LU87227A1 - HERBICIDE COMPOSITIONS CONTAINING AN ACTIVE SULFONYLUREA COMPONENT AND A GLYCINAMIDE ANTIDOTE - Google Patents

Description

ΥΧ -. _ L-3233 - - ^ - - _ _ '

/ 0 7 9 9 I 7 GRÀND-DÙCHÉ DE LUXEMBOURG

Patent No —O / ...... ws .......... ”·,. Minister of .... 26 ...... May ....... 1..9..8..8 ______________ Economy and the Middle Classes rrr j, yx · mgwffs ... Service..of Intellectual Property '

Title worked ....................... — ..................... will »LUXEMBOURG

Invention Patent Application -------------------------------------------- ----------------- (1) I. Request

Eszakmag.y.aE © E..szàgi.Lv © gyimüv © k ···, ^ C 2) presen.té.e .. ~. Par .... MQn.s.ieur ...... Jeari ...... Waxweiler., .— 5.5 „.. r..ue .... de.s ...... Br. uy.er.es .., -----------------

Howald, - „acting ....... as agent______________________________________________________________________________________ ''" ------------------------------- ---------------------------------------------------------- ---------------------------------------------------------- ---------------------------------------------------------- ----------------------------- (3) deposit) this twenty-one !! - 5ix.-inai.-mil-xieuf --cent-quatre = yijnq.U-fauiU --------------------------------------- ------- (4) at ..... 15 ..., ... 0..0 ....... hours, at the Ministry of the Economy and the Middle Classes, in Luxembourg : 1. the present request for obtaining a patent of invention concerning:

Herbicidal compositions containing an active component of the type (sulfonylurea and an antidote of the "glycinamide type 2. Description in French _______________________________________________ <je ^ invention in triplicate; '3 ................ ........ Z .----------------------------------- drawing boards, in three copies; · 4. receipt of the fees paid to the Luxembourg Registration Office, 2-6. ~ -ma.i ..... l.9.88 ____; 5. the delegation of power, dated „ .Sajôb.à.hQny ------------------------- le —1..2_JH.ai 1.9 ... 8..8—- -; 6. the successor document (authorization); declare) assuming responsibility for this declaration, that the inventor (s) is (are): (6) --------- v © 4r — appendix --------------------------------—------------- --------------------—------ claims (nt) for the above patent application the priority of one (s) application (s) of (7) ____________ patent .............................................. ......__.... filed in (8) Hungary____ l e (9) May 28, 1987 _________________; _______.

under N ° (10) __2455 / 84 _______________________: ___ — ___ — __ in the name of (11) Es.z.akmag.y.ar.or.s..zagi ..... ¥. & gy.imüv.ek ---------------- elect (elect) domicile for him / her and, if designated, for his / her representative, in Luxembourg ...... »...... ..........

55 rue des Bruyères, Howald_ '-___ (12) is requesting the grant of a patent for the invention for the subject described and represented in the abovementioned appendices, with postponement of this grant to ./—XJ--- ;-----------------month. (13)

The ^ OSSOt / agent: _______'— S ----------------- (14) Π. Deposit Minutes

The above application for a patent for invention has been filed with the Ministry of the Economy and the Middle Classes, Property Service Intdlert®IS% Luxembourg, dated: 26.05.1988 - / i% X ’^ vs.

/? 'ξΛ_. Pr. The Minister of the Economy and the Middle Classes, - at 15 ../ .. 0.0 ........... hours * ξί ’'/ ^ d.

^ \ jjj - The head of the department ^ intellectual property, _A68007 _-_ A J - _

. , EXPLANATIONS RELATING TO THE FORMULSIRBBET> EP6t. "! -. / JS ^” ~ ~ Z

H ~ ÎV \ ΛΙ venue "Request for certificate of addition to the main patent, to the main patent application No ... r ..,. / Yôii .........-.” - ( 2) enter the surname, first name, profession, / l rV address of the applicant, when the latter * is an individual hearing company name, legal form, address of the head office, when the applicant is a legal person - (3) enter the names, address of professional representative, industrial property attorney, with special powers, if there is one, represents parr ....... acting as representative ”

. % J

PRIORITY BETOICFLTIQN

Filing of the patent application in Hungary

Jy 28 May 1987 UNDER number 2455/87

DESCRIPTIVE MEMORY FILED IN SUPPORT OF A PATENT INVENTION APPLICATION IN THE GRAND DUCHY OF LUXEMBOURG

pqr * Eszakmagyarorszàgi Vegyimüvek * 3792 Sajôbâbony

Hungary po «.rj Herbicidal compositions containing an active component of sulfonylurea type and an antidote of glycinamide type.

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COHPOSITIOHS HERBICIDES COHTEHRHT UH ACTIVE COTEIPOSFIHT OF SULFOHVLUREA TVPE AND AN ANTIDOTE OF TVPE 6LVCINRI11DE

The present invention relates to herbicidal coapositions containing a derivative of formula (I):

Ri x icii H ~ (- S02— NH —C —NH - (O (l) 8 "Λ, coite coiposing herb here active and a derivative of g Iyc inaii of N-dichloroacetyl-N-substituted-N ' , Ν'-disubstituted of fonule (II): V / Cl / Nc-ch2-nc-ch ^ ai) r9 OR, 0 O ct couse antidote. These herbicidal cosposilions are very selective in crops of know and sorghum.

Since 1955 the sulfonylurea derivatives and in particular, the benzenesulfonylurea derivatives have taken on a great importance in oral anti-diabetic pods and then in anti-epiphetic pods.

Twenty years later, the herbicidal action and the action of

t I I

2 regulation of plant growth of this class of co-posed have also been recognized. Since that time, sulfonylurea derivatives have provided the most remarkable results from herbicide research. Several kinds of derivatives have been prepared and described, for example the 1,2,4-triazinyl derivatives (US-4t20691), 1,3,5-triazinyl (US-4,127,405 and 4,169,719) and the Hungarian patent applications. published under the numbers T / 35 475 and T / 39 322), pyridyle (DE-3 234 451), pyrimidinyle (US-4 339 266, Hungarian patent application published under the number T / 36 674 and HU-189 212) , pyrazoie (Hungarian patent application published under number T / 35 480), indole (Hungarian patent application published under number T / 30 918) and thiophene (Hungarian patent applications published under numbers T / 28 604, T / 30 169 and T / 30 489, as well as HU-190 675).

11 is described, in most of the literature known until now, the herbicidal action and the action of regulating the growth of plants presented by 1,3,5-triazinyl or pyrinidinyl derivatives in themselves , (HU-181 423; 181 869; 188 629; 190 702 and 191 006 as well as EP-0 071 951 and Hungarian patent applications published under the numbers T / 30 871; T / 34 167; T / 37 859 and T / 37,868), or their combinations with other active constituents such as ïso (thio) ureas (US-4,339,267), triazinediones (Hungarian patent application published under number T / 31,952) or with ureas , various carbonates, uracids, triazines, phenoxy or propi onic acid derivatives (Hungarian patent applications published under the numbers T / 39 338 and T / 41 220) have been the subject of reports.

fl Following the previous patent specifications, it is evident that sulfonylureas have an excellent herbicidal effect, mainly against a certain number of monocotyledonous or dicotyledonous weeds, in particular against broad-leaved and herbaceous weeds [J.H. Green and coII .: Proc. S. Ueed Sci. Soc. 34, 214 (1981)] and especially in wheat and barley crops (Hungarian patent application published under number T / 39 322). They are advantageous in that they

* * I

3 are active at a dose, generally as low as 5 to 50 g / hectare. Their disadvantages lie in that they exert a more or less harmful effect on cultivated plants. During practical use, it turns out that they have an acceptable selectivity for spiciferous kinds of cereals, but that they are highly phytotoxic in crops of nais and sunflower; their combination with antidotes is therefore judicious in the case of spiciferous plants and essential in the case of naïs.

EP-Q 127 169 describes antidotes which, used after senis in the pre-emergence period, can protect wheat and garlic from the harmful effects of herbicides of the sulfonylurea type. Ethyl 2 - [(aMinocarbonyl) -a & inosulfonyl] benzoate and its aiBoniuB salt, as well as 3 - [(aBinoearbonyl) -a "ethyl inosulfonyll-2-thiophene-carboxylate have been found to be very useful in this regard .

According to US-1 313 619, 1,8-naphtha-1ic acid anhydride, 1'ct- (cyanoeethoxyÎBino) benzeneacetonitrile and N, N-di-ally1-2,2-dichioroacétaiide, can be used with good results for increasing the selectivity of 2-chloro-H- [1-aethoxy-6-eethyI-1,3,5-tri az i n-2-yI) asinocarbonyI] -benzenesuI-fonaaide, of 2,5-dichloro -N- [1,6-diiethoxy-2-pyriaidinyl) -aBino-carbonyijbenzènesulfonaside and 2-carboBéthoxy-N- [1,6-dÎMéthoxy- 2-pyriMidinyl) -aMinocarbonyl3benzènesulfonaBÎde active as herbicides.

In seeking to reduce the detrimental (harmful) effects of sulfonylurea herbicides on cultivated plants, it has been noted that derivatives of glycinaeide H-dîch IoroacétyI-H-substituted-H ', H'-disubstituted of formula (II), can be used with good results to obtain protection against phytotoxicity. This observation led to the "ise to the point of the present invention, which relates to a herbicidal cosposition containing a sulfonylurea derivative of forula (I) cofiposing herbicidal pod and a glycinanide derivative N-dichioroacetyl-N-substi killed-H ', Η '- substituted formula (II) 4 with antidote.

In formula (I):

Rj is hydrogen, halogen, lower aicoyl, lower aicoxy, -NO2, -CO2R3, -CÜ-NH-OR4, -SO2-HH-OR4 or -OCF3, where R3 and R4 are groups lower alkyls; R2 is hydrogen, halogen, optionally substituted lower alkyl, lower alkoxy, -HCO, -CH, —MHCO2R5j -HHCOR5 or -HR6R7, where R5 is lower alkyl;

Rg and R7 are a hydrogen atom or a lower alkyl group; X and V, which are identical or different, represent a hydrogen or halogen atom, a lower alkyl group, lower aicoxy, lower alkylthio, a lower alkyl group or lower aicoxy substituted with one to three halogen atones, or a group -HO2 or di (lower alkyl) anino; and K represents CH or H.

In formula (II):

Rg and Rg, which are identical or different, represent a hydrogen atom, a C1-C6 alkyl group, C2-3 alkenyl, C6 cycloalkyl, benzyie or optionally substituted phenyl, or Rg and Rg, with the atone nitrogen to which they are attached, can also form a hexanethyleneinino group, provided that R9 is different from a phenyl group, when Rg is a hydrogen atom; and R10 is a C1-C6 alkyl, C2-6 alkenyl or benzyie group.

Preferred derivatives are the compounds of formula (I), in which:

Rj is a hydrogen, halogen atom, a Cj.g alkyl group, Cj_g aoxyoxy, -NO2, -CO2R3, -CO-NH-OR4, -SO2-HH-OR4 or -OCF3, where R3 and R4 are Cj_3 alkyl groups; R2 is hydrogen, halogen, C5_3 alkyl group optionally substituted with 1 to 3 halogen, Cj_3 alkoxy, -HCO, -CM, -NHCO2R5, -NHCOR5 or -NR5R7, where R5 is a C1-C6 alkyl group;

Rg and Ry are a hydrogen atom or a Ct_3i alkyl group X and V, which are identical or different, represent a hydrogen atom, halogen, a Cj_alkyl group, Cj_3 alkoxy, Cj.g, a Cj_3 alkyl or Cj_3 alkoxy group substituted by one to three halogen atoms, or an -HO2 or di (Cj.galkyl) anino group; and K represents CH or H.

Preferred formulas of formula (II) are those in which:

Rg and Rg, which are identical or different, represent a hydrogen atom, a Cj_g alkyl group, C2_g alkenyl, cycIoaIcoyIe in 05.5, benzyIe or phenyIe possibly ue11enent substituted by one or two Cj_3 alkyl groups and / or atones d halogen, or Rg and Rg, with the nitrogen atom to which they are attached, can also form a hexanethyleneinino group, provided that Rg is different from a phenyl group, when Rg is a hydrogen atom; and R10 is a Cjoy alkyl, C 2.5 alkenyl or benzyl group.

The compounds may contain fluorine, chlorine, brone or iodine or halogen conne.

The herb i c i compositions of the present invention contain the formulas of formula (I) and (II) in a total amount of 5 to 95 * in net, according to a weight ratio of between 1:20 and 1: 350.

The formulas (II) which can very advantageously be used as antidotes, are listed in Table I.

s 6

TABLE I

Constituted Substant

Ho. _

Ag Ag Ajq 1 phenyl ethyl nethyl 2 phenyl ethyl ethyl 3 phenyl ethyl n-propyl 1 phenyl ethyl isopropyl 5 phenyl ethyl allyl 6 phenyl ethyl n-butyl 7 phenyl ethyl sec-butyl 8 phenyl ethyl iso-butyl 9 phenyl ethyl ter- butyl 10 allyl allyl nethyl 11 allyl allyl ethyl 12 allyl allyl allyl 13 ethyl ethyl allyl 14 isobutyl isobutyl ethyl 15 nethyl nethyl n-propyl 16 nethyl nethyl iso-propyl 17 nethyl nethyl allyl 18 nethyl nethyl ethyl ethyl ethyl 19 ethyl iso-propyl 21 ethyl ethyl ethyl 22 cyclohexyl ethyl ethyl 23 phenyl n-propyl ethyl 24 allyl H allyl 25 n-propyl n-propyl allyl 26 cyclohexyl H allyl 27 phenyl n-propyl allyl 28 2,6-dinethyl nethyl ethyl 29 2, 6-diethyl nethyl ethyl 7 TABLE I (continued)

Substituents Compound

Ho. _

Rg Rg R10 30 hexaeethylene ethyl 31 3-chlopophenyl methyl ethyl 32 ethyl ethyl n-butyl 33 ethyl ethyl iso-butyl 34 ethyl ethyl sec-butyl 35 ethyl ethyl ter-butyl 36 phenyl »ethyl ethyl 37 phenyl» ethyl n-propyl 38 phenyl methyl allyl 39 phenyl isopropyl ethyl 40 phenyl isopropyl allyl 41 »ethyl H» ethyl 42 ethyl H ethyl 43 n-propyl H n-propyl 44 isopropyl H isopropyl 45 n-butyl H n-butyl 46 isobutyl H isobutyl 47 sec-butyl H dry -butyl 48 benzyl H benzyl 49 n-propyl n-propyl allyl 50 phenyl methyl methyl 51 phenyl "ethyl isopropyl 52 2,6-di" ethyl "ethyl" ethyl 53 2,6-di "ethyl" ethyl allyl 54 2.6 -diethyl »ethyl» ethyl 55 2,6-diethyl methyl allyl 56 allyl H n-butyl 57 allyl H iso-butyl 58 allyl H iso-propyl 8 TRBLERU I (end)

Constituted Substitutes

No. _ h Rg R ^ o 59 allyie H n-propyle 60 allyie H ethyl

These antidotes, as well as the process for their preparation and their use for reducing the phytotoxicity of herbicides of the thioicarbonate and chloroacetanide type, have been described in the Hungarian patent application published under number T / 35 471.

In order to protect plants in practice, the herbicidal compositions according to the invention can be used in the form of a reliable enulsi concentrate (CE), a nebulized powder (PU), a granule (G), as well as '' an aqueous or oily suspension.

The preparation of these compositions is illustrated in detail in the following non-illustrative examples.

EHEHPLE 1

Preparation of a labile noodle powder (PII 32.1) G, 1 * by weight of 1- (2-carbonethoxybenzenesulfonyD- 3- (4-nethyl-6-nethoxy-1,3,5-triazin-2-yl) urea in as an active herbicide component, 32% by weight of No. 41 in Table I as an antidote as well as 29% by weight of a synthetic silicate support (Zeolex 444), 28.9% by weight of a soil support diatomaceous earth, 2 * by weight of an aliphatic sodium sulfonate as a netting agent (Netzer IS), and also 3 * by weight of a condensation product of phenol-fornaldehyde (Oispergiernittel 1494) and 5 * by weight of powder of sulfite liquor as dispersing agents, 3 are homogenized and pre-ground in a noulin with 9 laboratory balls, then ground into fine particles with a Rlpine 100 LU type UItropIex grinder, to give a yes I labié powder containing the active component and the antidote in a total amount of 32, IX by weight, in a ratio of 1: 320 (in the order above).

Buoyancy: 83X at a concentration of IX.

Residue of tanis huai from (on a tanis DIN 100): 1.2X.

EXAMPLE 2

Preparation of an ooudre ”yes I labiated (ΡΠ 10.5) Û, 5X by weight of chloreulfuron, [1- (2-chlorophenyl-suIfonyI) -3- (4-nethyI-6-nethoxy-1,3,5-tr i az i n-2-yI) urea], as an active herbicide component, 40X by weight of the compound Ho. 41 of Table I as an antidote as well as 15X by weight of Zeolex 444 and 35X by weight of diatomaceous earth cosne supports, 3X by weight of Dispergiernittel 1494 as a dispersing agent, 2X by weight of Netzer IS as a soiling agent and 4.5X by weight of sulphite liquor powder, are homogenized and ground into fine particles according to the procedure which is described in exenple 1 to give a nouillabié powder containing the active component and the antidote in a total amount of 40.5X by weight, in a ratio of 1: 80.

EXAMPLE 3

Preparation of a nouillabié powder (PM 64.4) Û, 4X by weight of 1- (2-earbosethoxybenzenesulfonyl) -3- (4,6-dinethyl-2-pyriaidinyDuration as active herbicide component, 64X by weight of Ho compound. 60 of Table I as an antidote, 10X by weight of Zeolex 444 and ÎXX by weight of diatomaceous earth as carrier, 2X by weight of Hetzer 15 pod as a soiling agent as well as 3X by weight of Dispergiersittei 1494 and 4.6X by weight of powder of sulfite liquor as dispersing agents, are homogenized and ground into fine particles according to the procedure which is described in Example 1 to give a powder coated with the co-active ingredient and the antidote in a total amount of 64.4X by weight , at a ratio of 1: 160.

10 EXAMPLE 4

Preparation of an ewulsifiable concentrate (EC 18.3) 0.3¾ by weight of chiorsulfuron coaae coaposing active herbicide and 48¾ by weight of coapose No. 24 of Table I antidote coaae, are dissolved with stirring in a mixture containing 33.7¾ in weight of xylene and 10¾ by weight of diiethylfomaaide. With the addition of 6.5¾ by weight of EauIsogen IP-400 and 1.5¾ by weight of EauIsogen EL-40Û (a mixture of caicid docecyibenzenesulfonate and a fatty acid polygiycoi ester) coaae emulsifying agents, the solution is filtered to provide an aerosolizable concentrate containing the active coaposing agent and the antidote in a total amount of 48.3% by weight, in a ratio of 1; 160.

The stability of this coaposition at a concentration of 1¾ is excellent in water (CIPRC R and Cl PRO D) after two hours, while it is still good with foraation of ainiaua crea (gel) and reversible after a period of 24 hours.

EXAMPLE 5

Preparation of a reliable aerosolized concentrate (PII 80.25) 0.25¾ by weight of 1- (2-carboaethoxybenzenesulfonyl) -3- (4,6-dieethyl-2-pyriaidinyl) urea coaae coaposing active herbicide and 80¾ by weight of coapose No 43 of Table I, coaae antidote, are dissolved with stirring in a mixture containing 8% by weight of xylene and 3.75% by weight of diaethylforaamide. After the addition of 6¾ of EauIsogen IP-400 and 2¾ by weight of EauIsogen EL-40Q coaae agent aulsifiers, the solution is filtered to give a concentric rewarming agent containing the active co-agent and the antidote in one total amount of 80.25% by weight, in a ratio of 1 to 320.

EXAMPLE 6

Preparation of an aerosol concentrate (PM 61.5) 1.5¾ by weight of 1- (2-carboaethoxybenzenesulfonyl) -3- (4-aethyl-6-aethoxy-1,3,5-triazin-2-yl) urea coaae coaposing 11 active herbicide and 60% by weight of coapose Ho. 59 of Table i coaae antidote, are dissolved with stirring in a mixture containing 20X by weight of xylene and 10.5X by weight of diaethylforaaeide. After addition of 7X of EauIsogen IP-400 and IX by weight of EauIsogen EL-400 coaae emulsifying agents, the solution is filtered to give a waterable concentrate containing the active component and the antidote in a total amount of 61.5X by weight, in a ratio of 1:40.

EXAMPLE 7

Preparation of a suspension (S 71.75) 1.75X by weight of 1- (2-carboaethoxybenzenesulfonyi) -3- (4,6-disethyI-2-pyriaidinyDuration coaae active herbicidal component, 70X by weight of co-compound Ho. 60 of the Table I coaae antidote and IX by weight of Zeolex 444 coaae support, are homoogenized and pre-ground in a laboratory ball mill. The pulverulent mixture obtained is bis in suspension with stirring, in an mixture containing 5X of ethylene glycol, IX in weight of oleylaethyltauride (powder Rnkopon T) coaae netting agent, 4X by weight of ether poIygIycoIi that of nonyIphenoI (RrkopoI N-09Q) coaae dispersing agent and 11.25X of water, then ground into fine particles in a ball mill After separation of the charge, 6X by weight of thickened health solution with 2X of xanthan resin (Rhodopol 23) are added and hoaogenized by stirring to obtain a suspension containing the active co-depositor and the antidote in a total amount of 71.5X by weight, in a ratio of 1:40.

Buoyancy: 94.6X at IX concentration.

EKEHFLE 8

Preparation of a suspension (5 40.5) Û, 5X by weight of chiorsulfuron coaae coaposing active herbicide, 40X by weight of coaposed Ho. 41 of Table I coaae antidote and 5X by weight of Zeolex 444 coaie support are homogenized and pre-ground in a laboratory ball mill. The pulverulent mixture obtained is suspended in a mixture 12 containing 10% ethylene glycol, 2.5% by weight of firkopon T horn wetting agent, 5.51 by weight of Rkopol N-090 conse dispersant agent and 28 , 5% water, then ground into fine particles in a laboratory ball mill. After separation of the charge, 8.5% by weight of thickened health solution containing 2% of xanthan resin are added and hoaogenized by stirring to obtain a suspension containing the active constituent and the antidote in a total amount of 40.5% by weight, in a ratio of 1; 80.

EffilBELLi

Preparation of a suspension (S 16.1) 0.1% by weight of 1- (2-earboBethoxybenzenesulfonyl) -3- (4-nethyl-6-nethoxy-1,3,5-trlazin-2-yl) urea, 16¾ by weight of the coipose Ho. 24 of Table I and 10¾ by weight of Zeolex 444 counsel support, are homoogenized and pre-ground in a laboratory Boulin. The powder mixture obtained is suspended with stirring, in a mixture containing 15% ethylene glycol, 3% by weight of Rkopon T as a wetting agent, ÔX by weight of Rkopol H-090 as a dispersing agent and 39.9X of water, then crushed into fine particles in a laboratory ball mill. After separation of the charge, 10% by weight of a thickened solution containing 2% xanthan resin are added and homogenized by stirring, to obtain a suspension containing the active component and the antidote in a total amount of 16.1% by weight , according to a ratio of 1 to 160.

The biological activity of the compositions according to the present invention is shown in the following examples.

EXAMPLE 10

A laboratory study was carried out as follows.

400 g portions of soil were weighed and placed in culture flasks having an area of 0.8 dn ^ coated with PUC sheet. This upper chang soil had a hardness (inperneability) of 46, a hunus content of 1.95% and a pH of 5.7. We senna in each of these soils, 5 grains of naïs Pi 3732, 20 grains of sorghum fllfôid-1 and 0.5 g / pot of carnation. Each se> is has been covered with 200 g of self. The herbicidal component, chlorsulfuron, alone was sprayed on the soil in an amount of 5 g / hectare (g / ha) or 10 g / ha, respectively, as well as in co-combinations with co-poses No. 21, 11, 13, 59 or 60 of Table I antidote terminal in an amount of 0.4, 0.8 or 1.6 kg / ha, respectively. In the study, we measured the green cup or the length of the shoots of cultivated plants for H days; the results of four tests are summarized in Tables II and III.

For comparison, untreated plants and on the other hand, a preparation prepared with H, M-di allyl-2,2-dichloroacetamide (Code No. R-25788), were used.

TABLE II

Haïs Sorgho Ni Met Nais

Treatment green cup green cup long green cup, shoots g / plant g / pot g / pot ct / plant Untreated control 2.0 2.0 0.5 12

Chlorsulfuron 5 g / ha 0.8 2.5 0.5 22

Chlorsulfuron 5 g / ha + I / 24 * 0.4 g / ha 1.4 2.6 0.6 35 0.8 g / ha 1.7 2.0 0.0 33 1.6 g / ha 1.7 1 , 6 0.0 3?

Chlorsulfuron 5 g / ha + 1/41 * 0.4 g / ha 1.1 1.7 0.2 28 0.8 g / ha 1.5 2.8 0.0 37 1.6 g / ha 1.0 1 , 4 0.0 30 i t1aï3 Sorgho Millet Haïs

Treatment green mass green basket long green cup, shoots g / plant g / pot g / pot cs / plant 14 t i

'J

Chlor3ulfuron 5 g / ha + 1/43 * 0.4 g / ha 1.0 1.8 0.0 22 0.8 g / ha 1.1 2.6 0.8 25 1.6 g / ha 1.5 2 , 4 0.2 31

Chlorsui furon 5 g / ha + 1/59 * 0.4 g / ha 1.2 2.0 0.0 25 0.8 g / ha 1.1 1.8 0.2 2? 1.6 g / ha 1.0 2.3 0.9 38

Chlor3uJ furon 5 g / ha + 1/60 * 0.4 g / ha 1.3 1.9 0.9 28 0.8 g / ha 1.7 1.9 0.7 30 1.6 g / ha 2.0 2.1 1.5 35

Chlorsuifuron 5 g / ha + R-25788 0.4 g / ha 1.0 2.5 0.0 22 0.8 g / ha 1.2 2.5 0.0 26 1.6 g / ha 0.9 1, 5 0.0 24 * Island of abbreviation used here and thereafter: 1/41 * compound Ho. 41 of Table I (etc.).

TABLE 111

Haïs Sorgho ilï 11 and Haïs

Treatment green mass green basket long green mass, shoots g / plant g / pot g / pot cm / plant Untreated control 2.0 2.0 0.5 42

Chlorsuifuron 10 g / ha 0.7 1.3 0.4 17

Haïs Sorghum flΐ i Iet Haïs

Treatment »033e green basket green basket green uerte long, shoots g / pIant g / pot g / pot cn / pIant 15

Chlorsulfuron 10 g / ha + 1/24 * 0.4 g / ha 1.3 3.0 0.7 30 0.8 g / ha 1.0 2.3 0.0 28 1.6 g / ha 1.0 1 , 4 0.0 28

Chlorsulfuron 10 g / ha + 1/41 * 0.4 g / ha 1.0 1.6 0.0 23 0.8 g / ha 1.4 2.7 0.0 29 1.6 g / ha 0.8 1 , 3 0.0 24

Ch IorsuIfuron 10 g / ha + 1/43 * 0.4 g / ha 0.8 1.6 0.0 20 0.8 g / ha 1.0 2.4 0.6 24 1.6 g / ha 1.4 2.2 0.0 30

Chlorsulfuron 10 g / ha + 1/59 * 0.4 g / ha 1.0 1.8 0.1 23 0.8 g / ha 0.8 1.3 0.0 20 1.6 g / ha 0.9 2 , 2 1.0 24

Chlorsulfuron 10 g / ha + 1/60 * 0.4 g / ha 0.9 1.7 0.8 24 0.8 g / ha 1.5 1.7 0.5 31 1.6 g / ha 1.2 1 .9 1.2 32

Chlorsulfuron 10 g / ha + R — 25788 0.4 g / ha 1.2 2.0 0.6 26 0.8 g / ha 1.0 1.6 0.0 28 1.6 g / ha 1.4 1, 8 1.0 31 it is evident from the results shown in Tables II and III that the co-positions according to the present invention which contain chlorsulfuron as a constituent 16 active herbicide of forula (i) with a derivative of N-dichloroacetyl-N-substituted-N ^ N'-disubstituted glycine glycoside (li) coaae antidote according to a coaprie ratio between 1: 40 and 1: 320, led to obtaining healthy sorghum and aaïs and exeapts of syaptoae, while chlorsuifuron used as such (alone) damaged these two plants at both doses.

EHEIIPLE 11 The study described in exeaple 10 was carried out with 1- (2-carboaét hoxybenzènesuIfonyI) -3- (4-aét hyI-6-aét hoxy- 1,3,5-triazin-2-ylJurée in place of chlorsulfuron, conse active ingredient herbicide.

The results of these measurements are collated in Tables IU and U, in which the active coaposant is indicated by the Code Ho. OH-3.

UI TABLE

Haïs Sorghum Hillet Haïs

Green mass treatment Low green Long green low, shoots g / plant g / pot g / pot cm / plant Untreated control 2.0 2.0 0.5 42 OH-3 5 g / ha 0.8 1.3 1 , 3 24 OH-3 5 g / ha + 1/24 * 0.4 g / ha 0.9 1.2 0.5 29 0.8 g / ha 1.2 1.4 2.3 35 1.6 g / ha 1.0 2.5 0.8 30 OH-3 5 g / ha + 1/41 * 0.4 g / ha 0.9 1.1 1.3 29 0.8 g / ha 0.9 2, 1 1.4 33 1.6 g / ha 1.0 1.5 1.2 29

Hats Sorghum fli Met fiais

Treatment mass mass mass mass long, shoots g / plant g / pot g / pot cm / plant 17 ÛH-3 5 g / ha + 1/59 * 0.4 g / ha 0.9 1.1 1.9 29 0.8 g / ha 0.7 2.1 1.3 26 1.6 g / ha 0.8 1.4 1.4 29 OH-3 5 g / ha + 1/60 * 0.4 g / ha 1 , 2 1.1 0.8 31 0.8 g / ha 0.9 1.1 1.0 30 1.6 g / ha 0.9 1.5 0.5 29 OH-3 5 g / ha + R-25788 0.4 g / ha 1.0 1.4 1.3 28 0.8 g / ha 1.3 1.4 1.1 30 1.6 g / ha 1.3 1.5 1.0 36

TABLE U

ye Sorghum Millet ye

Treatment mass uert mass uert masee uerte long, shoots g / plant g / pot g / pot cm / plant Control not treated 2.0 2.0 0.5 42 OH-3 10 g / ha 0.8 1.8 0 , 1 20 OH-3 10 g / ha + 1/24 * 0.4 g / ha 1.0 2.7 0.0 30 0.8 g / ha 0.9 2.0 0.0 28 1.6 g / ha 1.7 1.0 0.0 37 OH-3 10 g / ha + 1/41 * 0.4 g / ha 1.1 1.4 0.4 24 0.8 g / ha 1.2 1, 4 1.0 31 1.6 g / ha 1.1 1.7 1.5 28 fiais Sorgho Millet Haïs

Treatment mass green mass long mass green, shoots g / plant g / pot g / pot cm / plant 18 OH-3 10 g / ha + 1/43 * 0.4 g / ha 1.0 1.8 0.5 26 0.8 g / ha 0.9 1.5 0.4 25 1.6 g / ha 0.8 1.1 0.7 19 ÛH-3 10 g / ha + 1/59 * 0.4 g / ha 0 .9 1.2 1.2 27 0.8 g / ha 1.2 1.4 0.8 29 1.6 g / ha 1.0 1.3 0.9 27 OH-3 10 g / ha + 1/60 * 0.4 g / ha 1.1 2.4 0.0 30 0.8 g / ha 0.7 1.7 1.0 24 1.6 g / ha 1.2 1.6 1.0 32 OH-3 10 g / ha + R-25788 0.4 g / ha 0.7 1.3 1.0 24 0.8 g / ha 1.0 2.0 1.6 28 1.6 g / ha 1.2 1.4 0.4 30

It is clearly seen from the data in Tables IU and U, that using the antidotes of the N-dichloroacetyl-N-substituted-N ', Ν'-disubstituted glycinaeide type of formula (II) with the 1- (2-carbomet hoxybenzènesuIfonyI) -3- (4-sethyI-6-met hoxy-1,3,5-triazin-2-yDuration according to formula (I) as active herbicidal component in a ratio between 40: 1 and 320: 1, we may prevent the harmful effect exerted by the active component on cultivated plants. The effect of these antidotes is similar or in several cases, even greater than that of the antidote corresponding to Code No. R-25788 suggested in US-4 343,649 to serve as an antidote to sulfonylurea herbicides.

19 EKEfIPLE 12 The study described in Example 10 was carried out with 1- (2-carbomethoxybenzenesulfonyl) -3- (4,6-dimethyl-2-pyrimidi-nyDuration in place of the known chlorsulfuron active herbicidal component. The results of these measurements are collated in Tables U1 and UH, in which the active component is simply indicated by Code No. QH-4.

TRBLERU Ul fiais Sorgho Millet fiais

Treatment green mass green mass long green mass, shoots g / plant g / pot g / pot cm / plant Untreated control 2.0 2.0 0.5 42 OH-4 5 g / ha 0.7 0.8 0 .9 21 OH-4 5 g / ha + 1/24 * 0.4 g / ha 0.9 1.1 1.3 22 0.8 g / ha 0.9 0.8 0.0 21 1.6 g / ha 0.8 0.9 0.9 18 OH-4 5 g / ha + 1/41 * 0.4 g / ha 0.7 1.2 1.0 17 0.8 g / ha 0.8 1, 0 0.4 23 1.6 g / ha 0.9 1.1 0.4 14 OH-4 5 g / ha + 1/43 * 0.4 g / ha 0.8 0.8 0.0 19 0.8 g / ha 0.7 1.3 0.6 20 1.6 g / ha 1.1 0.7 0.7 24 ÛH-4 5 g / ha + 1/59 * 0.4 g / ha 1.1 1, 6 0.8 20 0.8 g / ha 1.1 0.7 0.5 26 1.6 g / ha 0.6 1.1 0.3 14 hats Sorghum hillet hats

Trash net uert trap uerte basket uerte long, shoots g / plant g / pot g / pot cn / plant 20 OH-4 5 g / ha + 1/60 * 0.4 g / ha 0.8 1.3 0.0 20 0.8 g / ha 0.8 1.5 0.5 19 1.6 g / ha 1.1 1.0 0.7 23 OH-4 5 g / ha + R-25788 0.4 g / ha 0, 7 0.7 0.9 21 0.8 g / ha 0.3 1.4 0.7 26 1.6 g / ha 0.5 1.6 1.1 20 TABLE Ull hated Sorghum hillet hated

Treat green mass green basket green green basket long, shoots g / plant g / pot g / pot cn / plant Untreated control 2.0 2.0 0.5 42 OH-4 10 g / ha 0.6 0.7 0 .5 15 OH-4 10 g / ha + 1/24 * 0.4 g / ha 0.8 0.5 0.3 18 0.8 g / ha 0.6 0.5 0.2 13 1.6 g / ha 0.7 1.1 0.0 11 OH-4 10 g / ha + 1/41 * 0.4 g / ha 0.6 0.2 0.4 15 0.8 g / ha 0.4 0, 1 0.2 10 1.6 g / ha 0.5 0.0 0.4 12 OH-4 10 g / ha + 1/43 * 0.4 g / ha 0.8 0.6 0.4 18 0.8 g / ha 0.3 0.0 0.6 6 1.6 g / ha 0.6 0.4 0.7 16 *

Haïs Sorghum Hillet Haïs

Treat nasse uerte nasse uerle nasse uerte long. for g / plant g / pot g / pot cn / plant ♦ 21 ÛH-4 10 g / ha + 1/59 * 0.4 g / ha 0.5 0.3 0.5 11 0.8 g / ha 0 0.2 0.1 0.3 5 1.6 g / ha 0.3 0.3 0.4 11 OH-4 10 g / ha + 1/60 * 0.4 g / ha 0.2 0.3 0.2 7 0.8 g / ha 0.5 0.6 0.4 11 1.6 g / ha 0.3 0.5 0.3 8 OH-4 10 g / ha + R-25788 0.4 g / ha 0, 5 0.4 0.6 12 0.8 g / ha 0.4 0.7 0.2 8 1.6 g / ha 0.5 0.2 0.4 13

It is clear from the data in Table U1 that using the glycinanide antidotes H-dich IoroacétyI-H-substituted-H ', H * -d isubstituted of formula (II) with 1- (2-carbonethoxybenzenesulfonyl) ) -3- (4,6-dinethyl-2-pyrisi-dinyU-urea pod active herbicide component in a ratio of between 40 i 1 and 320: 1, we can prevent the harmful effect exerted by this active component on plants cultivated.

In addition, it can be seen from the data in Table UN, that a dose of 10 g / ha of 1- (2-carbonethoxybenzene-sulfonyl) -3- (4,6-dinethyl-2-pyrinidinyl) urea is a herbicide component active, induces a powerful harmful effect on the crops of naïs and sorghum which cannot be enough sound enêpé nêne with the antidote Ho. R-25788 largenent known and employed. A slightly better result can be obtained by using the compositions according to the present invention which contain the antidotes of formula (II).

Claims (3)

1. Herbicidal compositions containing an active herbicidal component of sulfonylurea type and an antidote of glycinamide type, which comprises a sulfonylurea derivative of formula (I) X R2 ~ '' £ ^ L- so2— nh— c— nh— (dv (, ) ON "\ Y in i aque11e R | is a hydrogen atom, halogen, lower alkyl, lower alkoxy, -HO2, -CQ2R3, -CO-NH-OR4, -SO2-HH-OR4 or - OCF3, where R3 and R4 are lower alkyl groups] FÎ2 is a hydrogen, halogen atom, an optionally substituted lower alkyl group, lower alkoxy, -HCO, -CN, -NHC02R5, -NHCOR5 or -NR6R7, where Rg is a lower alkyl group; Rg and R7 are a hydrogen atom or a lower alkyl group; X and V, which are the same or different, represent a hydrogen, halogen atom, a lower alkyl group, lower alkoxy , lower alkyl, a lower alkyl or lower alkoxy group substituted by one to three halogen atoms, or an “NO2 or di (lower alkyl) amino group, and K repr has CH or H, as active herbicidal component and an N-dichloroacetic-N-substituted-N ', N'-disubstituted glycinamide derivative of formula (II): R8 \ XI / NC-CH2-NC-CHr (II) R9 0 R10 O c> 1t 23 in which Rg and Rg, which are identical or different, represent a hydrogen atom, a Cj_g alkyl group, C2_g alkenyl, cycIoaIcoyIe en, benzyIe or optionally substituted phenyl, or Rg and Rg, with the nitrogen atom to which they are attached, can also form a hexanethyieneinino group, provided that Rg is different from a phenyl group, when Rg is a hydrogen atom; and Rjq is a Cj.g alkyl group, C2_s alkenyl or benzyl group, antidote conne. 2. The herbicidal composition according to claim 1, which comprises a sulfonylurea derivative of formula (I), in which: R | is a hydrogen atom, halogen a Cj_3 alkyl, Cj_3 alkoxy, -HO2, “CQ2R3, -CO-HH-OR4, -S02 ~ NH-0R ^ or -OCF3, where R3 and R ^ are Cj_3 alkyl groups; R2 is a hydrogen, halogen atone, a Cj_3 alkyl group optionally substituted by 1 to 3 halogen, Cj.g alkoxy, -NCO, -CH, -NHCQ2R5, -NHCOR5 or -NRgRf, where Rg is a C 1-6 alkyl group Rg and R7 are a hydrogen atom or a Cj_3 alkyl group; X and Y, which are the same or different, represent a hydrogen or halogen atom, a Cj.g3 alkoxy group, Cj_3 alkoxy group, Cj_3 alkyl group, a Cj_3 alkyl group or Cj_3 alkoxy group substituted by one to three halogen halves, or an -NO2 or di (C1-C6 alkyl) anino group; and K represents CH or H, conne constituting active herbicide and a derivative of glycinanide N-dichIoroacétyI-H-substituted-H ', H'-disubstituted of formula (II): in IaqueIIe Rg and Rg, which are identical or different, represent a hydrogen atom, a C 1 -C 6 alkyl group, C 2 -C 6 alkenyl, C 6 -C cycoylc, benzyIe or phenyIe possibly ue11enent substituted by one or two C 1 -C 6 alkyl groups and / or * 24 halogen atones, or R 6 and R 6 , with the nitrogen atom to which they are attached, can also form a hexanethyleneinino group, provided that Rg is different from a phenyl group, when Rg is a hydrogen atom; and R10 is a C1-5 alkyl, C2-5 alkenyl or benzyl group, as an antidote. 3. Herbicidal composition according to claim 1, which comprises the compounds of formulas (I) and (II) in a total amount of 5 to 95X by weight, in a ratio of between 1:20 and 1: 350.