CA1228244A - Herbicidal composition - Google Patents

Abstract

Case 5-14381/1+2/=
HERBICIDAL COMPOSITION
Abstract There are described herbicidal compositions containing, in addition to a) a herbicidally effective sulfonylurea of the formula (I) wherein X is halogen, C1-C3-haloalkenyl, C1-C3-alkoxycarbonyl, C3-C4-alkenyloxy, C1-C3-haloalkoxy, C1-C3-haloalkyl-thio, C1-C3-alkoxy-C1-C2-alkoxy or nitro, X1 is hydrogen, or together with X forms a bridge member 2-O-CH2CH2-3, or , Y is hydrogen or halogen, E is nitrogen -N= or methine -CH=, R1 is halogen, C1-C3-alkyl, C1-C3-alkoxy, C1-C4-haloalkoxy or cyclopropyl, and R2 is C1-C3-alkyl, C1-C3-alkoxy, C1-C4-haloalkoxy, cyclopropyl or dimethylamino, b) an oxime ether acting as an antidote and corresponding to the formula (II) wherein n is 1 or 2, R3 and R4 are each hydrogen or alkyl, R5 and R5 are each hydrogen, halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, alkylsulfinyl, alkylsulfonyl, haloalkylsulfinyl, halo-alkylsulfonyl or nitro, R7 and R8 separately are each alkyl or alkenyl, or together are a 1,2-ethylene or 1,3-propylene group each unsubstituted or substituted by one or more alkyl groups, and X is a cyano group or a fluorinated alkyl group which can also contain chlorine;
and also described is the use of these compositions for the selective control of weeds.

Description

~2~

Case 5 14381/1+2/=_ HERBICIDAL COMPOSITION
The present invention relates to a herbicidal compo-sition containing, besides a herbicidally active sulfonyl-urea, an oxime ether which acts as an antidote, to the use of this composition for selectively controlling weeds in crops of cultivated plants, and to the use of oxime ethers as antidotes.
Sulfonylureas as herbicidal agents for crops of cultivated plants are known for example from the U.S.
Patent SpeciEications Nos. 4,127,405, 4,169,719 and 4,238,621, from EP-A 84020 and from the South African Patent Specifications No. 4874/81 and 127/83. Compared with other herbicides, the sulfonylurea herbicides have the outstanding property of being highly effective. Against the advantages offered, with regard to cost and ecological factors, by the relatively low level of active substance involved with the use of sulfonylurea herbicides has to be set the increased risk of a resulting overdose possibly damaging the cultivated plants. The occurrence of a harmful side-effect of sulfonylurea herbicides can depend also on climatic conditions, on the weather and on the preliminary treatment of the soil.
After recognition of this problem, attempts were made a to find antidotes which would protect the cultivated plants from the said harmful effects occurring with the use of sulfonylurea herbicides, without at the same time lessening the herbicidal effectiveness of these compounds.
In the U.S. Patent Specification No. 4,343,649 there are described, as being such antidotes, 1,8-naphthalic acid anhydride, N,N-diallyl-2,2-dichloroacetamide and a-cyano.
These antidotes are used in herbicidal compositions, together with individual herbicidally effective sulfonyl-ureas.
The object of the present invention was to find suitable antidotes against the plant-damaging side-effect of herbicidally active sulfonylureas.
It has been found that the side-effect, which damages cultivated plants, of herbicidally active sulfonylureas of the general formula I can be eliminated or greatly reduced with the aid of oxime ethers of the general formula II as antidotes.
The sulfonylureas correspond to the general formula I

5~--6 N--4! --S02NHCONH~
\ / \ /
3~=~2 N=-x 1 X \R2 wherein X is halogen, Cl-C3-haloalkenyl, Cl-C3-alkoxycarbonyl, C3-C4-alkenyloxy, Cl-C3-haloalkoxy, Cl-C3-haloalkyl-thio~ Cl-C3-alkoxy-Cl-C2-alkoxy or nitro, Xl is hydroger-, or together with X forms a bridge member

2-o-CH2CH2-3, 2-OCH-CH2-3 or 2-o-S02CH-CH2-3, Y is hydrogen or halogen, E is nitrogen -N= or methine -CH=, ~1 is halogen, Cl-C3-alkyl, Cl-C3-alkoxy, Cl-C4-haloalkoxy or cyclopropyl, and R2 is Cl-C3-alkyl, Cl C3-alkoxy~ Cl-C4-haloalkoxy, cyclopropyl or dimethylamino.
Compounds in which Y = H are preferred.
- Halogen can be for example fluorine, chlorine and bromine, particularly however chlorine.
- By haloalkenyl is meant for example haloethenyl, halo-propenyl and, preferably, 3,3,3-trifluoropropenyl.
- Alkoxycarbonyl can be for example methoxy, ethoxy, propoxy or isopropoxycarbonyl, but preferably methoxycarbonyl.
- By alkenyloxy is meant for example: allyloxy, propenyloxy, buten-2-yloxy, buten-3-yloxy, l-methyl-alkyloxy, 2-methyl-alkyloxy, l-methylpropenyloxy and 3-methylpropenyloxy, especially however allyloxy and buten-2-yloxy.
- Haloalkoxy can be for example: halomethoxy, haloethoxy, halopropoxy and haloisopropoxy, preferably however chloromethoxy, chloroethoxy, fluoromethoxy or fluoroethoxy;
particularly preferred as X is 2-chloroethoxy and pentafluoroethoxy, and as Rl difluoromethoxy.
- By alkoxy-alkoxy is meant for example: methoxy-methoxy, 2-methoxy-ethoxy, ethoxy-methoxy, 2-ethoxy-ethoxy, n-propoxy-methoxy, isopropoxy-methoxy, 2-n-propoxy-ethoxy and 2-isopropoxy-ethoxy, but especially 2-methoxy-ethoxy.
- Y can be for example hydrogen or halogen, such as fluorine, chlorine or bromine, in particular hydrogen or chlorine.

- ~y alkyl is meant for example: methyl, ethyl, n-propyl or i-propyl, preferably methyl.
- Alkoxy is for example: methoxy, ethoxy, n-propoxy or i-propoxy, preferably methoxy and ethoxy.
Sulfonylureas which have proved particularly effective herbicidally are the compounds of the formula I wherein Y is H.
The following sulfonylureas are especially preferred herbicides:
N-[2-(2'-chloroethoxy)-phenyl sulfonyl]-N'-(4-methyl-6-methoxy-triazin-2-yl)-urea, N-[2-(2'-methoxyethoxy)-phenyl-sulfonyl]-N'-(4-methyl-6 methoxy-triazin-2-yl)-urea, N-[2 (2-butenyloxy)-phenyl-sulfonyl]-N'-(4-methyl-6-methoxy-triazin-2-yl)-urea, N-[2-(3-trifluoropropen-1-yl)-phenyl-sulfonyl]-N'-(4-methyl-6-methoxy-triazin-2-yl)-urea, N-(2,5-dichlorophenyl-sulfonyl)-N'-(4-methyl-6-methoxy-pyrimidin-2-yl)-urea, N-(2-methoxycarbonyl-phenyl-sulfonyl)-N'-(4-methyl-6-difluoromethoxy-pyrimidin-2-yl)-urea, N-(2-pentafluoroethoxyphenyl-sulfonyl)-N'-(4,6-dimethoxy-triazin-2-yl)-urea, N-(2-chlorophenyl-sulfonyl)-N'-(4-methyl-6-methoxy-triazin-2-yl)-urea., N-(2-methoxycarbonyl-phenyl-sulfonyl)-N'-(4,6-dimethyl-pyrimidin-2-yl)-urea, N-(2-allyloxy-phenyl-sulfonyl)-N'-(4-methyl~6-ethoxy-triazin-2-yl)-urea, N-(2-nitrophenyl-sulfonyl)-N'-(4-methyl-6-difluoromethoxy-pyrimidin-2-yl)-urea and N-(2-methoxy-carbonyl-phenylsulfonyl)-N'-(4-methyl-6-methoxy-triazin-2-yl)-urea, N-(2-difluoromethoxyphenylsulfonyl)-N'-(4-methyl-6-methoxy-pyrimidin-2-yl)-urea, N-(2-methoxyethoxyphenyl-sulfonyl)-N'-[4-me~hoxy-6-(2'92',2'-trifluoroethoxy)-1,3,5-triazin-2-yl]-urea, N-(2-methoxycarbonylphenyl-sulfonyl)-N'-(4-cyclopropyl-6-methoxy-1,3,5-triazin-2-yl)-urea, N-(2-difluoromethoxyphenyl-sulfonyl)-N'-(4-cyclo-~22~

propyl-6-methoxy-1,3,5-triazi.n-2-yl)-urea, N-[2-(3',-

3',3'-trifluoroprop-1-en-1-yl)-phenyl-sulfonyl]-N'-(4-methoxy-6-methyl-1,3~5-triazin-2-yl)-urea, N-(2-methoxycarbonylphenylsulfonyl)-N'-(2,4-difluoromethoxy-pyrimi.din-2-yl)-urea, N-(2-difluoromethoxyphenyl-sulfonyl)-N'-(4-dimethylamino-6-methoxy-1,3,5-triazin-2-yl)-urea, N-[2-(1',21-dichlorovinyloxy)-phenylsulfonyl~-N'-(4-methoxy-6-methyl-1,3,5-triazin~l-yl)-urea, N-(2,2-dioxo-3-methyl-1-oxa-2-thia-1,2,3,4-tetrahydro-naphthalen-8-yl)-N'-(4-methoxy-6-methyl-1,3~5-triazin-2-yl)-urea, N-(2,2-dioxo-3-methyl-1-oxa-2-thia-1,2 a 3,4-tetrahydro-napththalen-8-yl)-N'-~4-methoxy-6-methyl-pyrimidin-2-yl)-urea, N-(2-methoxycarbonylphenyl-sulfonyl)-N'-(4,6-dimethoxy-pyrimidin-2-yl)-urea, N-(2-methoxycarbonylphenyl-sulfonyl)-N'-(4-methoxy-6-methyl-pyrimidin-2-yl)-urea, N-(2-ethoxy-phenyl-sulfonyl)-N'-(4-difluoromethoxy-6-methoxy-pyrimidin-2-yl)-urea, N-(2-methoxyethoxyphenyl-sulfonyl)-N'-(4,6-dimethoxy-triazin-2-yl)-urea, N-(2-ethoxyphenyl-sulfonyl-N'-(4-chloro-6-methoxypyridin-2-yl)-urea, N-(2-ethoxy-phenylsulfonyl)-N'-(4-difluoromethoxy-6-methyl-pyrimidin-2-yl)-urea and N-[2-(2-chloroethylmercapto)-phenyl-sulfonyl]-N'-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-urea.
Oxime ethers which are suggested according to the present invention as being effective against the plant-damaging side-effect of herbicidally active sulfonylureas are those of the formula II

\ O_ - {} - X R O-R (II) / 4~0 ~(CH)n--CH

- 6 ~
wherein n is 1 or 2, R3 and R4 are each hydrogen or Cl-C4-alkyl9 R5 and R6 are each hydrogen, halogen, Cl-C4-alkyl~ Cl-C4-haloalkyl, Cl-C4-alkoxy, Cl-C4-haloalkoxy, Cl-C4-alkylthio, Cl-C4-haloalkylthio, Cl-C4-alkylsulfinyl, Cl-C4-alkylsulfonyl, C]-C4-haloalkylsulfinyl, Cl-C4-haloalkylsulfonyl or nitro, R7 and R8 separately are each Cl-C4-alkyl or C3-C4-alkenyl, or together are a 1,2-ethylene group or a 1,3-propylene group each unsubstituted or substituted by one or more alkyl groups, and X is a cyano group or a fluorinated Cl-C3-alkyl group which can also contain chlorine.
The radicals R3 - R8, as well as the Cl-C4-alkyl groups occurring in the radicals R3 - R8, can be straight-chain or branched-chain and are: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl and tert-butyl.
Preferred amongst these alkyl groups are Cl-C2-alkyl groups, and Rl as an alkyl group is preferably methyl.
This description ofalkyl groups applies also for the alkyl moieties of other substituent groups according to the definition of the formula II. Alkenyl can be for example: allyl, propenyl, i-propenyl, buten-2-yl, 2-methyl-propen-2-yl and 1-methyl-propen-2-yl, and is preferably an allyl group.
By halogen is meant for example fluorine, chlorine, bromine and iodine, especially fluorine or chlorine.
The fluorinated alkyl group X can be for example:
difluoromethyl, trifluoromethyl, chlorodifluoromethyl, tetrafluoroethyl, pentafluoroethyl and heptafluoropropyl.
Preferred among the stated X groups are perfluorinated alkyl groups, wherein a fluorine atom can be replaced by a chlorine atom. Particularly preferred groups X are trifluoromethyl, chlorodifluoromethyl and pentafluoroethyl.

:~L22~

The compounds of the :Eormula II in which R7 and R8 together form a 1,2-ethylene or 1,3-propylene group, each unsubstituted or substituted by one or more alkyl groups, constitute 1,3-dioxolane or 1,3-dioxane derivatives and correspond to the formula IIa ~ (R ) ~ ~ 19 P
'--C--XR O+CH
~ 3 / \2 (IIa) / O~D N O (CH) --CH ~CH2)m wherein n, R3, R4, R5, R6 and X have the meanings defined under the formula II, m is zero or 1, p is zero to 4, and R9 is a Cl-C3-alkyl group, preferably methyl. Preferred compounds of the formula IIa are those in which m is zero.
Preferred among the compounds of the formula II are the following subgroups:
a) compounds wherein n is 1, R3, R4 and R6 are hydrogen, R5 is hydrogen, halogen, methyl, difluoromethyl, trifluoro-methyl, chlorodifluoromethyl, methoxy, difluoromethoxy, trifluoromethoxy, chlorodifluoromethoxy, tetrafluoroethyl, tetrafluoroethoxy or trifluoromethylsulfonyl, X is a cyano group or perfluorinated Cl-C3-alkyl or chlorodifluoro-methyl, and R7 and R8 have the meanings defined under the formula II;
b) compounds wherein n is l, R3, R4 and R6 are hydrogen, R5 is hydrogen, fluorine, chlorine, methyl, difluoromethyl, trifluoromethyl, chlorodifluoromethyl, methoxy, difluoro-methoxy, trifluoromethoxy, chlorodifluoromethoxy, tetra-fluoroethyl, tetrafluoroethoxy or tetrafluoromethyl-sulfonyl, X is a cyano group or trifluoromethyl, chloro ~æ2~

difluoromethyl or pentafluoroethyl, and R7 and R8 together are a 1,2-ethylene group which is unsubstituted or substituted by 1-4 methyl groups;
c) compounds wherein n is 1, R3, R4 and R6 are hydrogen, R5 is hydrogen, fluorine, chlorine, trifluoromethyl or trifluoromethoxy, X is a cyano group or trifluoromethyl, chlorodifluoromethyl or pentafluoroethyl, and R7 and R8 together are a l,2-ethylene group which is unsubstituted or substituted by L-4 methyl groups;
d) compounds wherein n is 1, R3, R~ and R6 are hydrogen, R5 is fluorine or chlorine, X is a cyano group or trifluoro-methyl, chlorodifluoromethyl or pentafluoroethyl, and R7 and R8 together are a 1,2-ethylene group which is unsub-stituted or substituted by 1-4 methyl groups;
e) compounds wherein n is 1, R3, R4 and R6 are hydrogen, R5 is in the 3-position and is trifluoromethyl or nitro, X is a cyano group or trifluoromethyl, chlorodifluoro-methyl or pentafluoroethyl, and R7 and R8 together are a 1,2-ethylene group which is unsubstituted or substituted by 1-4 methyl groups;
f) compounds wherein n is 1, R3, R4 and R6 are hydrogen, R5 is hydrogen or fluorine, X is a cyano group, and R7 and R8 together are a 1,2-ethylene group which is unsubstituted or substituted by 1-4 methyl groups;
g) compounds wherein n is 1, R3, R4 and R6 are hydrogen, R5 is hydrogen or fluorine, X is a cyano group, and R7 and R8 together are a 1,2-ethylene group; and h) compounds wherein n is 1, R3, R~ and R6 are hydrogen, R5 is fluorine, X is a cyano group, and R~ and R8 together are a 1,2-ethylene group.

32~

g Preferred individual compounds are in particular:

l-phenyl-l-(1,3-dioxolan-2-yl-methoxyimino)-2,2,2-trifluoroethane, 1-(4-chlorophenyl)-1-(1,3-dioxolan-2-yl-methoximino)-2,2,2-trifluoroethane, 1-(4-chlorophenyl)-1-(2,2-diethoxyethoximino)-2,2,2-trifluoroethane, 1-(4-chlorophenyl)-1-(2,2-dimethoxyethoximino)-2,2,2-trifluoroethane, 1-(4-fluorophenyl)-1-(1,3-dioxolan-2-ylmethoximino)-2,2,2-trifluoroethane, 1-(2-fluorophenyl)-1-(1,3-dioxolan-2-yl-methoximino)-2,2,2-trifluoroethane, a-(1,3-dioxolan-2-ylmethoximino)-benzyl cyanide, a-(2,2-dimethoxyethoximino)-benzyl cyanide, a-(1,3-dioxan-2-yl-methoximino)-benzyl cyanide, a-(5,5-dimethyl-1,3-dioxan-2-yl-methoximino)-benzyl cyanide, a-~2,2-dimethoxyethoximino)-3,4-dichlorobenzyl cyanide, a-(1,3-dioxolan-2-yl-ethoximino)-3,4-dichlorobenzyl cyanide, a-(5,5-dimethyl--1,3-dioxan-2-yl-methoximino)-4-methoxy-benz~l cyanide, a-(2,2-diethoxyethoximino)-4-methoxybenzyl cyanide.
The oxime ethers of the formula II are suitable for protecting cultivated plants from the harmful effect of sulfonylureas. With regard to their use in combination with the aforementioned herbicides, the oxime ethers of the formula II can therefore be described as preventives or antidotes and also as safeners.
Of the compounds of the formula II there exist various stereoisomeric forms, namely the syn and anti forms of the oximes from which they are formed; and there also exist the individual enantiomers of those compounds of the formula II which possess an asymmetric centre. Such asymmetric centres are present when R3 has a meaning other than hydrogen, or when the radicals R7 and R8 differ from one another, or when the 1,2-ethylene or 1,3-propylene group formed by the radicals R7 and R8 is asymmetrically substituted. These stereoisomeric forms are likewise subject matter of the present invention.
Depending on the purpose of application, such an antidote of the formula II can be used for the pretreatment of the seed or seedlings of the cultivated plant (dressing of the seed or of cuttings), or can be introduced into the soil before or after sowing, or can be applied on its own or together with the herbicide before or after emergence of the plants. The treatment of the plant or of the seed or seedlings with the antidote can be carried out therefore essentially independently of the time of application of the phytotoxic chemicals. The treatment can however be effected by the simultaneous application of phytotoxic chemicals and antidote (tank mixture). The pre-emergence treatment includes both the treatment of the cultivated area before sowing (ppi = "pre-plant incorporation") and the treatment of the sown cultivated area before emergence of the plants.
The applied amounts of antidote in proportion to the herbicide depend largely on the mode of application. In the case of field treatment, where the herbicide and antidote are applied either simultaneously (tank mixture) or separately, the ratio of the amounts of antidote to herbicide is within the range of 1:10 to 10:1. The full protective action is however obtained as a rule with a :~22~

ratio of antidote to herbicide of 1:3 to 3:1. Which ratio is most suitable with regard to the optimum effect with a specific cultivated plant is determined from case to case, that is to say, depending on the type of herbicide to be used. With seed dressing and similar specific protective measures, however, the amounts of antidote required compared with for example the amounts of herbicide which would be applied later per hectar of cultivated land are much smaller. There are generally needed for seed dressing 0.5 to 50 g of antidote per kg of seed. As a rule, the maximum protective effect is obtained with amounts as low as 0.5 to 4 g of antidote per kg oE seed. When the antidote is to be applied shortly before sowing, by seed soaking, there are advantageously employed antidote solutions containing the active ingredient at a concen-tration of 1 - 10,000 ppm. The full protective action is as a rule obtained with a concentration o:E antidote of 10 - 1000 ppm.
Protective measures, such as seed dressing and treatment of cuttings with an antidote of the formula II, and possible subsequent field treatment with agricultural chemicals are as a rule separated by a considerable interval of time. Pretreated seed and plant material can subsequently come into contact, in agriculture, horticulture and forestry, with various chemicals. The present invention relates therefore also to protective compositions for cultivated plants, which compositions contain as active ingredient an antidote of the formula II, together with customary carrier materials. These prep-arations can if required additionally contain those agricultural chemicals against which the cultivated plant is to be protected.
~ ultivated plants applying within the scope oE the ~2~ 4 present invention are all those which in some form produce productive materials (seeds, roots, stalks, tubers, leaves, flowers, or components such as oils, sugar, starch, protein, and so forth), and which for this purpose are cultivated and preserved. These plants include for example varieties of cereals, such as wheat, rye, barley and oats, in addition particularly rice, sorghum, maize~ cotton, sugar beet, sugar cane, soybean, beans, peas, and the like.
The antidote of the invention can be used in all cases where a cultivated plant of the aforementioned varieties has to be protected against the harmful action of sulfonylureas of the formula I.
For the dressing of the seed of the cultivated plant, the seeds are thoroughly mixed in the desired ratio with the antidote of the formula II.
For application, the compounds of the formulae I and II are used either in an unmodified form or preferably together with auxiliaries customarily employed in formulation practice, and are thus processed in a known manner for example into the form of emulsion concentrates, directly sprayable and dilutable solutions, diluted emulsions, wettable powders, soluble powders, dusts or granulates, and also encapsulations in for example poly-meric substances. The application processes, such as spraying, atomising, dusting, scattering or pouring, and likewise the type of composition, are selected to suit the objectives to be achieved and the given conditions.
The formulations, that ls to say, the compositions or preparations containing the active ingredients of the formulae I and II and optionally a solid or liquid additive, are produced in a known manner, for example by the intimate mixing and/or grinding of the active ingredients with - 13 ~
extenders, such as with solvents, solid carriers and optionally surface-active compounds (tensides).
Suitable solvents are: aromatic hydrocarbons, prefer-ably the fractions C8 to C12, such as xylene mixtures or substituted naphthalenes, phthalic esters, such as dibutyl-or diocty~phthalate, aliphatic hydrocarbons, such as cyclohexane or paraffins, alcohols and glycols, as well as ethers and esters thereof, such as ethanol, ethylene glycol, ethylene glycol monomethyl or -ethyl ethers, ketones, such as cyclohexanone, strongly polar solvents, such as N-methyl-2-pyrrolidone, dimethyl sulfoxide or dimethyl-formamide, as well as optionally epoxidised vegetable oils, such as epoxidised coconut oil or soybean oil; or water.
The solid carriers used, for example for dusts and dispersible powders, are as a rule natural mineral fillers, such as calcite, talcum, kaolin, monomorillonite or attapulgite. In order to improve the physical properties, it is also possible to add highly dispersed silicic acid or highly dispersed absorbent polymers.
Suitable granulated adsorptive carriers are porous types, for example pumice, ground brick, sepiolite or bentonite;
and suitable nonsorbent carriers are materials such as calcite or sand. There can also be used a great number of pre-granulated materials of inorganic or organic nature, such as in particular dolomite or ground plant residues.
Suitable surface-active compounds are, depending on the nature of the active ingredients of the formulae I and II
to be formulated, nonionic, cationic and/or anionic tensides having good emulsifying, dispersing and wetting properties.
By 'tensides' are also meant mixtures of tensides.
Suitable anionic tensides are both so-called water-soluble soaps and water-soluble, synthetic, surface-active compounds.
Soaps which are applicable are the alkali metal, alkaline-earth metal or optionally substituted ammonium salts of higher fatty acids (C10-C22), for example the Na or K salts of oleic or stearic acid, or of natural fatty acid mixtures, which can be obtained for example from coconut oil or tallow oil. ~lso to be mentioned are the fatty acid-methyltaurine salts.
So-called synthetic tensides are however more frequently used, particularly fatty sulfonates, fatty sulfates, sulfonated benzimidazole derivatives or alkylarylsulfonates.
The fatty sulfonates or sulfates are as a rule in the form of alkali metal, alkaline-earth metal or optionally substituted ammonium salts, and contain an alkyl group having 8 to 22 C atoms, 'alkyl' including also the alkyl moiety of acyl groups, for example the Na or Ca salt of ligninsulfonic acid, of dodecylsulfuric acid ester or of a fatty alcohol sulfate mixture produced from natural fatty acids. Included among these are the salts of sulfuric acid esters and sulfonic acids of fatty alcohol ethylene oxide adducts. The sulfonated benzimidazole derivatives preferably contain 2 sulfonic acid groups and a fatty acid group having 8 - 22 C atoms. Alkylaryl-sulfonates are for example the Na, Ca or triethanolamine salts of dodecylbenzenesulfonic acid, of dibutylnaphthalene-sulfonic acid or of a naphthalenesulfonic acid-formaldehyde condensation product.
Also suitable are corresponding phosphates, for example salts of the phosphoric ester of a p-nonylphenol-(~
ethylene oxide adduct, or phospholipides.

~2~

Suitable nonionic tensides are in particular polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, saturated or unsaturated fatty acids and alkylphenols, which can contain 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon radical and 6 to 18 carbon atoms in the alkyl moiety of the alkylphenols.
Further suitable nonionic tensides are the water-soluble polyethylene oxide adducts, which contain 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups, with polypropylene glycol, ethylene-diaminopolypropylene glycol and alkylpolypropylene glycol having 1 to 10 carbon atoms in the alkyl chain. The compounds mentioned usually contain 1 to 5 ethylene glycol units per propylene glycol unit.
Examples of nonionic tensides which may be mentioned are: nonylphenolpolyethoxyethanols, castor oil polyglycol ethers, polypropylene/polyethyleneoxy adducts, tributyl-phenoxypolyethoxyethanol, polyethylene glycol and octyl-phenoxypolyethoxyethanol.
Suitable also are fatty acid esters of polyoxyethylene-sorbitan, such as polyoxyethylenesorbitan-trioleate.
In the case of the cationic tensides, they are in particular quaternary ammonium salts which contain as N-substituents at least one alkyl group having 8 to 22 C atoms and, as further substituents, lower, optionally halogenated alkyl, benzyl or lower hydroxyalkyl groups.
The salts are preferably in the form of halides, methyl sulfates or ethyl sulfates~ for example stearyltrimethyl-ammonium chloride or benzyldi(2-chloroethyl)ethylammonium bromide.
The tensides customarily used in formulation practice are described, inter alia, in the following publications:

~2~2~2~

" Mc Cutcheon's Detergents and Emulsifiers Annual", MC Publishing Corp., Ridgewood, New Jersey, 1979; and Slsely and Wood, "Encyclopedia of Surface Active Agents", Chemical Publishing Co., Inc. New York, 1964.
These preparations contain as a rule 0.1 to 99%, particularly 0.1 to 95%, of active ingredients, 1 to 99%
of a solid or liquid additive, and O to 25%, especially 0.1 to 25%, of a tenside.
Whereas commercial products are preferably in the form of concentrated compositions, the preparations employed by the end-user are as a rule diluted. The applied forms can be diluted down to 0.001% of active ingredient. The amounts applied are as a rule 0.1 to 10 kg of active ingredient (a.i.) per hectare, preferably 0.25 to 5 kg of active ingredient (a.i.) per hectare.
The compositions can also contain further additives, such as stabilisers, antifoam agents, viscosity regulators, binders and adhesives, as well as fertilisers or other active ingredients for obtaining special effects.
The active ingredients of the formulae I and II can be produced by known methods.
Compounds of the formula I are produced in an inert organic solvent.
One process for obtaining the compounds of the formula I comprises reacting a phenylsulfonamide of the formula III
Y SO ~H
\ / 2 2 ll (III) a ~ x wherein ~ and Y have the meanings defined under the formula I, in the presence of a base, with an N-pyrimidinyl-or N-triazinylcarbamate of the formula IV
~R
O N~
// \ 11 // ~
~C NH-- E
I ll \ / (IV) O ~ ~-. ~/ \
R
wherein E, Rl and R2 have the meanings defined under the formula I.
A second process for producing compounds of the formula I comprises reacting a phenylsulfonylisocyanate of the formula V
Y
\//\
2~=C=
~/\
x wherein X and Y have the meanings defined under the formula L, optionally in the presence of a base, with an amine of the formula VI
~R
N---H2N - ~ E (VI) \ /
N=;

wherein E, Rl and R2 have the meanings defined under the formula I~
Compounds of the formula I are produced using a further process by reacting a sulfonamide of the formula III given above, optionally in the presence of a base, with an ~2Z~

isocyanate or isothiocyanate of the formula VII
Rl ~o O=C=N E
\ / (VII) ;

wherein E, Rl and R2 have the meanings defined under the formula I.
Finally, the compounds of the formula I can be obtained also by reacting an N-phenylsulfonylcarbamate of the formula VIII
y ~, o ~
\ // \ 11 //
SO ~Uff~- -: ! 11 2 \ / (VIII), \\ / \
x wherein X and Y have the meanings defined under theformula I, with an amine of the given formula VI.
The resulting ureas of the formula I can, if desired, be converted by means of amines, alkali metal hydroxides or alkaline-earth metal hydroxides or quaternary ammonium bases into basic addition salts. This is effected for example by reaction with the equimolar amount of base and removal of the solvent by evaporation.
The starting materials of the formulae III, V and VIII can be produced by the following methods:

The sulfonamides of the formula III used as inter-mediates are obtained from the corresponding anilines by diazotisation and exchange of the diazo group for sulfur dioxide in the presence of a catalyst, such as copper-(I) chloride, in hydrochloric acid or acetic acid, and reaction of the formed phenylsulfonyl chloride with an ammonium hydroxide solution.
The compounds of the formula III can be obtained also by oxygen-alkylation or -alkenylation of hydroxyphenyl-sulfonamides with the corresponding halides or sulfuric acid esters.
The alkoxyphenylsulfonamides for their part can be obtained from the corresponding alkoxyanilides, as already mentioned9 or by chlorosulfonylation of alkoxybenzoles, and reaction of the resulting phenylsulfonyl chlorides with an ammonium hydroxide solution. Such reactions are known from J. Am. Chem. Soc. 62, 603 (1940).
The phenylsulfonylisocyanates of the formula V can be obtained by reactions of the sulfonamides of the formula III with phosgene in the presence of butylisocyanate, in a chlorinated hydrocarbon as solvent, at the reflux tempera ture. Similar methods of preparation are described in "Newer Methods of Preparative Organic Chemistry", Vol. VI, 223-2~1, Academic Press New York and London.
The N-phenylsulfonylcarbamates of the formula VII are obtained by reaction of the sulfonamides of the formula II
with diphenylcarbamate in the presence of a base. Similar processes are mentioned in the Japanese Patent Specification No. 61 169.
The starting materials of the formulae IV, VI and VII
are known or can be produced by known methods.
Isocyanates of the formula VII can be produced by reaction of amines of the formula VI with oxalyl chloride in a chlorinated hydrocarbon. Amines of the formula VI
are known and some are obtainable commercially~ or they 2~

- ~o ~
can be produced by known methods: cp. "The Chemistry of Heterocyclic Compounds", Vol2 XIV, Interscience Publishers, New York, London.
These reactions to compounds of the formula I are advantageously performed in aprotic, inert organic solvents, such as methylene chloride, tetrahydrofuran, acetonitrile, dioxane and toluene.
The reaction temperatures are preferably between -20 and +120C. The reactions in general proceeed slightly exothermically, and can be carried out at room temperature.
For shortening the reaction time or for initiating the reaction, it is advantageous to apply heat for a short period up to the boiling point of the reaction mixture.
The reaction times can be shortened also by the addition of a few drops of a base or of isocyanate as a reaction catalyst.
The final products can be isolated by means of concentration by evaporation and/or removal of the solvent by evaporation, and can be purified by recrystallisation or trituration of the solid residue in solvents in which they do not readily dissolve, such as in ethers, aromatic hydrocarbons or chlorinated hydrocarbons.
The oxime ethers of the formula II are produced by reacting a salt of an oxime of the formula IX

~_0 ~-x (IX), o~o N-OM

wherein M is an alkali metal cation or alkaline-earth metal cation, and R4, R5, R6 and X have the meanings given 2~L

under the formula II, with a 2-haloalkylacetal of the formula X

R~ O-R
Hal ( CH) --CH (X) \

wherein Hal is a halogen atom, especially a chlorine atom or a bromine atom, and n, R3, R7 and R8 have the meanings defined under the formula II. Suitable salts of an oxime of the formula IX are in particular the sodium and potassium salts. The reaction of the oxime of the formula IX with the haloacetal of the formula X is advantageously performed in an inert organic solvent. Polar solvents, such as acetonitrile, dimethylformamide, dimethyl sulfoxide, dimethylacetamide, methylpyrrolidone and tetramethylurea, are especially suitable. The reactants are used as a rule in an equimolar amount. For the reaction to proceed to completion, it is however possible to use the cne or the other reactant in excess. The reaction is advantageously carried out at elevated temperature, preferably between 50 and 90C. The reaction can also be performed in another solvent, for example toluene, but at a higher temperature and with a longer reaction time.
Those oximes of the formula IX in which X has the meaning defined under the formula II, with the exception of the cyano group~ can be produced in a known manner by reaction of the corresponding ketones with hydroxylamine.
The ketones required for this purpose can, depending on the structure, be produced by various procedures. Thus, the reaction of Grignard compounds of the formula XI

R~, ~MgHal (XI) R 5 ~0 wherein Hal is chlorine, bromine or iodine, and R4, R5 and R6 have the meanings defined under the formula II, with a carboxylic acid X-COOH, an acid chloride X-COCl or a nitrile X-CN, wherein X has the meaning defined under the formula II, with the excep~ion of the cyano group, yields the desired ketones (U.S. Patent No. 3,74~3,361).
The oximes of the formula IX in which X is a cyano group can be prepared by reaction of a benzyl cyanide of the formula XII
R~

o ~H ~N (XII), wherein R4, R5 and R6 have the meanings defined under the formula II, with butyl nitrile in the presence of a base, for example sodium methylate or sodium ethylate (S.J. Org.
Chem. 192-193/1937, or U.S. Patent 3,483,246 or German Offenlegungsschrift No. 2,150,399). It is possible in this manner to synthesise the following:
l-hydroximino-ortho-fluorobenzyl cyanide, l-hydroximino-meta-fluorobenzyl cyanide, and l-hydroximino~para-fluorobenzyl cyanide.
The corresponding o-, m- and p-fluorobenzyl cyanides are obtainable commercially.
The ring-~luorinated benzyl cyanides for their part 2~244 are obtainable from the correspondingly ring-substituted benzyl chlorides by reaction with potassium cyanide or sodium cyanide. The 4-fluorobenzyl cyanide can be produced for example by chloromethylation of fluoro-benzene (Bl. [5] 20 C 45 (1953)). The 2- or 3-fluorobenzyl chloride is produced by side-chain chlorination of the 2- or 3-fluorotoluene obtainable, by a Sandmayer reaction, from 2- or or 3-aminotoluene.
The more simple oximes can be bought: 2-hydroximino-acetonitrile is a known intermediate.
The haloalkyl-acetals of the formula X can be produced by condensation of the corresponding alcohols and haloaldehydes. The more simple ones, for example 2-bromomethyl-1,3-dioxolane and 2-chloromethyl-1,3-dioxolane are known as intermediates.
Example 1: Production of N-(1,3-dioxolan-2-yl-methoxy)-imino-ortho-fluoroacetonitrile.
In a 100 ml round-bottomed flask, 2.3 g (0.1 mol) of metallic sodium are dissolved in 50 ml of absolute ethanol, and 18.6 g (0.1 mol) of l-hydroximino-ortho-fluorophenylacetonitrile are added. After completion of the addition, stirring is maintained for half an hour at room temperature, and the solvent is then evaporated off.
There are added dropwise to the solution of the residue in 75 ml of dimethyl sulfoxide, with stirring, 18.4 g (0.11 mol) of 2-bromomethyl-1,3-dioxolane, and stirring is continued for 4 hours at an internal temperature of 60-70C. The formed suspension is afterwards cooled and poured into an ice-water mixture. The reaction product is obtained from the resulting mixture by extraction with methylene chloride. The extract is dried over sodium sulfate and the solvent is evaporated off. There is ~Z~32 obtained as crude product a crystalline precipitate, which is purified by recrystallisation from ethanol.
The yield is 14.0 g (56% of theory) of N-(1,3-dioxolan-Z-yl-methoxy)-imino-ortho-fluorophenylacetonitrile, m.p. 46-47~C.
There are obtained in an analogous manner, starting from l-hydroximino-meta-fluorophenylacetonitrile and l-hydroxyimino-para-phenylacetonitrile, or the sodium salts thereof, by reaction with 2-bromomethyl-1~3-dioxolane:
N-(1,3-dioxolan-2-yl-methoxy)-imino-meta-fluorophenyl-acetonitrile and N-(1,3-dioxolan-2-yl-methoxy)-imino-para-fluoroacetonitrile, m.p. 68-71C.
Example 2: a-(1,3-Dioxolan-2-ylmethoxyimino)-benzyl cyanide (Z ~orm).
15.4 g of the sodium salt of a-phenylacetonitrile oxime (Z form) are dissolved in 70 ml of DMS0; 16.7 g of bromomethyl-dioxolane are added and the mixture is stirred at 60C for 4 hours. There are then added 150 ml of ether and washing is performed three times with 100 ml of H20 each time. The ether phase is dried with MgS04 and concentrated by evaporation. The crude product (17.8 g9 m.p. 67C) is crystallised from ether/hexane 1:3 and yields 16.7 g of a-(1,3-dioxolan-2-ylmethoximino)-benzyl cyanide (Z form), m.p. 76C.

~ 8 Example 3 .

Formulation Examples for active ingredients of the formula II or for mixtures of these active ingredients with herbicides of the formula I
a) Wettable powders a) b) c) active ingredient of the formula II 20% 60% 0.5%
or mixture thereof with a herbicide of the formula I
sodium lignin sulfonate 5% 5% 5%
sodium lauryL sulfate 3%
sodium diisobutylnaphthalene sulfonate - 6% 6%
octylphenolpolyethyleneglycol ether - 2% 2%
(7-8 mols of ethylene oxide) highly dispersed silicic acid 5% 27% 27%
~aolin 67%
sodium chloride - - 59.5%
The active ingredient is well mixed with the additives and the mixture is thoroughly ground in a suitable mill.
Wettable powders which can be diluted with water to give suspensions of the required concentration are obtained.
b) Emulsion concentrates a) b) -active ingredient of the formula II 10% 1%
or mixture thereof with a herbicide of the formula I
octylphenolpolyethylene glycol ether 3% 3%
(4-5 mols of ethylene oxide) calcium dodecylbenzene sulfonate 3% 3%
castor oil polyglycol ether 4% 4%
(36 mols of ethylene oxide) cyclohexanone 30% 10%
xylene mixture 50% 79%
Emulsions of any desired concentration can be obtained from these concentrates by dilution with water.

~L22~32~

c) Dusts a) b) actlve ingredient oE the formula II 0.1% 1%
or mixture thereof with a herbicide of the formula I
talcum 99 9%
kaolin - 99%
Dusts ready for use are obtained by mixing the active ingredient with the carriers and grinding the mixture in a suitable mill.
d) Extruder ~ranulate_ a) b) active ingredient of the formula II 10~/o 1%
or mixture thereof with a herbicide of the formula I
sodium lignin sulfonate 2% 2%
carboxymethylcellulose 1% 1%
kaolin 87% 96%
The active ingredient is mixed and ground with the additives, and the mixture is moistened with water. This mixture is extruded and then dried in a stream of air.
e) Coated granulate active ingredient of the formula II 3%
or mixture thereof with a herbicide of the formula I
polyethylene glycol (M.W. 200) 3%
kaolin 9~%
The finely ground active ingredient is evenly applied, in a mixer, to the kaolin moistened with polyethylene glycol. Dustfree coated granulates are obtained in this manner.

f) Suspension concentrates ~) b) active ingredient of the formula II 40% 5%
or mixture thereof with a herbicide of the formula I
ethylene glycol 10% 10%
nonylphenolpolyethylene glycol ether ~% 1%
(15 mols of ethylene oxide) sodium lignin sulfonate 10% 5%
carboxymethylcellulose 1% 1%
37% aqueous formaLdehyde solution0.2% 0.2%
silicone oil in the form of a 75%o.8a/o0.8%
aqueous emulsion water 32% 77%
The finely ground active ingredient is intimately mixed with the additives. There is thus obtained a suspension concentrate from which can be produced, by dilution wi~h water, suspensions of the concentration required.
g) Salt solution active ingredient of the formula II 5%
or mixture thereof with a herbicide of the formula I
isopropylamine 1%
octylphenolpolyethylene glycol ether 3%
(78 mols of ethylene oxide) water 91%
Biological Examples The capability of the compounds of the formula II to protect cultivated plants against the action of strong herbicides can be seen from the following Examples. In the test descriptions, the compounds of the formula II
are designated as antidotes.

2~
. .

Example ~: Seed dressing with_antidote: herbicide in t_ post-emergence process on maize ~ aize seeds of the "LG 5" variety are mixed in a glass container with the substance to be tested as antidote.
Seeds and product are thoroughly mixed together by shaking and rotation. Pots oE the same shape (11 cm upper diameter) are filled with soil, and the dressed seeds are sown therein. The herbicide is applied in the post-emergence process (three-leaf stage of the plant), and 21 days after application oE the herbicide, the protective action of the antidote is estimated in per cent.
The plants treated with the herbicide alone and the completely untreated control plants provide reference values.
As can be seen from the results summarised in the Table, the antidote affords a high level of protection.
(a.i. = active ingredient) Nerbicide:
N-[2-(2-butenyloxy)-phenyl-sulfonyl]-N'-(4-methyl-6- 1.5 1.0 0.5 methoxy-triazin-2-yl)-urea kg of a.i./ha Ant ido t e: _ _ _ _ h- (1,3-dioxolan-2-ylmethox-i~ino)-ben~yl cyanide (Z form) 4 2 1 4 2 1 4 2 g of a.i./1~g of seeds _ _ rela~ive protective action50 635063 63 63 25 25 25 ~L~28~

Herbicide:
N-(2-methoxycarbonyl-phenyl-sulfonyl)-N'-(4,6-difl~loro- ~.5 0.25 0.125 methoxy-pyrimidin-2-yl)-kg of a.i./ha Antidote: _ _ _ _ _ ~-(1,3-dioxolan-2-ylmethox-imino)-benzyl cyanide 4 2 14 2 1 4 2 g of a.i./kg of seeds _ _ _ _ _ _ ~
relative protective action 50 63 12.5 j3 63 50 38 38 38 Example 5: Seed dressin~ with antidote: herbicide in the pre-emergence process on maize Maize seeds of the "LG 5" variety are mixed in a glass container with the substance to be tested as antidote, Seeds and product are well mixed together by shaking and rotation. Pots of the same shape (upper diam. 11 cm) are filled with soil, and the dressed seeds are sown therein.
After the seeds have been covered with soil, the herbicide is applied in the pre-emergence process. The protective action of the antidote is estimated in per cent 14 days after application of the herbicide. The plants treated with ~he herbicide alone and the cornpletely untreated plants provide reference values.

The results given in the Table below illustrate the protective action of the antidote:

Herbicide:
N-[2-(2-butenyloxy)-phenyl-sulfonyl]-N'-(4-methyl-6- l.S 1.0 0.5 methoxy-triazin~2-yl)-urea kg of a.i./ha . __ _ . _ .
Antidote:
a~-(1,3-dioxolan-2-ylmethox-ililino)-benzyl cyanide (Z form) 4 2 1 4 2 1 4 2 1 g of a.i./kg of seeds .. _ . _ relative protective action 25 38 38 25 2512.5 25 12~, 12.5 in % .. __ . __.. ~._ . __ Herbicide:
N-(2-methoxycarbonyl-phenyl-sulfonyl)~N'-4,6 difluoro- 0.25 0.125 0.062 methoxy-pyrimidin-2-yl)-urea kg of a.i./'na . _ _ Antidote: 2 ~-(1,3-dioxolan-2-yl- 2 2 methoximino)-benzyl cyanide ~ of a.i./kg of seeds relative protective action 38 38 5 in ~
. __ ~L2;2~

Antidote: _ ~-(1,3-dioxolan-2-ylmethox- 2 1 O.S 2 1 0.5 ilnino)-benzyl cyanide (Z ~orm) g of a.i./kg of seeds _ Herbicide:
N-(2-chlorophenyl-sulfonyl)-0.062 kg a.i./ha 0.031 kg a.i./ha N'-(4-methyl-6-dimethoxy-triazin-2~yl)~urea relative protective action 12.5~ 12.5~ 12.5~ 12.5~ 12.~ 12-5 .
~erbicide:
N-[2-(2'-chloroethoxy)-0,062 kg a.i./ha 0.032 kg a.i./ha phenyl-sulfonyl]-N'-(4-methyl-6-methoxy-triazin-2-yl)-urea relative protective action: 38~ 25~ 12.5~ 38~ 38%
. . _ ~erbicide:
N-[2-(2'-methoxyethoxy)-0.062 kg a i /ha 0.031 kg a i /ha phenyl-sulfonyl]-N'-(~i- . . . .
methyl-6-methoxy-triazin-2 yl-urea relative protective action: 38~ 25~ 12.5~o 38~ 25~ 38~

Example 6: Seed dressin~ with antidote: herbicide in the pre-emer~ence process on barley Barley seeds are mixed in a glass container with the substance to be tested as antidote. Seeds and product are well mixed together by shaking and rotation. Pots of the same shape (upper diameter 11 cm) are filled with soil, and the dressed seeds are sown therein. After the seeds have been covered with soil, the herbicide is applied in the pre-emergence process. The protective action of the antidote is estimated in per cent 14 days after application of the herbicide. The plants treated with the 32~

herbicide alone and the completely untreated plants provide reference values.
The results show that a considerable protective action is afforded by the antidote:

_ ., ..
Herbicide:
N-[2-(2'-methoxyethoxy)-phenyl-sulfonyl]-N'- 0.125 0.062 0.031 (4-methyl-6-methoxy~
tria~in-2-yl)-urea kg of a.i./ha Antldote: ~ _ _ ~-(1,3-dioxolan-2-yl)-~ethoximino)-benzyl 2 1 0.5 2 1 0.5 21 0.5 cyanide (Z fo~m) g of a.i./kg o~ seeds .. _._ . _ _ relative protective l12.5 12.5 12.5 12.5 12.5 12.5 38 38 38 action in % _ I _ _ _ _ Exam~ : Seed dressin~ with antidote: herbicide in the pre-emergence process on sorghum Sorghum seeds are mixed in a glass container with the substance to be tested as antidote. Seeds and product are well mixed together by shaking and rotation. Pots of the same shape (upper diameter 11 cm) are filled with soil, and the dressed seeds are sown therein. After the seeds have been covered with soil, the herbicide is applied in the pre-emergence process. The protective action of the antidote is estimated 14 days after the application of the herbicide. The plants treated with the herbicide alone and completely untreated plants provide reference values.

~2~

The results clearly show the protective action obtained by use of the antidote:

. __ _ I
Antidote:
~-(1,3-dioxolan- 2 1 0.52 1 0.5 2 1 0.5 2-ylmethoximino)-benzyl cyanide (Z form) g of a.i./kg of seeds _ _ Herbicide:
N-(2-chlorophenyl- 0.125 0.062 0.031 sulfonyl)-N'-(4- kg a.i./ha kg a.i.~la kg a.i./ha methyl-6-methoxy-triazin-2-yl)-urea relative protective 25~ 12.5~ 25~50~ 50~ 50~ 50~ 65~ 63 action: _ Herbicide:
N-[2-(2'-chloroethoxy- 0.125 0.062 0-031 phenyl--sulfonyl]-N'- kg a.i./ha kg a.i.~la kg a.i./ha (4-methyl-6-methoxy-triazin-2-yl)-urea relative protective 12.5~ 12.5~ 12.5 38~ 38~ 12.5~ 50~ 50~ -action:
Herbicide:
N-[-2-(2'-methoxy- 0.125 0.062 0.031 ethoxy)-phenyl- kg a.i./ha kg a.i./ha kg a.i./ha sulfonyl]-N'-(4-methyl-6-methoxy-triazin-2-yl)-urea relative protective action~ 12.5~ - - S0~ 38~ 25~ 75~ 50~ 38 _ Herbicide:
N-[2-(3-trifluoro- 0.1250.062 0.031 propen-l-yl~- kg a.i./hakg a.i./ha kg a.i./ha phenyl-sulfonyl]-N'-(4-methyl-6-methoxy-triazin-2-yl)-urea action 38~ 63~ 50%38~ 50~ 38~ 12.5~ 25~ 38 _ _ . . _ Herbicide:
N-(2-pentafluoroethoxy-phenyl-sulfonyl) N'- 0.l25 0.125 0.062 (4,6-dimethoxypyrimidi~ kg a.i./ha kg a.i./ha kg a.i~ha 2-yl)-urea action 50~ _- 38~ - - 25~ ~
Herbicide- _ N-[2-(2~-methoxyethoxy) .
phenyl-sulfonyl]-N'-(4- 0.062 0.031 methyl-6-methoxy- g a.i./ha g a.i./ha triazin-2-yl)-urea _ _ Antidote: relative protective action a-(2,2-dimethoxy- 50~ 63 ethoxyimino)-benæyl cyanide 2 g of a.i./kg of seeds ~-(1,3-dioxan-2-yl)-methoximino)-benzyl 50~ 63 cyanide 2 g of a.i./kg of seeds _ ~-(5,5 dimethyl-1,3-dioxan-2-yl-methox- 50~ 63 imino)-benzyl cyanide 2 g of a.i./kg of seeds .
~-(2,2-dimethoxy-ethoxyimino)-3,4- 12.5~ 12.5 dichlorobenzyl cyanide 2 g of a.i./k~ of seeds ~ .

2~

Example 8: Tank mixture in the pre-emergence process on wheat . .
Wheat seeds are sown, in a greenhouse, in pots of the same shape (upper diameter 11 cm) each containing .5 1 of soil. After the seeds have been covered with soil, the substance to be tested as antidote and the herbicide are applied together as a tank mixture to the surface of the soil. The protective action of the antidote is estimated in per cent 21 days after application. The plants treated with the herbicide alone and the completely untreated plants provide reference values.
A~ clear protective action is obtained as a result of the antidote:

. Herbicide: . .

N-(2-chlorophenyl-sulfonyl)-~'-(4-methyl- 0.125 0.0620.031 O.OIS

6-methoxy-triazin-2-yl)-kg of a.i./ha .

Antidote:
~-(1,3-dioxolan-2-ylmethoxy-0.125 0.0620.031 O.OlS
imino)-ben~yl cyanide (Z fonn) ._. , relative protective action in % 50 33 ZS 12.5 ~%2~

Exam~le 9: Tank mixture in the pre-emergence process on barley Barley seeds are sown, in a greenhouse, in pots of the same shape (upper diameter 11 cm) each containing 0.5 litre of soil. After the seeds have been covered with soil, the substance to be tested as antidote and the herbicide are applied together as a tank mixture to the surface of the soil. The protective action of the antidote is estimated in per cent 21 days after application. The plants treated with the herbicide alone and the con~pletely untreated plants provide reference values.

Antidote:

~-(1,3-dioxolan-2-ylmethoximino)- 0.125 0 062 benzyl cyanide (Z form) kg of a.i./ha Herbicide:

N-[-(2'-chloroethoxy)-phenyl-sulfonyl]-ii'-(4-methyl-6- 0.125 0.062 methoxy-triazin-2-yl)-urea kg of a.i./ha relative protective action in % 50 25

Claims (24)

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

1. A herbicidal composition which comprises:
(a) a herbicidally active amount of a sulfonylurea of the formula I

(I) wherein X is halogen, C1-C3-haloalkenyl, C1-C3-alkoxycarbonyl, C3-C4-alkenyloxy, C1-C3-haloalkoxy, C1-C3-haloalkylthio, C1-C3-alkoxy-C1-C2-alkoxy or nitro, X1 is hydrogen, or together with X forms a bridge member 2-O-CH2CH2-3, or , Y is hydrogen or halogen, E is nitrogen -N= or methine -CH=, R1 is halogen, C1-C3-alkyl, C1-C3-alkoxy, C1-C4-haloalkoxy or cyclopropyl, and R2 is C1-C3-alkyl, C1-C3-alkoxy, C1-C4-haloalkoxy, cyclo-propyl or dimethylamino, and (b) a herbicide antagonistic amount of an oxime ether of the formula II

(II) wherein n is 1 or 2, R3 and R4 are each hydrogen or C1-C4-alkyl, R5 and R6 are each hydrogen, halogen, C1-C4-alkyl, C1-C4-halo-alkyl, C1-C4-alkoxy, Cl-C4-haloalkoxy, C1-C4-alkylthio, C1-C4-haloalkylthio, C1-C4-alkylsulfinyl, C1-C4-alkylsulfonyl, C1-C4-haloalkylsulfinyl, C1-C4-haloalkylsulfonyl or nitro, R7 and R8 separately are each C1-C4-alkyl or C3-C4-alkenyl, or together are a 1,2-ethylene group or 1,3-propylene group each unsubstituted or substituted by one or more alkyl groups, and X is a cyano group or a fluorinated C1-C3-alkyl group which can also contain chlorine, and (c) if desired, an agriculturally acceptable carrier.

2. A herbicidal composition according to claim 1, wherein the quantity ratio of antidote to herbicidal active ingredient is between 1:10 and 10:1.

3. A herbicidal composition according to claim 1, which contains as herbicidal active ingredient a sulfonyl-urea selected from the group comprising: N-[2-(2'-chloroethoxy)-phenyl-sulfonyl]-N'-(4-methyl-6-methoxy-triazin-2-yl)-urea, N-[2-(2'-methoxyethoxy)-phenyl-sulfonyl]-N'-(4-methyl-6-methoxy-triazin-2-yl)-urea, N-[2-(2-butenyloxy)-phenyl-sulfonyl]-N'-(4-methyl-6-methoxy-triazin-2-yl)-urea, N-[2-(3-trifluoropropen-1-yl)-phenyl-sulfonyl]-N'-(4-methyl-6-methoxy-triazin-2-yl)-urea, N-(2,5-di-chlorophenyl-sulfonyl)-N'-(4 methyl-6-methoxypyrimidin-2-yl)-urea, N-(2-methoxycarbonyl-phenyl-sulfonyl)-N'-(4-methyl-6-di-fluoromethoxy-pyrimidin-2-yl)-urea, N-(2-pentafluoroethoxyphenyl-sulfonyl)-N'-(4,6-dimethoxytriazin-2-yl)-urea, N-(2-chlorophenyl-sulfonyl)-N'-(4-methyl-6-methoxy-triazin-2-yl)-urea, N-(2-methoxy-carbonyl-phenyl-sulfonyl)-N'-(4,6-dimethyl-pyrimidin-2-yl)-urea, N-(2-allyloxy-phenylsulfonyl)-N'-(4-methyl-6-ethoxy-triazin-2-yl)-urea, N-(2-nitrophenyl-sulfonyl)-N'-(4-methyl-6-difluoro-methoxypyrimidin-2-yl)-urea and N-(2-methoxycarbonyl-phenyl-sulfonyl)-N'-(4-methyl-6-methoxy-triazin-2-yl)-urea, N-(2-difluoromethoxyphenylsulfonyl)-N'-(4-methyl-6-methoxy-pyrimidin-2-yl)-urea, N-(2-methoxyethoxyphenyl-sulfonyl)-N'-[4-methoxy-6-(2',2',2'-trifluoroethoxy)-1,3,5-triazin-2-yl]-urea, N-(2-methoxycarbonylphenyl-sulfonyl)-N'-(4-cyclopropyl-6-methoxy-1,3,5-triazin-2-yl)-urea, N-(2-difluoromethoxyphenyl-sulfonyl)-N'-(4-cyclo-propyl-6-methoxy-1,3,5-triazin-2-yl)-urea, N-[2-(3',3',3'-trifluoroprop-l-en-l-yl)-phenyl-sulfonyl]-N'-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-urea, N-(2-methoxycarbonyl-phenyl-sulfonyl)-N'-(2,4-difluoromethoxy-pyrimidin-2-yl)-urea, N-(2-difluoromethoxyphenyl-sulfonyl)-N'-(4-dimethyl-amino-6-methoxy-1,3,5-triazin-2-yl)-urea, N-[2-(1',2'-dichlorovinyloxy)-phenyl-sulfonyl]-N'-(4-methoxy-6-methyl-1,3,5-triazin-1-yl)-urea, N-(2,2-dioxo-3-methyl-1-oxa-2-thia-1,2,3,4-tetrahydro-naphthalen-8-yl)-N'-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-urea, N-(2,2-dioxo-3-methyl-1-oxa-2-thia-1,2,3,4-tetrahydro-naphthalen-8-yl)-N'-(4-methoxy-6-methyl-pyrimidin-2-yl)-urea, N-(2-methoxy-carbonylphenyl-sulfonyl)-N'-4,6-dimethoxypyrimidin-2-yl)-urea, N-(2-methoxycarbonylphenyl-sulfonyl)-N'-(4-methoxy-6-methylpyrimidin-2-yl)-urea, N-(2-ethoxyphenyl-sulfonyl)-N'-(4-difluoromethoxy-6-methoxy-pyrimidin-2-yl)-urea, N-(2-methoxyethoxyphenyl-sulfonyl)-N'-(4,6-dimethoxy-triazin-2-yl)-urea, N-(2-ethoxyphenyl-sulfonyl)-N'-(4-chloro-6-methoxypyrimidin-2-yl)-urea, N-(2-ethoxy-phenylsulfonyl)-N'-(4-difluoromethoxy-6-methylpyrimidin-2-yl)-urea and N-[2-(2-chloroethylmercapto)-phenyl-sulfonyl)-N'-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-urea, which herbicidal composition also contains as antidote an oxime ether of the formula II according to claim 1.

4. A herbicidal composition according to claim 1 containing a herbicidal active ingredient of the formula I, which composition contains, as antidote, an oxime ether of the formula II according to claim 1, wherein n is 1, R3, R4 and R6 are hydrogen, R5 is hydrogen, halogen, methyl, difluoromethyl, trifluoromethyl, chlorodifluoromethyl, methoxy, difluoromethoxy, trifluoromethoxy, chlorodifluoro-methoxy, tetrafluoroethyl, tetrafluoroethoxy or trifluoro-methylsulfonyl, X is a cyano group or perfluorinated C1-C3-alkyl or chlorodifluoromethyl, and R7 and R8 have the meanings defined in claim 1.

5. A herbicidal composition according to claim 1 containing a herbicidal active ingredient of the formula I, which composition contains, as antidote, an oxime ether of the formula II according to claim 1, wherein n is 1, R3, R4 and R6 are hydrogen, R5 is hydrogen, fluorine, chlorine, methyl, difluoromethyl, trifluoromethyl, chloro-difluoromethyl, methoxy, difluoromethoxy, trifluoromethoxy, chlorodifluoromethoxy, tetrafluoroethyl, tetrafluoroethoxy or tetrafluoromethylsulfonyl, X is a cyano group or trifluoromethyl, chlorodifluoromethyl or pentafluoroethyl, and R7 and R8 together are a 1,2-ethylene group which is unsubstituted or substituted by 1-4 methyl groups.

6. A herbicidal composition according to claim 1 containing as active ingredient a sulfonylurea of the formula I, which composition contains, as antidote, 1-phenyl-1-(1,3-dioxolan-2-yl-methoximino)-2,2,2-tri-fluoroethane.

7. A herbicidal composition according to claim 1 containing as active ingredient a sulfonylurea of the formula I, which composition contains, as antidote, 1-(4 chlorophenyl)-1-(1,3-dioxolan-2-yl-methoximino)-2,2,2-trifluoroethane.

8. A herbicidal composition according to claim 1 containing as active ingredient a sulfonylurea of the formula I, which composition contains, as antidote, 1-(4-chlorophenyl)-1-(2,2-diethoxyethoximino)-2,2,2-trifluoroethane.

9. A herbicidal composition according to claim 1 containing as active ingredient a sulfonylurea of the formula I, which composition contains, as antidote, 1-(4-chlorophenyl)-1-(2,2-dimethoxyethoximino)-2,2,2-trifluoroethane.

10. A herbicidal composition according to claim 1 containing as active ingredient a sulfonylurea of the formula I, which composition contains, as antidote, 1-(4-fluorophenyl)-1-(1,3-dioxolan-2-ylmethoximino)-2,2,2-trifluoroethane.

11. A herbicidal composition according to claim 1 containing as active ingredient a sulfonylurea of the formula I, which composition contains, as antidote, a-(1,3-dioxolan-2-ylmethoximino)-benzyl cyanide.

12. A herbicidal composition according to claim 1 containing as active ingredient a sulfonylurea of the formula I, which composition contains, as antidote, .alpha.-(2,2-dimethoxyethoximino)-benzyl cyanide.

13. A herbicidal composition according to claim 1 containing as active ingredient a sulfonylurea of the formula I, which composition contains, as antidote, 1-(2-fluorophenyl)-1-(1,3-dioxolan-2-yl-methoximino)-2,2,2-trifluoroethane.

14. A herbicidal composition according to claim 1 containing as active ingredient a sulfonylurea of the formula I, which composition contains, as antidote, .alpha.-(1,3-dioxan-2-ylmethoximino)-benzyl cyanide.

15. A herbicidal composition according to claim 1 containing as active ingredient a sulfonylurea of the formula I, which composition contains, as antidote, .alpha.-(5,5-dimethyl-1,3-dioxan-2-yl methoximino)-benzyl cyanide.

16. A herbicidal composition according to claim 1 containing as active ingredient a sulfonylurea of the formula I, which composition contains, as antidote, .alpha.-(2,2-dimethoxyethoximino)-3,4-dichlorobenzyl cyanide.

17. A herbicidal composition according to claim 1 containing as active ingredient a sulfonylurea of the formula I, which composition contains, as antidote,.alpha.-(1,3-dioxolan-2-ylethoximino)-3,4-dichlorobenzyl cyanide.

18. A herbicidal composition according to claim 1 containing as active ingredient a sulfonylurea of the formula I, which composition contains, as antidote, .alpha.-(2,2-dimethyl-1,3-dioxan-2-ylmethoximino)-4-methoxybenzyl cyanide.

19. A herbicidal composition according to claim 1 containing as active ingredient a sulfonylurea of the formula I, which composition contains, as antidote, .alpha.-(2,2-diethoxyethoxyimino)-4-methoxybenzyl cyanide.

20. A process for protecting crops of cultivated plants from damage caused by sulfonylureas, which process comprises combining the application of a herbicidally active amount of a sulfonylurea of the formula I according to claim 1 to the crop area of the cultivated plants, to the seeds or seedlings of the plants, or to the plants themselves, with the application of a herbicide-antagonistic active amount of an oxime ether of the formula II
according to claim 1.

21. A process according to claim 20 for protecting cultivated plants from damage that could otherwise occur on appli-cation of a sulfonylurea of the formula I according to claim 1, which process comprises a) treating the cultivated area for the plants before or during application of the sulfonylurea, or b) treating the seeds or seedlings of the plants themselves with an effective amount of an oxime ether of the formula II
according to claim 1.

22. A process according to claim 20 for protecting culti-vated plants from damage that could otherwise occur on application of a sulfonylurea of the formula I according to claim 1, wherein the oxime ether used is .alpha.-(1,3-dioxolan-2-ylmethoximino)-benzyl cyanide.

23. A process according to claim 20 wherein from 0.1 to 10 kg/ha of herbicide-antidote active mixture is applied.

24. A process according to claim 20 wherein from 0.25 to 5 kg/ha of herbicide-antidote active mixture is applied.