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; and b) 10 parts of active substance, 3 parts of a mixture of the sodium salts of - saturated fatty alcohol sulfates, parts of naphthalenesulfonic acid/formaldehyde condensate, and 82 parts of kaolin~
The artive 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 , 3~ Z

~4 wettable powders which have excellent wetting and suspension properties, and which can be diluted with ~ater to give suspensions of the desired concentration.
' ~ ', -.
Emulsifiable concentrate: The following substances are . _ used to produce a 25% emulsifiable concentrate:
parts of active substance, 2.5 parts of epoxidised vegetable oil, parts of an alkylarylsulfonate/fatty alcohol polyglycol ether mixture, S parts of dimethylformamide, and 57.5 parts of xylene.
Emulsions of the desired concentration can be pre-pared from these concentrates by dilution with water.

113~31Z

`~ ~ Pre-emer~ence 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 granu-exP~ Jer~ c / f e lated ~cr.~ e~ e~ rm ~'ulitc)- which is contained in a plastic flower pot having a pierced bottom (upper diameter 6 cm). This pot is placed into a second tran-parent 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 nutxient solution to 50 ml. Three weeks after commencement of the test, an 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 of the plants. The control 801ution 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 ~55~,h ~ of the "Funk G-522l' variety;
2) 4 ppm of 4-ethylamino-6-tert-butylamino-2-chloro-s-triazine in wheat of the 'IFarnese" variety;-3) 4 ppm of a-[4-(p-trifluoromethylphenoxy)-phenoxy3-propionic acid-n-butoxyethyl ester in barleY of the '~azurka'l variety;

.

1~

4) 5 ppm of Metolachlor = N-(l-methyl-2-methoxy-ethyl)-N-chloroacetyl-2-ethyl-6-methylaniline in sor~hum-millet of the "Funk G-522" variety; and

5) 1 ppm of 2-methoxy-4,6-bis-(~-methoxy-pro wlamino)-s-triazine in sugar beet of the "Kleinwanzleben" variety.
Compounds of the formula I exhibited in these tests a good antidote action.
.

- Post-emer~ence antidote test in-nutrient solution General procedure .

Plastic flower pots (upper diameter 6 cm), which have a pierced bottom, are filled with granulated 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 1 1/2- to 2-leaf stage, there is added to the nutrient solution, made up again to 59 ml, a) 10 ppm of the antidote to be tested ~
- -~ the amount of herbicide given below, and b) 1 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 duration of thP test, the temperature is 20 23C 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 linear scale from 1 to 9, with 1 signifying total plant destruction, and 9 an unimpaired conditions of health of the cultivated plants.

.

.. ,.. . . , , . ., . . ., ... 5 .

::

113~3 ~1 -- 2~- - ' Test variants 1) 15 ppm of a-[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-s-triazine in wheat of the "Zenith" variety;
3) 2 ppm of a-[4-(p-trifluoromethylphenoxy)-phenoxy]-propionic acid-n-butoxyethyl ester in maize of the "Orla" variety;
4) 8 ppm of a-l4-(p-trifluoromethylphenoxy)-phenoxy]-propionic acid-n-butoxyethyl ester in sorghum-millet 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)-phenoxy]-propionic acid methyl ester in wheat of the "Zenith"
variety.
Compounds of the formula I have a good antidote action Ln these tests, for example Compound No. 1.

. , , , ' '-. .
.

,~

Antidote test with seed soakin~
Rice seeds of the IR 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 8 cm, 10 cm in height) are filled up to within 2 cm of the edge with sandy 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~ methyl-2-methoxyethyl)-N-chloroacetyl-2-ethyl-6-methylaniline or N-propoxyethyl-N-chloroacetyl-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 o 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.
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Claims (9)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A process for the protection of cultivated plants against harmful agricultural chemicals, which process comprises using as an antidote an oxime derivative of the formula I

( I ) in which R1 is (a) a radical -OR2, wherein R2 is C1 to C4 alkyl or cyclopropyl, (b) a radical -NH - CO - NH - R4 or (c) a radical - N(R3) (R4), wherein R3 and R4 each independently hydrogen or C1 to C4 alkyl, and Q is hydrogen, - CH2 - CN or a quaternized ammonium salt.

2. A process according to claim 1, comprising use of an oxime derivative of the formula I in which Q is a quaternary ammonium salt, possible substituents being hydrogen, lower alkyl, benzyl or hydroxyethyl.

3. A process according to claim 2, comprising use of an oxime derivative of the formula wherein R3 and R4 independently represent hydrogen or methyl, as well as its quaternary ammonium salts comprising one, two or three alkyl and/or hydroxy alkyl groups the sum of whose carbon atoms is at most 6.

4. A process according to calim 2, comprising use of an oxime derivative of the formula as well as its quaternary ammonium salts the latter comprising one, two or three alkyl and/or hydroxy alkyl groups the sum of whose carbon atoms is at most 6.

5. A process according to claim 1, comprising use of the oxime derivate of the formula

6. A process according to any one of claims 3 to 5 wherein the crop area of cultivated plants is treated with the antidote of the formula I either before or after application of a herbicide selected from 1, 3, 5-triazines or chloroacetanilides.

7. A process according to any one of claims 3 to 5, wherein the crop area of cultivated plants is treated simultaneously with the antidote of the formula I and a herbicide selected from 1, 3, 5-triazines or chloroacetanilides.

8. A process according to any one of claims 3 to 5, wherein parts of the plant are treated before cultivation.

9. The compound of formula