CA1136878A - Antidote-containing compositions for combatting weeds - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
The invention relates to antidote-oontaining new compositions for combatting weeds. These new compositions contain at least one he?cidally active agent selected from the group consisting of thiol OE bamate, sub-stituted urea, substituted triazine, chloroacetanilide and uracil type com-pounds and 1 to 50 % by weight, calculated for the weight of the herbicid-ally active agent, of at least one antidote of the general formula (I),

Description

ll~t~

This invention relates to antidote-containing new oonpositions for ccmbatting weeds which exert reduced phytotoxic effects on cultivated plants and contain as herbicidally active agent at least one compound select-ed from the group consisting of thiol OE bamate, substituted urea, chloro-acetanilide, triazine and uracil-type substances, along with 1 to 50% by weight, calculated for the weight of said herbicidally active agent, of an antidote. Furtherm~re, the invention relates to a process for combatting weeds with the simultaneous reduction of the phytotoxic side effects of the herbicidally active agents by applying the herbicidally active agents along with antidotes.
The antidotes utilized according to the invention correspond to ~he general formula (I) ~ O
Y ~ C - X
wherein X stands for hydroxy, amino, Cl 5 alkylamino, di-(Cl 5aIkyl)- amino, Cl 5 hydroxyalkylamino or Cl 5 alkoxyalkylamino group, and Y stands for hydrogen, halogen, nitro group or a ~ 5 alkyl group.
mus, this invention provides an antidote-containing oamposition for oombatting weeds, characterized by containing at least one herbicidally

2~ active agent selected from the group consisting of thiolcarbamate, sub-stituted urea, substituted triazine, chloroacetanilide and uracil type oompounds and 1 to 50% by weight, calculated for the weignt of the herbicidally active agent, of at least one antidote of the general formula (I), ~
YV,~ C - X

wherein X stands for hydroxy, amino, Cl 5 aIkylamino, di-(Cl_5alkyl)- amino, Cl_5 ~ydroxyalkylamino or Cl 5 alkoxyalkylamino group, and Y stands for hydrogen, halogen, nitro group or a Cl 5 alkyl group, in a total amount of 10 to 90% by weight, along with 90 to 10% by weight ,.~,s of one or more conventional formulation aids.
This inventionalso provides a method for combatting weeds, characterized in that a herbicidally active amount of at least one herbi-cidally active agent selected from the group consisting of thiolcarbamate, substituted urea, substituted triazine, chloroacetanilide and uracil type co~pounds, furthermore an effective amount of 1 to 50% by weight, calculated for the weight of the herbicidally active agent, of at least one compound of the general formula (I), as defined above are applied onto the soil either separately or simultaneously, before or after sowing the seeds of the cultivated plant.
This invention still further provides a method for oombatting weeds, characterized in that the seeds of the cultivated plant are treated before sowing with an effective amount of 1 to 50% by weight, calculated for the weight of the herbicidally active agent, of at least one compound of the general formula (I), as defined a~ove and the soil is treated with a herbicidally active amount of at least one herbicidally active agent selected from the group consisting of thiolcarbamate, substituted urea, substituted triazine, chloroacetanilide and uracil type compounds either before or after sowing the seeds.
It is well known from the literature that a substantial part of herbicidally active agents damages the cultivated plants to be protected as well. This view is also supported bypractical experiences. The extent of phytotoxicside effects depends primarily on the dosage of the active agent, but it is also influenced by the treatment conditions (weather - 2a -conditlons, na~ure o~ ~oil, etc.). Some other herbicidellg agents exert, ln f~ct, selective activity, in the do~ages required to attsin effective protection against weeds they ~re, however, less selective and tend to in~luence adv~rsely the growth and development o~ cultivated plants.
In order to suppress the harm~ul side effects o~
herbicidally active substances it was recommended to apply them i~ admixture with 1,8-naphthalic scid or derivative~
(~uch a8 anh~dride, amide~ and e3ters) thereof (U.S. patent ~pecification No. 3,131,509).
According to the Hungarian pa~ent specification No.
165~76~ the adverse side ef~ects of thiolcarbamates can be 8uppressed by admixing t~em with 0.0001 to 30 ~ by weight Or ~ N,N-disubstituted dichloroacetamide.
The problems emerged in con~ection with phytotoxic herbicides can be solved, however~ only in part by utilizing these two types of antidotes widely applied in practice.
Ta~ing into accou~t that the scale of phytotoxic herbicides 1~ extremel~ wide a~d the individual types of cultivatsd 20 ~18nt8 show d~fere~t reactions to the~e herbicides it i8 obviou~ that the be~eficial e~fects of the known a~tidote~
are restr1cted to aertain combinatio~s of herbicide~ and plants.
Our investigations directed to the suppression oi 25 th~ phytotoxic side effects of herbicidally active agents ~imed ~t the elaboration and utilization of a new group of ~ntidotes which, beside exerting a favourable phytotoxicity-supprsssing e~fect, also meet the requirements o~ environmental protection and ensure a more economical utilization of the ~erbicidal a~e~t~.

Now it has been found that the compounds of the general formula (I) suppr~ss effectively th~ phytotoxic 3ide effects of a wide variety of herbicidal agents;
Owi~g to their effective phytotoxicity-suppressing 5 activ~ty, the compounds of the general formuls (I) ma~e po~eible to utilize the herbicidally active a~ents i~
increased dosageæ without damaging the cultivated plants, which is particularly important e.g. in the treatment o~
areas heavily infe~ted with weeds. Furthermore, upon the utilization of the compounds of the general formula (I) the demages arising from inaccurate or irregular dosi~g of the herbicidally ~ctive sgents can be avoided.
The compounds of the general formula (I) can be applied onto the plants or area to be treated in an amoun~
oi 1 to 50 % b~ weight, calculated ~or the weight of the herbicidslly active agent, either prior to or æi~ultaneously wiSh the applicatio~ of the herbicidal substance. ~hus the compounds of the general formula (I) can be utilized e.g.
88 seed dressing agents, or they can be applied onto the 20 80il be~ore or after sowing, either alone or together with the herbicidally active substance. ~hs protecting effect of the compou~d~ of the general formula (I) does ~ot depen~
on the ~act how the herbicidally active substances are applied; i.e~ the herbicidally active substances can be ~pplied onto the area to be treated either before or aftar 80Wi~g (in a pr~- or post-emergent treatment), without ~nfluencing the phytotbxicity-suppressing effact ~f the ~ntidote.
Some typical representatives of the naphth31e~e-~0 oarboxylic acid derivatives of the general for~ula (I) ar~

listed in Table 1. ~his table also contain~ the physicalcons~ants o~ the compounds and the re~erences whiah describe their~preparation. ~he other repre~entatives o~ the ~ormula (I) oompound~ not li~ted in Table 1 can be prepared accord-$ag to bhe methods re$erred to in the table. ~he preparationof 80me compound~ listed in ~zble 1 i~ described in deta~l in the E~amples. -a O ~
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Based on the above, the invention relates to novel conpositions for ccmbatting weeds. m e novel compositions according to the invention con-tain at least one herbicidally active agent selected from the group consist-ing of thiolcarbamate, substituted urea, substituted triazine, chloro-aoe tanilide and uracil type compounds and 1 to 50 % by weight, calculated for the weight of the herbicidally active agent, of at least one antidote of the general formula (I), wherein X stands for hydroxy, amino, Cl 5 aIkylamino, di-(Cl 5 alkyl)-amino, Cl 5 hydroxyalkylamino or Cl 5 alkoxyalkylamino group, and Y stands for hydrogen, halogen, nitro gr~up or a Cl 5 aIkyl group, in a total amount of 10 to 90 % by weight, along with 90 to 10 % by weight of one or more conventional form~lation aids.
The herbicidally active agents to be applied in the compositions according to the invention are known per se (see "Guide to the Chemicals Used in Crop Protection"; ed. Spenoer, E.Y., Research Branch of the Depart-ment of Agriculture, Canada /1968/ and the more recent issues thereof).
The compositions according to the invention may contain as herbicidally a~tive agent one or m~re herbicides of the same type, or a mix-ture of different types of herbicides.
Of the thiolcarbamate-type herbicides usable in the compositions according to the invention S-ethyl-N,N-dipropyl-thiolcarbamate, S-ethyl-N,N-diisobutyl-thiolcarbamate, S-propyl-N,N-dipropyl-thiolcarbamate, S-(2,2,2-trichloroallyl) N,N-dipropyl-thiol~rbamate and S-ethyl-N-cyclohexylethyl-_ 9 _ ~hiolcal~bama~e are the mos~ preferred one.
~he mo~t preferred repre~entative~ of the urea-type herbicidally active agents are N-phenyl-N',N'-dimethylurea, N-(4-ahlorophenyl) N',~'-dimethylurea, N-(3,4-dichlorophe~yl)-~',N'-dimethylurea, ~-(3-chloro-4-methylphenyl)-N~,N'-di-methylurea, N-~4-bromophenyl)-~'-methoxg-~i-methylurea, N-(3,4-dichlorophenyl)-~'-methoxy.-N'-methylurea and N-(3-chloro-4-bromophe~yl)~ methoxy-N'-methylurea.
~he compo~itions according to the invention contai~
as ~riazine-type herbicide3 preferably the following compound~:
2-chloro-4,6-bi~ (ethylamino)-1,~,5-triazine, 2-chloro-4-ethylami~o-6-isopropylamino-1,3,5-triazine, 2-chloro~4,6-bis-(isopropylamino)-1,3,5-triazine, 2-chloro-4-ethylamino-6-(tert.-butylamino~ 3,5-triazine~ 2-(2-chloro-4-et~ylamino-1,~,5-triazin-6-yl-amino~-2-methyl-propionitrile, 2-me.th~l-mer~apto-4,6-bis-(isopropylamino)-1,3,5-triazine, 2-methyl-mercapto-4-ethyl~mi~o-5-isopropylamino-1,3,5-triazine, 2-methylmercapto-4-eth~lami~o-6-(tert.-butylamino)-1,3,5-tri-azine ~nd 4-ami~o-5-(tert.-butyl)-3-methylthio-1,2,4-tri-ezi~e-5-one.
Of ~he chloroaceta~ilide type herbicides usable i~
the compositio~s according to the inve~tion ~-isopropyl-2- .
chloroacetan~lide~ 2' 9 6 ' ~die t~yl-~-metho~ymeth~1-2-chloro-acetanilide, 2'-ethyl-69-methyl-~-methoxymethyl-2-chloroacet-~nilid~ s~d N-chloroacetyl-~-butoxymethylene-2',6'-diethyl-a~iline are the most preferred.
The most pxe~er~ed representetives of the uracil type herbicide~ to be used in the compo~itions accordinl~, to the i~ventio~ are 3 (~sc.-butyl)-5-bromo-6-methyluracil, cyclohexyl-5,6-trimethyle~euracil and 3-(tert.-bu~yl~-5-chloro^G-~ethylurac~
The formulation aids usable in the compositions according to the invention are additives generally applied in the preparation o~ pesticides and described in detail in numerous textbooks. ~he formulation aids may be e.g. inert carriers, diluent~, surfactants, antifoam sgents, corro3ion inhibitors, anti-caki~g agents, et~.
The compositions according to the invention can be formulated in any of the convsntional foxms of pesticides, such a~ wettable powders, emulsifyable concentrates, powder dusts, granule s, e tc.
~he invention relates further to methods for combatti~g weeds.
` According to one of the methods of the in~ention a herbicidally active amount of at least one herbicidally active age~t selacted from tha group consisting of thiol-c~rbamate~ sub~tituted urea, substituted`triazine, chioro-~cetan~llde and uracil type compounds, furthermora an e~fect-ive amount of 1 to 50 % by weight, calculated for the weight of the he:~bicidally active agent, of at least one compound of the general ~ormula (I) are applied onto the soil eiSher ~eparate~y or simultaneously, before or after sowing. In a pre~erred method both the herbicidally active agent and the antidote are applied a8 pre-formulated compositio~s.
One ma~ al~o proceed so that tha seeds of the cultivated plan~ are traated before sowing v~ith an effect-ive amou~t o~ 1 to 50 % by weight7 calculated for the ~eigh~
o~ the herbicidally active agent, of at le~st o~e antidoSe o~ th~ goneral ~ormula (I), a~d the soil is traated ~ith a herbicidally active amount of at lea~t ona herblcid311y ~ t~

active a~ent s~lected from the ~roup consisting of thiol-cnrbamalte, substituted urea, substituted triazine, chloro-ucetanilide and uracil type compounds either before or after sowing the seeds. In this l~tter instance again it i8 pre-~erred to apply both the herbicidally active agent and the entidote a~ pre-formulated compositions.
~he antidotes of the general formula (I) can be ~ormulated subskantially in the same manner as given abo~e for the compositions containing the antidote together w~h 9 h9rbicidally active agent.
Accordi~g to the method of the invention the ~
herbicidally active agent and the antidote are applied in the same ratio as given above ~or the compositions. The dosage o~ the herb~cidall~ active agent applied onto the area to be treated may be the conventional one; with regard of the protecting effect exerted by the antidobe, however~
the herbicidally activa a~ents can also be applied in do8ages higher khsn the conventional without any risk o~
damsgi~g the cultivated plant. ~he sctual dosage of the 2G herbicidally active agent i~ detarmined by ~umèrous factor8 such as the type of weeds to be combatted, the nature o~
the herbicide and antidote applied, the manner of applica-tion, waather and soil conditions, etc., it varies, howevar~
g~nerally between 1 kg/ha and 15 kg/ha.
The i~vention is elucidated in detail by the s~d o~ thc followinO non-limiti~g Examples.
Example 1 l-I~aphthalenecarboxylic acid_amide Gaseous ammonia is introduced into a stirred and cooled solution of 95.3 g (0.5 moles) o~ naphthalena-carboxylic acid chloride in 2000 ml of diethyl ether for 2 hours. This operation is performed at 0 to 5 & . Thereafter the reaction mixture is allowed to warm to room temperature, the separated substan oe is filtered off, washed with water and dried. 81.0 g (94.6 %) of l-naphthalene-carboxylic acid amide are obtained; m.p.: 203-204 C.
Analysis:
calculated: N: 8.18 %, O: 9.34 %, found: N: 8.22 %, O: 9.37 %.
Example 2 2-Naphthalene~rboxylic acid amide Gaseous am~onia is introdu oe d at 0 to 5 & . into a constantly stirred and cooled solution of 95.3 g (0.5 moles) of 2-naphthalenecarboxylic acid chloride in 2000 ml of diethyl ether. The separated substan oe is filtered off, washed with water and dried. 70 g of 2-naphthalenecarboxylic acid amide are obtained; m.p.: 192-193 & .
Analysis:
calculated: N: 8.18 %, O: 9.34 %, found: N: 8.83 %, o: 9.53 %.
Example 3 l-Naphthalenecarboxylic acid-N-(2-hydroxyethyl)-amide 13.2 g (0.22 moles) of amin oe thanol are added dropwise at 0 to 5 &
to a constantly stirred and cooled solution of 19.0 g (0.1 moles) of l-naphthalene~rboxylic acid chloride in 450 ml of diethyl ether. m e reac-tion mixture is stirred at room temperature for 3 hours. m e separated pre-cipitate is filtered off~ washed with a large amount of water and dried.
14.5 g (67.6 %) of l-naphthalenecarboxylic acid-N-(2-hydroxyethyl~-amide are obtained; m.p.: 104 C.

Analysis:
caleulated: N: 6.51~, 0: 14.86~.
found: N: 6.70$, 0: 15.01%.
E~ample 4 2-Naphthaleneearboxylie add-N-(2-hydroxyethyl)-amide 13.2 g (0.22 moles) of aminoethanol are added dropwise at 0 to 5C to a constantly stirred and ccoled solution of 19.0 g (0.1 moles) of 2-naphthalenecarkoxylie acid ehloride in 450 ml of diethyl ether. The reaetion mixture is stirred at room temperature for 3 hours. The separated precipitate is filtered off, washed with water and dried. 11.6 g (54%) of white, crystalline 2-naphthalenecarkoxylie aeid-N-(2-hydroxyethyl)-amide are obtained; m.p.: 132-134& .
Analysis:
calculated: N:6.51%, 0:14.86%, found: N:6.58%, 0:14,87%.
Example 5 Spray dust composition containing l-naphthalene earboxylie acid (eompound No. 1) 70 g of l-naphthaleneearboxylie aeid are admixed with 17 g of kaoline, 6 g of amorphous silieie aeid (Ultrasil)*, 2.5 g of fatty aleohol sulfonate and 2.5 g of powdered sulfite waste liquor, and the mixture is ground in an air jet mill. The floatability of the resulting spray dust is 95%.
Example 6 Spray dust ecmposition containing 7-methyl-2-naphthalenecarkoxylie aeid (eompound No. 9) 70 g of 7-methyl-2-naphthalenecarkoxylic acid are admixed with 17 g of kaoline 8 g of amorphous silicic acid, 2.5 g of fatty alcohol sulfonate and 2.5 g of powdered sulfite waste liquor, and the mixture is ground in an air jet mill. The floatability of the resulting spray dust is 90% .

* Trade Mark 1 l ~ 6 i ~

Example 7 Spray dust composition containing l-naphthalene-car~oxylic acid -n-propyl-amide (compound No. 5) 70 g of l-naphthalenecarboxylic acid-n-propyl-amide are admixed with 25 g of silicic acid, 2.5 g of fatty alcohol sulfonate and 2.5 g of powdered sulfite waste liquor, and the mixture is ground in an air jet mill.
The floatability of the resulting spray dust is 93%.
Example 8 Spray dust composition containing l-naphthalene-carboxylic acid (compound No. 1) and Afalon*
50 g of Afalon* (N-/3,4-dichlorophenyl/-N'~nethoxy-N'~nethylurea) are admixed with 15 g of l-naphthalenecarboxylic acid, 35 g of silicic acid, 2.5 g of fatty alcohol sulfonate and 2.5 g of powdered sulfite waste liquor, and the mixture is ground in an air jet mill. me floatability of the resulting spray dust is 95%.
The following Examples describe the tests performed to examine the phytotoxic side-effects of the compositions according to the invention and the phytotoxicity-suppressing effect of the antidotes having the general formula (I).
me herbicides utilized in the tests were as follows:
Afalon:* a herbicide containing N-(3,4-dichlorophe~yl)-N'- methoxy-N'-methylurea as active agent, produced by finn Hoechst, German Federal Republic;
Eptam:* a herbicide containing S-ethyl-N,N-dipropylthiolcarbamate as active agent, produced by the firm Stauffer Chemical Co., United States;
Sencor:* a herbicide containing 4-amino-5-(tert.-butyl)-3~nethylthio-1,2,4-triazine-5-one as active agent, produced by the firm Bayer, Germ~n Federal Republic;
Lasso:* a herbicide containing 2-chloro-2',6'-diethyl~N-methoxymethyl-acetanilide as active agent, produced by the firm Mbnsanto Cb., United States;
*Trade Mark --~. 14 -~, . ~

Venzar:* a herbicide containing 3-cyclohexyl-5,6-trimethylene-uracil as active agent, produced by the firm DuPont de Nemours Co., United States.
Example 9 The tests were performed on sunflower. In the first test series the phytotoxic side-effect on Afalon* was determined, and then the phytotoxicity-suppressing effects of the formula (I) compounds were examined.
In the ocmparative tests N,N-diallyl-2,2-dichloroacetamide, a kncwn antidote, was utilized as phytotoxicity-suppressing agent.
m e tests were performed on 10 m2 parcels in four-fold replic-ations. Afalon* was applied in the form of a wettable powder with 50%
active agent content in a dosage of 5 kg/ha. The antidotes were applied in varying dosages; the antidote-containing aqueous suspensions were sprayed onto the soil simult~neously with the spraying of Afalon*.
The parcels serving as controls in the evaluation of the damaging effects were weeded mechanically. The four-weed-old sunflowers were cut and weighed, and the green weight of the plants harvested from the treated parcels was ccmpared to that of the plants harvested from the control.

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~ h~ test re~ults li~ted in Table 2 clearly demoustrate that the composition~ according to the in~ntio~
containing Af~lon 910ng with en sntidote of the gener~l formula ~I~, exert ~ gnificantly less damaging e~ects on '~ the cultivated plant~ than Afalon alone or in co~bi~ation with the known antidote N,N~diallyl-2,2-dichloroacetsmide.
~hen ~pplying the compo~ition~ according to the inve~tion, particularly tho~e co~taining compou~d~ ~08. 1 s~d 2 as anti-dote~, the green weight o~ sun~lower approaches to tha$
obtsinsd on the control parcels of mechanical w~eding.
ExamPle L0 ~ he te~ts were performed a~ dsscribed in Example 9 with the diff~rence th~t the an~idotes were not ~prayed onto ~he ~oil, but the ~unflower ~eeds were dresssd with the a~ti- -~otes prior to ~owi~g~ and the parcels were ~p~yed after ~ow~næ with 5 kg~ha o~ Afalon (~ wettabl~ ~owder cont~i~ing 50 % of the aative agent). ~he results are swmmarizea in Table ~.

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The date o~ Table 3 clearly demonstrate that the phytotoxicity-~uppres~i~g e~fect oY the formuls (I) anti-dotes gets ev6n mora pronounced ~Ivhen appl;ying them 88 seed dressing ~genta. ~he green weight o~ the four-week-old ~un-ilower~ harvested ~rom the trested parcels was pra¢tic~ily bhe same as observed on the control parcel~ w1~h mechanical weedi~g .
Exam~le 11 ~he test~ were performed on 10 m2 parcel~ our-fold replicatio~s~ utili~ing '~eke 270" t~pe ~or~ seeds as test plant~.
ta~k mixkure o~ a ~pra~ solutio~ correspondi~g to ~ do~age of 13 1/~ o~ ~tptam 6 E (a liquid herbicide) and 0.5, 1.0 or 200 kg/h~ of the antidote wa8 sprayed onto the 15 ' parcel~ prior bo sowing.
~he ~o~r-week~ old pl~nt~ were h~rvested and weighed~
The results were evaluated by comparlng ths gree~ weiBht 4f the pla~ts har~e~ted from the treated par~el~ to thet of tbs plente hsr~eRted ~rom the control parcel~ with ~echanical w~eding. ~he re~ults are ~ummarized in ~able 4.

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_ 21 -The data o:f Table 4 indicate that the oompounds of the general ~or~ul~ (I) exert f~r more ~evourable protecting effect than the known en~idote~, i.e. 1,8-n~phtheli¢ an-bydride ~nd ~ dially1-2,2-d~hloroacet~mlde.
xsmple 12 The 8uppre89ing o~ the harmful side ef~ec~s of Ept~m W~3 exsmined i~ 3eed dre~sing tests 8~ well. In these te8t3 0.25 kg, 0.50 kg and 1.00 kg oP the 3ntidote were sppliea to drese 100 kg of co~ ~eed~. ~he ~eeds were 80W~ into percels pre-trested with 13 l/he o~ Eptam 6 ~.
~he tests wers per~ormed on 10 m2 parcels in ~ourfold repli¢ation~. ~he r~sult~ were evalu~ted ~8 described in the previou~ examples~ by oonsidering the green weight~ o~
the four-wee~-old plant~. ~he re~ults ara ~umm~rized in Table 5.

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0.
J ~ 0 v ~ I

- 2~ -The data of ~able S indicate that the harmful slde e~fects of Eptam can be ~uppres~ed pracbically to zero when dre~si~g the seeds wibh the anbidotes of the general formula ;ExamPle 13 ~he ~ests were per~ormed on soybea~, utiliæing Sencor a~ herbicide. The phytotoxicity-suppressi~g effect of the antidotes of the ge~eral ~ormula (I) was exami~ad in compari~on with the effect of two known antidotes, i.e. 1,8-~aphthalic anbydride ~nd ~ d~allyl-2,2-dichloroacetamide.
The tesbs were per~ormed on 10 m2 parcels in fourfold repll¢ations. A suspensio~ corre~po~ding to a dosag~ of 1.5 kg/ha e~ Se~cor and 1.0 kg/ha or 2.0 kg/ha of the anti-dote wa~ appliea to ~he soil after sowing. ~he results were ev~lueted a~ de~cr~bed in the previous example~, by consider-i~g the greeh wHights o~ the ~our-week-old planbs.
~he resulto are li~ted i~ Table 6.

t;~
-- 24 _ ~eW~

VW~P ~ g ~D ~D 1 I I I
~o I I 1.
~D ~ I I . I
~ I 1. , .V
~ l l l0.~1~' I I I .
~o ~ ~ g wll ~1 1 1 1 1 E~ .1 1 ~ ,.
. I ~ , '.,.
I ~1 1 I '~ ~ I
. ~ ~, , ~ N W
I ~
. ~ ~ 0 ~0 ~0 ~0~0 ~
I ~ ~1 1 ~ ~ ~ ~ ~ I t>
~rl _II tO
P. ~ ~d o o O o o :o P. i ~ It ~
I ~ ~1 o oo o o I ~
~n ~ ~ o v~ .
~ ~ ~ + ~
J:~ O I O O I o OO O O ¦ h o~ t? C,~ ~ C) C) ;~ V C) J:~
I ~ P I d d ~i d d i P
~ ~a~ O
cq c~ I t~ t~

t;l~

The data o~ ~able 6 i~dicate that bhe compo~ition~
according to the invention e~ert ~ar less harm~ul side effects on soybea~ than Sencor alo~e or in combinstion with the two known antido~e~.
Example 14 In this te~t the protecting effect o~ the formula (I) compou~ds was compared to th~t o~ 1~8-~ephthalic a~hydride e~d N,N-diall~1-2,2-dîchloroacetamidej each applied as seed dressin~ age~t~. 0.25 kg and 0.5Q kg of the antidote were applied to dress 100 kg o~ so~bea~ seeds. ~he 3eeds were 80Wn into parael~, a~d the parcels were sprayed with 1.5 kg/ha - o~ Se~cor after 80Wi~g.
~he test results.were evaluated as described i~ ~he previous examples, by oonsideri~g the gree~ weights o~ the iour week-old plantR. ~he rs~ults ar0 listed i~ Table ~.

bO
B~ l l l v; Cl ~2) --I ~ N~X) I ~ I O

t I .
~ l l l dV , ~ 1 1.
o~ ~I~D g10 ~ O ~10 C~O
$
.
~' .
~1 El . I 1. ~' 1 ~1 1 . la)~l I
~ h l ~

. I O ~ ~ ~ ~ . o ~ ~ ~ O oO I B
. 1 ~
Q. I ~ I I
I ~ _l o oo ~ I ~
~ I ,t z; I O I 'a ~ h ~ h ~ ~ h h h o I ~ ~
1~ si I ~
~ ~ ~
CQ U~

11;3t;~

The data of ~ble 7 clearly demonstrate that the harmful ~ide offe¢ts of Sencor can be suppressed even more . when the entido~es ara applied as seed dre~sing agents;
Wi~h the an~idotes ~08~ 16 and 18 the hsrm~ul side e~fects of ~encor can be suppressed practically to ~ero.
xample 15 The te ~ were performed o~ c~rrot seeds, utilizing the antidotes a~ seed dre~ing agents to suppr~ss the phyto-~oxic ~ide e~facts o~ Venz~r. In the comparative tests 1~ ~,N-diellyl-2,2-d~chloroace~amide, a k~own antidote, was ~pplied.
0025 kg and 0~50 kg o~.the antidote were ~pplied to dress lO0 kg o~ the seeds~ The parcels were ~reated with Venz~r (~ composition containing 80 % of active agent) a~tar ~owiDg.
~he tests were performed on lO m2 parcels in iour-iold replications. ~he result~ were evaluated by Go~sideri~g the graen weight~ o~ the ~our-week-old plents. ~he results ere summar.~zed i~ ~abla 80 ;8 ,'~
2~ _ q~ 1~', .' bO ~ ~ ~.
. I .
,i ~ ~ I I b6 ~ I o .
bOJ~ l l l . ba I 1. 'I ..
.1 ~ .~
d 7~ l l l . ' ~ a~,l v l ~ ~ ~1 o ., ~0 . I l l .

' . ~ ~I 'n .' lW~ I

. . ~ 0 ..

I ~ I a aD' V ~ 10 1 0 ~O tD I h D p ~~ ~ N N N I d !:~ ~ p p ~ ~ o

3~

The deta of Teble 8 clearly 1ndicate that the harm-ful side e~fects can be reduced practically to zero whcn applying the formula (I) antidotes as ~eed dre~sing agents.
The results of the tests described in EXemples 9 to 15 and summerized in ~ables 2 to 8 prove unambiguously that the an~ldote~ o~ ~he general ~ormula (I) suppres~ the h~rm~ul side e~fects of ~he known herbicides to a great ex-tent; in some instances the3e harmful side effects can be reduced to ~ ro.

Claims (10)

What we claim is:

1. An antidote-containing composition for combatting weeds, characterized by containing at least one herbicidally active agent selected from the group consisting of thiol-carbamate, substituted urea, substituted triazine, chloro-acetanilide and urecil type compounds and 1 to 50 % by weight, calculated for the weight of the herbicidally active agent, of at least one antidote of the general formula (I), wherein X stands for hydroxy, amino, C1-5 alkylamino, di-(C1-5 alkyl)-amino, C1-5 hydroxyalkylamino or C1-5 alkoxyalkylamino group, and Y stands for hydrogen, halogen, nitro group or a C1-5 alkyl group, in a total amount of 10 to 90 % by weight, along with 90 to 10 % by weight of one or more conventional formulation aids.

2. A composition as claimed in claim 1, characterized by containing as thiolcarbamate type harbicidally active agent at least one compound selected from the group consist-ing of S-ethyl-N,N-dipropyl-thiolcarbamate, S-ethyl-N,N-di-isobutyl-thiolcarbamate, S-propyl-N,N-dipropyl-thiolcarbamate, S-(2,2,2-trichloroallyl)-N,N-dipropyl-thiolcarbamaate and S-ethyl-N-cyclohexylethyl-thiolcarbamate.

3. A composition as claimed in claim 1, characterized by containing as urea type herbicidally active agent at least one compound selected from the group consisting of N-phenyl-N?N'-dimethylurea, N-(4-chlorophenyl)-N',N'-dimethyl-urea, N-(3,4-dichlorophenyl)-N',N'-dimethylurea, N-(3-chloro-4-methylphenyl)-N',N'-dimethyluree, N-(4-bromophenyl)-N'-methoxy-N'-methylurea, N-(3,4-dichlorophenyl)-N'-methoxy-N'-methylurea,and N-(3-chloro-4-bromophenyl)-N'-mebhoxy-N'-methylurea.

4. A composition as claimed in claim 1, characterized by containing as triazine type herbicidally active agent at least one compound selected from the group consisting of 2-chloro-4,6-bis-(ethylamino)-1,3,5-triazine, 2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine, 2-chloro-4,6-bis-(isopropylamino)-l,3,5-triazine, 2-chloro-4-ethylamino-6-(tert.-butylamino)-1,3,5-triazine, 2-(2-chloro-4-ethylamino-1,3,5-triazin-6-yl-amino)-2-methyl-propionitrile, 2-methyl-mercapto-4,6-bis-(isopropylamino)-1,3,5-triazine, 2-methyl-mercapto-4-ethylamino-6-isopropylamino-1,3,5-triazine, 2-methylmercapto-4-ethylamino-6-(tert.-butylamino)-1,3,5-tri-azine and 4-amino-5-(tert.-butyl)-3-methylthio-1,2,4-triazine--5-one.

5. A composition as claimed in claim 1, characterized by containing as chloroacetanilide type herbicidally active-agent at least one compound selected from the group consist-ing of N-isopropyl-2-chloroacetanilide, 2',6'-diethyl-N-methoxymethyl-2-chloroacetanilide, 2'-ethyl-6'-methyl-N-meth-oxymethyl-2-chloroacetanilide or N-chloroacetyl-N-butoxy-methylene-2',6'-diethylaniline.

6. A composition as claimed in claim 1, characterized by containing as uracil type herbicidally active agent at least one compound selected from the group consisting of - 32 _ 3-(sec.-butyl)-5-bromo-6-methyluracil, 3-cyclohexy1-5,6-tri-methyleneuracil and 3-(tert.-butyl)-5-chloro-6-methyluracil.

7. A method for combatting weeds characterized in that a herbicidally active amount of at least one herbi-cidally active agent selected from the group consisting of thiolcarbamate, substituted urea, substituted triazine, chloroacetanilide and urecil type compounds, furthermore an effective amount of 1 to 50 % by weight, calculated for the weight of the herbicidally active agent, of at least one compound of the general formula (I), wherein X stands for hydroxy, amino, C1-5 alkylamino, di-(C1-5 alkyl)-amino, C1-5 hydroxyalkylamino or C1-5 alkoxyalkylamino group, and Y stands for hydrogen, halogen, nitro group or a C1-5 alkyl group, are applied onto the soil either seperately or simultaneously, before or after sowing the seeds of the cultivated plant.

8. A method as claimed in claim 7, characterized in that both the herbicidally active agent and the antidote of the general formula (I) are applied as pre-fromulated compositions.

9. A method for combatting weeds, characterized in that the seeds of the cultivated plant are treated before sowing with an effective amount of 1 to 50% by weight, calculated for the weight of the herbicidally active agent, of at least one compound of the general formula (I), wherein X stands for hydroxy, amino, C1-5 alkylamino, di-(C1-5alkyl)- amino, C1-5 hydroxyalkylamino or C1-5 alkoxyalkylamino group, and Y stands for hydrogen, halogen, nitro group or a C1-5 alkyl group, and the soil is treated with a herbicidally active amount of at least one herbicidally active agent selected from the group consisting of thiolcarbamate, substituted urea, substituted triazine, chloroacetanilide and uracil type compounds either before or after sowing the seeds.

10. A method as claimed in claim 9, characterized in that both the herbicidally active agent and the antidote of the general formula (I) are applied as pre-formulated compositions.