GB2205241A

GB2205241A - Herbicide compositions containing a sulfonylurea type active ingredient and a glycinamide type antidote

Info

Publication number: GB2205241A
Application number: GB08812701A
Authority: GB
Inventors: Karoly Balogh; Angela Bartfai; Zsolt Dombay; Erzsebet Grega; Erno Lorik; Erzsebet Mile; Istvan Nagy; Jozsef Nagy; Csaba Pavliscsak; Karoly Pasztor; Agnes Szabo; Gyula Tarpai; Istvan Toth; Eszter Urszin
Original assignee: Eszakmagyarorszgi Vegyimuvek
Current assignee: Eszakmagyarorszgi Vegyimuvek
Priority date: 1987-05-28
Filing date: 1988-05-27
Publication date: 1988-12-07
Anticipated expiration: 2008-05-27
Also published as: PT87607B; PL272728A1; GR1000144B; CS274430B2; DK291788A; IT1218022B; CS363188A2; HUT46993A; DK291788D0; DD272592A1; GB8812701D0; FR2615694A1; GR880100353A; BE1002454A5; ES2009199A6; RO100368B1; NL8801373A; IT8820792A0; PT87607A; HU201445B

Description

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2205241 HERBICIDE COMPOSITIONS CONTAINING A SULFONYLUREA TYPE ACTIVE INGREDIENT AND A GLYCINAMIDE TYPE ANTIDOTE This invention relates to herbicide compositions containing a sulfonylurea derivative of formula (I) (I) as herbicidally active ingredient and an N-dichloroacetyl-N-substituted- N',N'-disubstituted glycinamide derivative of formula (II) (II) as antidote. This herbicide compositions are very selectively effective in maize and sorghum cultures.

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Since 1955, sulfonylurea derivatives and particular- ly the benzenesulfonylurea derivatives gained a high importance as oral antidiabetics and later as antiepileptics.

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Twenty years later, the herbicidal and the plant growth regulating action of this compound class were also recognized. Since that time, sulfonylurea derivatives became the most prominent results of the herbicide research. Several kinds of derivatives have been prepared and described, e.g. 1,2,4-triazinyl (US-PS 4,120,61), 1,3,5-triazinyl (US-PS 4,127,405; 4,169,715 and Hungarian patent applications published under the numbers T/35,475 and T/39,322), pyridyl (OE-0S 3,234,451), pyrimidinyl (US-PS 4,339,266, Hungarian patent application published under the number T/36,674 and HU-PS 185,212), pyrazole (Hungarian patent application published under the number T/35,480), indole (Hungarian patent application published under the number T/30,18) and thiophene (Hungarian patent applicationspublished under the numbers T/28,604; T/30, 169 and T/30,489 as well as HU-PS 190,675) derivatives.

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In the most part of the literature known up to now the herbicidal and plant growth regulating action of 1,3,5-triazinyl or pyrimidinyl derivatives as such have been described (HU-PS 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 1/30,871; T/34,167; T/37,B59 and T/37,868) or the combinations thereof with other active ingredients such as iso(thio)ureas (US-PS 4,339,267), triazinediones (Hungarian patent epplicatio published under te number T/31,952) or with the most var ureas, carbamates, uracils, triazines, phenoxy or propionic acid derivatives (Hungarian patent applications published under the number T/39,338 and T/41,220) have been reported.

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It is evident from these patent specifications that sulfonylureas possess an excellent herbicidal eflect, first of all against a number of monocotyledonous or dicotyledonous weeds, particularly against broad-leaf and grassy weeds -0. M. Green at al.: Proc. S. Weed Sci. $oc. 34, 214 (19817 and particularly in wheat and barley cultures (Hungarian patent application published under the number T/39,322). Their advantage consists in that they are active in a dose, usually as low as 5 to 50 g/hectare. Their disadvan age appears in their more or less harmful effect on the cultivated plants. During the practical use they proved to show an acceptable selectivity for spicierous sorts of cereals but to be strongly phytotoxic in maize and sunflower cultures; thus, their combination with antidotes, in case of spiciferous plants, is advisable, and in case of maize, is essential.

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In EP 0,127,46 antidotes have been described which, when used post sowing in the pre-emergent period, can protect the wheat and millet from the harmful effects of he sulfonylurea type herbicides. Methyl 2-(aminocarbonyl)aminosulfonyTbenzoate and its ammonium salt'as well as methyl 3--(aminocarbonyl)aminosulfony7-2-thiophenecarboxylate proved to be most useful for this purpose.

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According to US-PS 4,343,649 1,8,naphhalic acid anhydride, alpha(cyanomethoxyimino)benzeneacetonitril and N,N-diallyl-2,2-dichloroacetamide can be employed with good resu3ts for enhancing the selectivity of the herbicidally active 2-chloro-N--(4methoxy-6-methyl-l,3,5-triazin-2-yl)aminocarbonyTbenzenesulfonamide, 2,5dichloro-N-L-4,6-dimethoxy-2-pyrimidinyl)aminocarbonyTbenzenesulfonamide and 2-carbomethoxy-N--(,6-dimethyl-2pyrimi'dinyl)aminocarbonyTbenzenesulfonamide.

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During our investigations aimed to diminish the damaging (harmful) effects of sulfonylurea herbicides on cultivated plants, it has been observed that N-dichloroacetyl-N-substituted-N',N'-disubtitutedw glycinamide derivatives of formula (II) can be used with good results for the protection against phytotoxicity. This recognition led to the working out o the present invention which relates to a herbicide composition containing s sulfonylurea derivative of the formula (I) as herbicidally active ingredient and an N-dichloroacetyl-N-substituted-N',N'- disubstituted glycinamide derivative of the formula (II) as antidote.

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In formula (1) RI stands for a hydrogen, halogen, a lower alkyl, lower alkoxy, -NO2, -C02R3, -CO-NH-OR4, -S02-NH-OR4 or -OCF3 group, wherein R3 and R4 are lower alkyl groups; R2 stands for hydrogen, halogen, an optionally substi u ed lower a!kyl, lower alkoxy, -NCO, -CN, -NHCO2R5 -NHCOR5 or -NR6R7 group, wherein R5 R and R stands for a lower alkyl group; stand for a hydrogen or a lower alkyl group; X and Y, which are the same or different, represent a hydrogen, halogen, a lower alkyl, lower alkoxy, lower alkylthio group, a lower alkyl or lower alk'oxy group substituted by 1 to 3 halogen atoms, an -NO2 or a di(lower alkyl)amino group; and K stands for CH or N.

In formula (II) R8 and R9, which are the same or different, represent a hydrogen, a Cl_8 alkyl, C2_8 alkenyl, C5_6 cycloalkyl, benzyl or an optionally substituted phenyl group, or R8 and R9, together with the nitrogen to which they are attached, may also form a hexamethylene- RIO imino group, with the proviso that R9 is different from phenyl group, when R8 stands for a hydrogen; and stands for a Cl_5 alkyl, C2_5 alkenyl or benzyl grgup. Preferred derivatives are the compounds of formula (I), wherein R1 stands for a hydrogen, halogen, a Cl_3 alkyl, Cl_3 alkoxy, -NO2, -C02R3, -CO-NH-OR4, -S02-NH-OR4 or -OCF] group, wherein R3 and R4 stand for a CI_3 alkyl groups; R2 stands for a hydrogen, halogen, a Cl_3 alkyl group optionally substituted by i to 3 halogen atoms, a CI_3 alkoxy, -NCO, -CN, -NHCO2R5, -NHCOR5 or -NR6R7 group, wherein R5 stands for a el_4 alkyl group; R6 and R7 stand for a hydrogen or a el_3 group alkyl X and Y, which are the same or different, represent a K hydrogen, halogen, a gl_3 alkyl, Cl_3 alkoxy, Cl_3 alkylthio group, a Cl_3 alkyl or alkoxy group substituted by 1 to 3 halogen atoms, or a di(Cl_3 aikyl)amino or -NO2 group; and stands for CH or N.

Preferred compounds of formula (II) are those, wherein R8 and R which are the same or different, represent a hydrogen, a Cl_8 alkyl, C2_8 alkenyl, C5_ cyclo- alkyl or benzyl group as well as a phenyl group optionally substituted by one or two Cl_3 alkyl group(s) and/or halogen atom(s), or RB and Rg, together with the nitrogen to which they are attached, may also form a hexamethyleneimino group, lO with the proviso that R9 is different from phenyl group, when R8 stands for a hydrogen; and stands for a Cl_5 alkyl, C2_5 alkenyl or benzyl group.

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The compounds may contain fluorine, chlorine, bromine or iodine as halogens.

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The herbicide compositions according to the present in,ention contain the compounOs of formulae (I) and (Ii) in a total amount of 5 to 95 by mass, in a ratio by mass of between 1: 20 and 1:

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The compounds preferably be used as - 7 350. of formula antidotes, (II), which may most are summarized in Table I, Table I .DTD:

Compound No.

R Su bstituents R9 RIO I phenyl 2 phenyl 3 phenyi 4 phenyl 5 phenyl phenyl ? phenyl 8 phenyl phenyl lO allyl ll allyl 12 allyl 13 ethyl isobutyl 15 methyl 16 methyl 17 methyl 18 methyl ethyl ethyl methyl ethyl ethyl ethyln-propyl ethyl isopropyl ethyl allyl ethyln-butyl ethylsec.-butyl ethyl isobutyl ethyl tert.-butyl allyl methyl allyl ethyl allylallyl ethylallyl isobutyl ethyl methyl n-propyl methyl isopropyl methyl allyl methyl ethyl ethyln-propyl continuation of Table I Compound S u b s t i t u e n t s No. R8 R9 Rl0 ethyl ethyl isopropyl 21 ethyl ethyl ethyl 22 cyclohexyl ethyl ethyl 23 phenyl n-propyl ethyl 24 allyl H allyl n-propyl n-propyl allyl 26 cyclohexyl H allyl 27 phenyl n-propyl allyl 28 2,6-dimethyl- phenyl methyl ethyl 29 2,6-diethyl- phenyl methyl ethyl hexamethylene ethyl 31 3-chlorophenyl methyl ethyl 32 ethyl ethyl n-butyl 33 ethyl ethyl isobutyl 34 ethyl ethyl sec.-butyl ethyl ethyl tert.-butyl 36 phenyl methyl ethyl 37 phenyl methyl n-propyl 38 pheny! methyl aliyl 39 phenyl isopropyl ethyl phenyl isopropyl allyl continuation of Table I Compound No.

R8 - 9 Substi R9 rue ts RIO 41 methyl 42 ethyl 43 n-propyl 44 isopropyl 45 n-butyl isobutyl 47 sec.-butyl 48 benzyl 49 n-propyl 50 phenyl 51 phenyl 52 2,6-dimethyl-phenyl 53 2,6-dimethyl-phenyl 54 2,6-diethyl-phenyl 2,6-diethyl-phenyl 56 allyl 57 allyl 58 allyl 59 allyl 60 allyl H H H H H H H H n-propyl methyl methyl methyl methyl methyl methyl H H H H H methyl ethyl n-propyl isopropyl n-butyl isobutyl sec.-butyl benzyl allyl methyl isopropyl methyl allyl methyl allyl n-butyl isobutyl isopropyl n-propyl @thyl These antidotes as well as the process for their preparation and their use to diminish the phytotoÎicity of hiolcarbamae and chloroacetanilide herbicides have been described in the Hungarian patent application published under the number T/35,471.

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In the practical use for plant protection, "the herbicide compositions according to the invention may be employed in the form of an emulsifiable concentrate (EC), wettable powder (WP), granulate (G) as well as aqueous or oily suspension.

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The preparation of these compositions is illustrated in detail in the following non-limiting Examples.

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Example i .DTD:

Preparation of a wettable powder (32.1 WP) O.l by mass of 1-(2-carbomethoxybenzenesulfonyl)-3-(4-methyl-6-methoxy-l, 3,5-triazin-2-yl)urea as herbicidally active ingredient, 32 by mass of the compoundNo. 41 in Table I as antidote as well as 299 by mass of a synthetic silicate carrier (2eolex 444), 28.9 by mass of a diatomaceous earth carrier, 2 by mass of an aliphatic sodium sulfonate as wetting agent (Netzer IS), furthermore 3 by mass of a phenol-formaldehyde condensation product (Dispergiermittel 144) and 5 by mass of sulfite liquor powder as dispersing agents are homogenized and pre-ground in a laboratory ball mill, then ground to fine particles by using an Alpine lO0 LU type UltrapleÎ mill to give a wettable powder containing the active ingredieqt and the antidote in a total amount of 32.1% by mass, in a ratio of 1: 320 (in the above order). Floatability: 83%, in a concentration of 1%. Wet sieve residue (on a DIN lO0 sieve): 1. 2%.

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Example 2 .DTD:

Preparation of a wettable powder (40.5 WP) 0.5% by mass of chlorsulfuron Z-l-(2-chlorophenylsulfonyl)-3-(4-methoxy-6methyl-l,3,5-triazin-2-yl)ure7 as herbicidally active ingredient, 40% by mass of the compound No. 41 in Table I as antidote as well as 15% by mass of Zeolex 444 and 35% by mass of diatomaceous earth as carriers, 3% by mass of Dispergiermittel 1494 as dispersing agent, 2% by mass of Netzer IS as wetting agent and 4.5% by mass of sulfite liquor powder are homogenized and ground to fine particles as described in Example 1 to obtain a wettable powder containing the active ingredient and the antidote in a total amount of 40.5% by mass, in a ratio of 1: 80.

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Example 3 .DTD:

Preparation of a wettable powder (64.4 WP) 0.4% by mass of 1-(2-carbomethoxybenzenesulfonyl)-3-(4,6-dime hyl-2- pyrimidinyl)urea as herbicidally active ingredient, 64% by mass of the compound No. 60 in Table I as antidote, 10% by mass of Zeolex 444 and 16% by mass of diatomaceous earth as carriers, 2% by mass of Netzer IS as wetting agent as well as 3% by mass of Dispergiermittel 1494 and 4.6% by mass of sulfite liquor owder as dispersing agents are homogenized and ground to line particles as described in Example l to give a wettable powder containing the active ingredient and the antidote in a total amount of 64.4 by mass, in a ratio of i: 160.

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Example 4 .DTD:

Preparation of an emulsifiable concentrate (48.3 EC) 0.3 by mass of chlorsulfron as herbicidally active ingredient and 48 by mass of the compound No. 24 in Table I as antidote are dissolved while stirring in a mixture containing 33.7 by mass of xylene and lO by mass of dimethylformamide. After adding 6.5 by mass of Emulsogen IP-400 and 1.5 by mass of Emulsogen EL-&O0 (a mixture of calcium dodecylbenzenesulfonate and a fatty acid polyglycol ester) as emulsifying agents, the solution is filtered to result in an emulsifiable concentrate containing the active ingredient and the antidote in a total amount of 48.3 by mass, in a ratio of 1: 160.

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The stability of this composition in a concentration ol l is excellent in water (CIPAC A and CIPA.C D) after 2 hours, whereas it is still good with a minimum and reversible cream (gel) formation after 24 hours.

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Example 5 .DTD:

Preparation of an emulsifiable concentrate (80.25 EC) 0.25 by mass of 1(2-carbomethoxybenzenesulfonyl)-3-4,6-dimethyl-2-pyrimidinyl)urea as herbicidally active ingredient and 80 by mass of the compound No. 43 in Table I as antidote are dissolved under stirring in a mixture containing 8% by mass of xylene and 3.75% by mass of dimethylformamide. After adding 6% by mass of Emulsogen IP-400 and 2% by mass of Emulsogen EL-400 as emulsifying agents, the solution is filtered to give an emulsifiable concentrate containing the active ingredient and the antidote in a total amount of 80.25% by mass, in a ratio of 1: 320.

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Example 6 .DTD:

Preparation of an emulsifiable concentrate (61.5 EC) 1.5% by mass of 1-(2carbomethoxybenzenesulfonyl)-3-(-methyl-6-methoxy-l,3,5-triazin-2-yl)urea as herbicidally active ingredient and 60% by mass of the compound No. 59 in Table I as antidote are dissolved while stirring in a mixture containing 20% by mass of xylene and 10.5% by mass of dimethylformamide. After adding 7% by mass of Emulsogen IP-400 and 1% by mass of Emulsogen EL-400 as emulsifying agents, the solution is filtered to obtain an emulsifiable concentrate containing the active ingredient and the antidote in a total amount of 61.5% by mass, in a ratio of 1: 40.

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Example 7 .DTD:

Preparation of a suspension (7"1.75 FW) 1.75% by mass of l-(2-carbomethoxybenzenesulfonyl)-3-(4,6-dimethyl-2- pyrimidinyl)urea as herbicidally active ingredient, 70% by mass of the compound No. 60 in Table I as antidote and 1% by mass of Zeolex 444 as carrier are homogenized and pre-ground in a laboratory ball mill. The powder mixture obtained is suspended in a mixture containing 5% by mass of ethylene glycol, 1% by mass of oleylmethyltauride (Arkopon T powder) as wetting agent, 4% by mass of nonylphenol polyglycol ether (Arkopol N- 090) as dispersing agent and 11.25% by mass of water under stirring, then ground to fine particles in a laboratory pearl mili. After separation of the charge, 6% by mass of 2% xanthane resin thickening solution (Rhodopol 25) are added and homogenized by stirring to obtain a suspension containing the active ingredient and the antidote in a total amount of 71. 5% by mass, in a ratio of 1: 40.

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Floatability: 94.6%, in a concentration of 1%.

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Example 8 .DTD:

Preparation of a suspension (40.5 FW) 0.5% by mass of chlorsulfuron as herbicidally active ingredient, 40% by mass of the compound No. 41 in Table I as antidote and 5% by mass of Zeolex 444 as carrier are homogenized and pre-ground in a laboratory ball mill. The powder mixture obtained is suspended in a mixture containing I0% by mass of ethylene glycol, 2.5% by mass of Arkopon T as wetting agent, 5.5% by mass of Arkopol N-090 as dispersing agent and 28.5% by mass of water and then ground to fine distribution in a laboratory pearl m311. After separation of the charge, 8.5% by mass of 2% xanthane resin thickening solution are added and homogenized by stirring to obtain a scspension containing the active ingredient and the antidote in a total amount of 40.5% by mass, in a ratio of 1: 80.

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Example 9 .DTD:

Preparation of a suspension (16.1 FW) 0.1% by mass of 1-(2-carbomethoxybenzenesulfonyl)-3-(4-methyl-6-methoÎy-l, 3,5-triazin-2-yl)urea, 16% by mass of the compound No. 24 in Table I and 10% by mass of Zeolex 444 as carrier are h6mogenized and prs-ground in a laboratory ball mill. The powder mixture obtained is suspended in a mixture containing 15% by mass of ethylene glycol, 3% by mass of Arkopon T as wetting agent, 6% by mass of Arkopol N-090 as dispersing agent and 39.9% by mass of water under stirring, then ground to fine distribution in a laboratory pearl mill. After separation of the charge, 10% by mass of 24 xanthane resin thickening solution are added and homogenized by stirring to result in a suspension containing the active ingredient and the antidote in a total amount of 16.1% by mass, in a ratio of 1: 160.

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The biological activity of the compositions according to the invention are shown in the following Examples.

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Example I0 .DTD:

A laboratory investigation was carried out as follows. 400 g of soil each were weighed in culture bottles with a surface of 0.8 dm2 lined with PVC foil. This upper field soil had a hardness (impermeabilitY) of 46, a humus content of 1.95% and a pH value of 5.7. In this soil, grains of Pi 3732 maize each, 20 grains of AlfSld-i sorghum each and 0.5 g/pot of millet each were sown. The sowing was covered with 200 g of soil each. The'chlorsulfuron herbicide ingredient as such in an amount of 5 g/hectare (thereinafter g/ha) or lO g/ha, respectively as well as in combinations with the compounds Nos. 24, 41, 43, 59 or 60 in Table I as antidotes taken in an amount of 0.4, 0.8 or 1.6 kg/ha, respectively were sprayed onto the soil. The investigation was carried out by measuring the green mass or sprout length of the plants cultivated for 14 days; the average results of four repetions are summarized in Tables II and III.

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For comparison, untreated plants and on the other hand, a combination prepared with N,N-diallyl-2,2-dichloroacetamide (Code No. R-25788) as antidote were used.

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Table II .DTD:

Treatment Maize Sorghum Millet Maize green mass green mass green mass sprout length g/plant g/pot g/pot cm/plant Untreated control 2.0 2.0 0.5 42 Chlorsulfuron g/ha 0.8 2.5 0.5 22 Chlorsulfuron g/ha + +I/24 0.4 g/ha 1.4 2.6 0.6 35 0.8 g/ha 1.7 2.0 O.O 33 1.6 g/ha 1.7 1.6 O.O 37 continuation of Table II Treatment Maize Sorghum Millet green mass green mass green mass g/plant g/pot g/pot Maize Sprout length cm/plant Chlorsuluron g/ha + + 1/41 0.4 g/ha 0.8 g/ha 1.6 g/ha I.i 1.7 0.2 28 1.5 2.8 0.0 37 1.0 1.4 O.O 30 Chlorsulfuron g/ha + + 1/43 0.4 g/ha 0.8 g/ha 1.6 g/ha 1.0 1.8 O.O 22 i.i 2.6' 0.8 25 1.5 2.4 0.2 31 ChlorsulIuron g/ha + + 1/59 0.4 g/ha 0.8 g/ha 1.6 g/ha 1.2 2.0 0.0 25 i.i 1.8 0.2" 27 1.0 2.3 0.9 38 Chlorsulfuron g/ha + + 1/60 0.4 g/ha 0.8 g/ha 1.6 g/ha 1.3 1.9 0.9 28 1.7 1.9 0.7 30 2.0 2.1 1.5 35 continuation of Table II Treatment Maize Sorghum Millet green mass green mass green mass g/plant g/pot g/pot Maize sprout length cm/plant Chlorsulfuron g/ha + +R-25788 0.4 g/ha 1.0 0,8 g/ha 1.2 1.6 g/ha 0.9 2.5 0.0 22 2.5 0.0 26 1.5 0.0 24 Mode of abbreviation here and hereinafter: 1/41 = compound No. 41 in Table I (etc.) Table III .DTD:

Treatment Maize Sorghum Millet Maize green mass green mass green mass sprout length g/plant g/pot g/pot cm/plant Untreated control 2.0 Chlorsulfuron i0 g/ha 0.7 Chlorsulfuron g/ha + + 1/24 O.a g/ha 1.3 O.B g/ha 1.O 1.6 g/ha 1.0 2.0 0.5 42 1.3 0.4 17 3.0 0.7 30 2.3 0.0 28 1.4 0.0 28 t % continuation of Table III Treatment Chlorsulfuron lO g/ha + + II41 0.4 g/ha 0.8 g/ha 1.6 g/ha Maize green mass g/plant 1.O 1.4 0.8 Sorghum green mass g/pot 1.6 2.7 1.3 Millet green mass g/pot 0.0 0.0 0.0 Maize sprout length cm/plant Ch!orsulfuron i0 g/ha + + 1/43 0.4 g/ha 0.8 0.8 g/ha 1.0 1.6 g/ha 1.4 1.6 2.4 2.2 0.0 0.6 0.0 Chlorsulfuron I0 g/ha + + 1/59 0.4 g/ha 1.0 0.8 g/ha 0.8 1.6 g/ha 0.9 1.8 1.3 2.2 0.i 0.0 1.0 Chlorsulfuron i0 g/ha + + 1/60 0.4 g/ha 8.9 0.8 g/ha 1.5 1.6 g/ha 1.2 1.7 1.7 1.9 0.8 0.5 1.2 continuation of Table III Treatment Maize green mass g/plant Sorghum Millet Maize green mass green mass sprout length g/pot g/pot cm/plant Chlorsulfuron lO g/ha + +R-25788 0.4 g/ha 1.2 0.8 g/ha 1.O 1.6 g/ha 1.4 2.0 0.6 26 1.6 O.O 28 1.8 1.0 31 It is obvious from the results shown in Tables II and III that the compositions according to the invention which contain chlorsulfuron as herbicidally active ingredient of formula (I) with an N- dichloroacetyl-N-substituted-N,N'-disubstituted glycinamide derivative of formula (II) as antidote in a ratio between 1: 40 and 1: 320 resulted in a symptom-free, healthy maize and sorghum, whereas chlorsulfuron used as such (in itself) damaged both these cultivated plants in both doses.

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Example ii .DTD:

The investigation described in Example i0 was carried out, except that l(2-carbomethoxybenzenesulfonyl)-3-(4-methyl-6-methoxy-l,5,5-triazin-2yl)urea was used as heroicidally active ingredient instead of chlorsulfuron.

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The results of these measurements are summarized in Tables IV and V wherein the active ingredient is simply labelled by the Code No. OH-3.

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Table IV .DTD:

Treatment Maize Sorghum Millet Maize green mass green mass green mass sprout length g/plant g/pot g/pot cm/plant Untreated control 2.0 OH-3 5 g/ha 0.8 OH-3 5 g/ha+ + 1/24 0.4 g/ha 0.9 O.B g/ha 1.2 1.6 g/ha 1.O OH-3 5 g/ha + 1/41 0.4 g/ha 0.9 0.8 g/ha 0.9 1.6 g/ha 1.O 2.0 0.5 42 1.3 1.3 24 1.2 0.5 29 i. 4 2.3 35 2.5 0.8 30 I.I 1.3 29 2.1 1.4 33 1.5 1.2 29 OH-3 5 g/ha + + 1/59 0.4 g/ha 0.9 0.8 g/ha 0.7 1.6 g/ha O.B i.i 1.9 29 2.1 1.3 26 1.4 1.4 29 continuation of Table IV Treatment Maize Sorghum Millet green mass green mass green mass g/plant g/pot g/pot Maize sprout length cm/plant OH-3 5 g/ha + +I/60 O.& g/ha 1.2 0.8 g/ha 0.9 1.6 g/ha 0.

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i.I 0.8 31 i.i i.0 30 1.5 0.5 28 OH-3 5 g/ha+ +R-25788 0.4 g/ha 1.0 0.8 g/ha 1.3 1.6 g/ha 1.3 1.4 1.3 28 1.4 i.i 30 1.5 1.0 36 Table V .DTD:

Treatment Maize Sorghum Millet green mass green mass green mass g/piant -g/pot g/pot Maize sprout length cm/plant Untreated control 2.0 OH-3 i0 g/ha 0.8 OH-3 i0 g/ha + 1/24 0.4 g/ha 3.0 0.8 g/ha 0.

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1.6 g/ha 1.7 2.O 0.5 42 1.8 O.1 20 2.7 0 0 30 2.0 0.0 28 !.0 0.0 37 continuation of Table V "Treatment Maize Sorghum green mass green mass g/plant g/pot Millet green mass g/pot Maize sprout length cm/plant OH-3 i0 g/ha + + 1/41 0.4 g/ha i.i O.B g/ha 1.2 1.6 g/ha 1.1 1.4 1.4 1.7 0.4 1.0 1.5 OH-3 i0 g/ha + + 1/43 0.4 g/ha 1.0 0.8 g/ha 0.9 i. G g/ha O. 8 0H-3 iO g/ha + + 1/59 0.4 g/ha 0.9 O.B g/ha 1.2 1.6 g/ha 1.0 1.8 1.5 i.I 1.2 1.4 1.3 0.5 0.4 0.7 1.2 0.8 0.9 OH-3 i0 g/ha + + 1/60 0.4 g/ha i.i 0.8 g/ha 0.7 1.6 g/ha 1.2 OH-3 10 g/ha + +R-25788 0.4 g/ha 0.7 0.8 g/ha 1.0 1.6 g/ha 1.2 2.4 1.7 1.6 1.3 2.0 1.4 0.0 1.0 1.0 1,0 1.6 0.4 It can clearly be seen from the data of Tables IV and V that the N-dichloroacetyl-N-substituted-N',N'-disubstituted glycinamide antidotes of formula (Ii), when used together with 1-(2carbomethoxybenzenesulfonyl)-3-(4-methyl-6-methoxy-l,3,5-triazin-2yl)urea according to the formula (I) as herbicidally active ingredient in a ratio between 40: I and 320: l, are capable to prevent the harmful effect of this active ingredient on the cultivated plants. The effect of these antidotes approaches or in several cases even exceeds that of the antidote Code No. R-25788 suggested in US-PS 4,343,649 for the antidotation of sulfonylurea herbicides.

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Example 12 .DTD:

The investigation described in Example lO was carried out, except that instead of chlorsulfuron, 1-(2-carbomethoxybenzenesulfonyl)-3-(4,6dimethyl-2-pyrimidinyl)urea was used as herbicidally active ingredient. The results of these measurements are summarized in Tables VI and VII, wherein the active ingredient is simply labelled by the Code No. OH-4.

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- 25 Table VI .DTD:

Treatment Maize green mass g/plant Sorghum green mass g/pot Millet green mass g/pot Maize sprout length cm/plant Untreated control 2.0 OH-4 5 g/ha 0.7 OH-4 5 g/ha+ + 1/24 0.4 g/ha 0.9 0.8 g/ha 0.9 1.6 g/ha 0.8 OH-4 5 g/ha+ + 1/41 0. g/ha 0.7 0.8 g/ha 0.8 1.6 g/ha 0.9 2.0 0.8 i.I 0.8 0.9 1.2 1.0 i.i 0.5 0.9 1.3 0.0 0.9 1.0 0.4 0.4 OH-4 5 g/ha + + 1/43 0.4 g/ha 0.8 0.8 g/ha 0.7 1.6 g/ha i.i 0.8 1.3 0.7 0.0 0.6 0.7 OH-4 5 g/ha + + 1/59 0.4 g/ha i.I 0.8 g/ha I.i 1.6 g/ha 0.6 1.6 0.7 i.I 0.8 0.5 0.3 continuation of Table VI Treatment Maize green mass g/plant Sorghum green mass g/pot Millet green mass g/pot Maize sprout length cm/plant OH-4 5 g/ha + + 1/60 0.4 g/ha O.B 0.8 g/ha 0.8 1.6 g/ha 1.1 1.5 1.5 1.0 0.0 0.5 0.7 OH-4 5 g/ha + + R-25788 0.4 g/ha 0.7 0.8 g/ha 0.5 1.6 g/ha 0.5 0.7 1.4 1.6 0.9 0.7 i.i Table VII .DTD:

Treatment Maize green mass g/plant Sorghum green mass g/pot Millet green mass g/pot Maize sprout length cm/plant Untreated control OH-& i0 g/ha OH-4 i0 g/ha + 1/24 0.4 g/ha 0.8 g/ha 1.6 g/ha 2.0 0.6 0.8 0.6 0.7 2.0 0.7 0.5 0.5 i.i 0.5 0.5 0.3 0.2 O.O 18 ii continuation of Table Vll Treatment Maize green mass g/plant Sorghum green mass g/pot Millet green mass g/pot Maize sprout length cm/plant OH-4 I0 g/ha+ + 1/41 0.4 g/ha 0.8 g/ha 1.6 g/ha 0.6 0.4 0.5 0.2 O.1 0.0 0.4 0.2 0.4 i0 OH-4 10 g/ha + 1/43 0.4 g/ha 0.8 g/ha 1.6 g/ha 0.8 0.3 0.6 0.6 0.0 0.4 0.4 0.6 0.7 OH-4 10 g/ha+ + 1/59 0.4 g/ha O.B g/ha 1.6 g/ha 0.5 0.2 0.3 0.3 0.i 0.3 0.5 0.3 0.4 ii Ii OH-4 10 g/ha+ + 1/60 0.4 g/ha 0.8 g/ha 1.6 g/ha OH-4 10 g/ha +R-25788 0.4 g/ha 0.8 g/ha 1.6 g/ha 0.2 0.5 0.3 0.5 0.4 0.5 0.3 0.6 0.5 0.4 0.7 0.2 0.2 0.4 0.3 0.6 0.2 0.4 ii 12 8 Based on the data of Table VI it is obvious that the N-dichloroacetyl-N-substituted-N',N'-disubstituted glycinamide antidotes of formula (II), when used together with 1-(2carbomethoxybenzenesulfonyl)-3-(4,6-dimethyl-2-pyrimidinyl)urea as herbicidally active ingredient in a ratio between 40: 1 and 320: l, are capable to prevent the harmful effect ol the active ingredient on the cultivated plants.

.DTD:

Further on, it is shown by the data of Table VII that a dose of lO /ha of l-(2-carbomethoxybenzenesulfonyl)-3-(4,6-dimethyl-2-pyrimidinyl)urea as herbicidally active ingredient induces such a high harmful effect on the maize and sorghum cultures which cannot sufficiently be prevented even by usin the widely known and employed antidote R-25788. A somewhat better result can be achieved by using the compositions according to the invention which contain the antidotes of formula (II).

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Claims

Claims i. Herbicide compositions containing a sulfonylurea type

herbicidally active ingredient and a glycinamide type antidote, which c omp r i s e a sulfonylurea derivative of formula (I) RI N R2 SO2- NilC,,. NH N-'y (I) wherein R stands for a hydrogen, halogen, a lower alkyl, lower alkoxy, -NO2, -C02R3, -CO-NH-OR4, -S02-NH-OR4 or -OCF3 group, wherein R3 and R4 are lower alkyl group; R2 stands for hydrogen, halogen, an optionally substituted lower alkyl, lower alkoxy, -NCO, -CH, -NHCO2Rs, -NHCOR5 or -NR6R7 group, wherein R5 stands for a lower alkyl group; R6 and R7 stand for a hydrogen or a lower alkyl group; X and Y, which are the same or different, represent a hydrogen, halogen, a lower alkyl, lower alkoxy, lower alkyl- thio group, a lower alkyl or lower alkoxy group substituted by 1 to 3 halogen atoms, an -NO2 or a di(lower alkyl) amino group; and K stands for CH or N as herbicidally active ingredient and an N-dichloroacetyl-N-substituted- N',N'-disubstituted glycinamide derivative of formula (II) R8 N--C-- CH2 N-- C II I II Rg 0 RI0 0 (II) wherein R8 and R, which are the same or different, represent a hydrogen, a Cl_8 alkyl, C2_B alkenyl, C 5-6 cyclo- alkyl, benzyl or an optionally substituted phenyl group, or R8 and R, together with the nitrogen to which they are attached, may also form a hexamethylene- imino group, with the proviso that R9 is different from phenyl group, when R8 stands for a hydrogen; and RIO stands for a Cl_5 alkyl, C2_5 alkenyl or benzyl group as antidote.

.CLME:
2. A herbicide composition as claimed in claim l, which c o mp r i s e s a sulfonylurea derivative of formula (I), wherein R1 R2 stands for a hydrogen, halogen, a Cl_3 alkyl, Cl_3 alkoxy, -NO2, -C02R3, - CO-NH-OR4, -S02-NH-OR4 or -OCF3 group, wherein R3 and R4 stand for a Cl_] alkyl groups; stands for a hydrogen, halogen, a Cl_3 alkyl group optionally substituted by 1 to 3 halogen atoms, a Cl_3 alkoxy, -NCO, -CN, -NHCO2R5, -NHCOR5 or -NR6RV group, wherein R5 stands for a Cl_4 alkyl group; R6 and R7 stand for a hydrogen or a Cl_3 alkyl group; X and Y, which are the same or different, represent a hydrogen, halogen, a Cl_3 alkyl, Cl_3 alkoxy, alkylthio group, a C1-3 alkyl or alkoÎy group C1-3 substituted by 1 to 3 halogen atoms, or a di(Cl_3 alkyl)amino or -NO2 group; and K stands for CH or N as herbicidally active ingredient and an N-dichloroacetyl-N-substituted- N',N'-disubstituted glycinamide derivative of formula (II), wherein R8 and R9, which are the same or different, represent a hydrogen, a Cl_8 alkyl, C2_8 'alkenyl, C5_6 cycloalkyl or benzyl group as well as a phenyl group optionally substituted by one or two Cl_3 alkyl group(s) and/or halogen atom(s), or R8 and R9, together with the nitrogen to which they are attached, R i0 may also form a hexamethyleneimino group, with the proviso that R9 is different from phenyl group, when R8 stands for a hydrogen; and stands for a Cl_5 alkyl, C2_5 alkenyl or benzyl group as antidote.

.CLME:
3. A herbicide composition as claimed in claim l, which c o mpr i s e s the compounds of the formulae (I) and (II) in a total amount of 5 to 95% by mass in a ratio of between 1: 20 and 1: 350.

.CLME:
4. A herbicide composition substantially as hereinbefore described in any one of Examples 1 to 9.

.CLME:
5. A method of killing weeds in a plot which comprises applying to the plot a suifonylurea derivative of the general formula (I) as defined in claim 1 or claim 2 and also applying to the plot a glycine derivative of the general formula (II) as defined in claim 1 or claim 2.

.CLME:
6. A method as claimed in claim 5, wherein the ratio of the amount of the compound of the general formula (I) to the amount of the compound of the general formula (II) lies in the range of 1:20 to 1:350.

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7. A method as claimed in claim 5 or claim 6, wherein maize or sorghum is growing in the plot.

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8. A method as claimed in claim 5, which is substantially as hereinbefore described in any one cf Examples i0 to 12.

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Published 1988 at The Patent Ofqce, State House, 66,I lqh Holborn, London WCIR 4TP. Further coples may be obtained from The Patent Oce, Sales Branch, St Mary Cray, 0rpington, Kent BRS SRD. Printed by Multiplex techniques ltd, St Mary Cray, Kent. Con. 1/87.

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8. A method as claimed in claim 5, which is substantially as hereinbefore described in any one of Examples i0 to 12.

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33- Amendments to the claims have been filed as follows Claims i. Herbicide compositions containing a sulfonyl- urea type herbicidally active ingredient and s glycinamide type antidote, which comprise - a sulfonylurea derivative of formula (I) --NH,,.

.CLME:

X c-..--< K II 0 N-- y (I) wherein RI stands for a hydrogen, halogen, a lower alkyl, lower alkoxy, -NO2, -C02R3, -CO-NH-OR4, -S02-NH-OR4 or -OCF3 group, wherein R3 and R4 are lower alkyl group; R2 stands for hydrogen, halogen, an optionally substituted lower alkyl, lower alkoxy, -NCO, -, -NHCO2R5, -NHCOR5 or -NR6R7 group, wherein R5 stands for a lower alkyl group;.- R6 and R7 stand for a hydrogen or a Iower alkyl group; X and Y, which are the same or different, represent a hydrogen, halogen, a lower alkyl, lower alkoxy, lower alkyl- thio group, a lower alkyl or lower alkoxy group substituted by 1 to 3 halogen atoms, an -NO2 or a di(lower alkyl) amino group; and K stands for CH or N with the proviso that if K stands for -CH then X and Y cannot both stand for difluoromethoxy as herbicidally active ingredient and an N-dichlor0acetyl-N-substituted-N',N'-disubstituted glycinamide derivative of formula (If) C I!1 Rg 0 RIO 0 CH<C!- C! (II) wherein R8 and Rg, which are the same or different, represent a hydrogen,.a C i-8 alkyl, C2_B alkenyl, C5_6 cycloalkyl, benzyl or an optionally substituted phenyl group, or R8 and R9, together with the nitrogen to which they are attached, may also form a hexamethylene- imino group, ID with the proviso that R9 is different from phenyl group, when R8 stands for a hydrogen; and stands for a el_5 alkyl, C2_5 alkenyl or benzyl group as antidote.

.CLME:

2. A herbicide composition as claimed in claim I, which c c m p r i s e s a sulfonylurea derivative of formula (]).

.CLME:

wherein R stands for a hydrogen, halogen, a CI_3 alkyl, Ci_3 alkoxy, -NO2, -C02R3, -CO-NH-OR4, -S02-NH-OR4 or -OCF3 group, wherein R3 and R4 stand for a Cl_3 alkyl groups; R2 stands for a hydrogen, halogen, a CI_3 alkyl group optionally substituted by i to 3 halogen atoms, a Cl_3 alkoxy, -NCO, -CN, -NHCO2Rs, -NHCOR5 or -NR6R7 group, wherein R5 stands for a Cl_4 alkyl group; R6 and R7 stand for a hydrogen or a Cl_3 alkyl group; X and Y, which are the same or different, represent a hydrogen, halogen, a Cl_3'alkyl, Cl_3 alkoxy, Cl_3 alkylthio group, a Cl_3 alkyl or alkoÎy group substituted by 1 to 3 halogen atoms, or a di(Cl_3 alkyl)amino or NO2 group; and K stands for CH or N as herbicidally active ingredient and an N-dichloroacetyl-N-substituted- N',N'.-disubstituted glycinamide derivative of formula (II), wherein R8 and Rg, which are the same or different, represent a hydrogen, a Cl_8 alkyl, C2_8 alkenyl, C5_6 cycloalkyl or benzyl group as well as a phenyl group optionally substituted by one or two el.3 alkyl group(s) and/or halogen atom(s), or R8 and Rg, together with the nitrogen to which they are attached, RlO group as antidote.

.CLME:

may also form a hexamethyleneimino group, with the proviso that R9 is different from phenyl group, when R8 stands for a hydrogen; and alkyl, C alkenyl or benzyl stands for a Cl_5 2-5 3. A herbicide composition as claimed in claim l, which c o mp r i s e s the compounds of the formulae (I) and (II) in a total amount of 5 to 95% by mass in a ratio of between 1: 20 and 1 350.

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4. A herbicide composition substantially as hereinbefore described in y cne of Examples 1 to
9.

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5. A method of killing weeds in a plot which comprises applyinK to the plot a sulfonylurea derivative of the general formula (I) as defined in claim I or claim 2 and also app!yin to the plot a glycine derivative of the general formula (II) as defined in claim 1 or claim 2.

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6. A method as claimed in claim 5, wherein the ratio of the amount of the compound of the general formula (I) to the amount of the compound of the general formula (iI) lies in the range of 1:20 to 1:350.

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7. A method as claimed in claim 5 or clair 6, wherein maize or sorghum is growing in the plot.

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