CA1148164A - 5-imino-imidazolidin-2-ones, herbicides containing them, and processes for combating unwanted plant growth with these compounds - Google Patents

Abstract

O.Z. 0050/034008 ABSTRACT OF THE DISCLOSURE: 5-Imino-imidazolidin-2-ones of the formula

Description

816~

o . z . ooso/034008 5-IMINO-IMIDAZOLIDIN-2-ONES, HERBICIDES CONTAINII~G THEM, AND
PROCESSES FOR COMBATING UNWANTED PLANT GROWTH WITH THESE CO~OUNDS

The present invention relates to new and valuable 5-imino--imidazolidin-2-ones, herbicides containing these compounds as active ingredients, and processes for combating unwanted plant growth with these compounds.
2C The use of 4-alkyl-5-imino-imidazolidin-2-ones as herbicides has been disclosed (Belgian Patent 728,537). The examples of this patent relate to the control of a few broadleaved unwanted plants in various cereals, carrots and flax.
We have now found that 5-imino-imidazolidin-2-ones of the formula CH~ I, NH

. 1148164 o.z. 0050/034008 where R1, R2 and R3 are identical or different and each denotes hydrogen, halogen (e.g., fluorine, chlorine, bromine or iodine), unsubstituted or halogen-substituted alkyl, alkoxy or alkylthio, each of from 1 to 4 carbon atoms (e.g., methyl, ethyl, 2-chloro-ethyl, 1-chloro-2-propyl, isopropyl, tert-butyl, methoxy, ethoxy, tert-butoxy, trifluoromethyl, tetrafluoroethoxy, or methylthio), cyano or nitro, control, preferably on preemergence application, a number of agriculturally important broadleaved weeds and un-wanted grasses without damaging important crop plants, such as ~ groundnuts, soybeans and sorghum.
m e following compounds are examples of the novel active ingredients:
1-phenyl-3-methyl-5-imino-imidazolidin-2-one, 1-(2-fluorophenyl)-3-methyl-5-imino-imidazolidin-2-one, 1-(2-chlorophenyl)-3-methyl-5-imino-imidazolidin-2-one, 1-(3-chlorophenyl)-3-methyl-5-imino-imidazolidin-2-one, 1-(4-chlorophenyl)-3-methyl-5-imino-imidazolidin-2-one, 1-(4-ethylphenyl)-3-methyl-5-imino-imidazolidin-2-one, 1-[(4-(2-chloroethyl)-phenyl]-3-methyl-5-imino-imidazolidin-2-one, 2C 1-[3-(1,1,2,2-tetrafluoroethoxy)-phenyl]-3-methyl-5-imino--imidazolidin-2-one, 1-(3-isopropylphenyl)-3-methyl-5-imino-imidazolidin-2-one, 1-(4-isopropylphenyl)-3-methyl-5-imino-imidazolidin-2-one, 1-t4-(1-chloro-2-isopropyl)-phenyl]-3-methyl-5-imino--imidazolidin-2-one, 1-(3-tert.-butylphenyl)-3-methyl-5-imino-imidazolidin-2-one, 1-(4-tert.-butylphenyl)-3-methyl-5-imino-imidazolidin-2-one,

- 2 -. ~1481~4 o.z. oo50~034008 1-(3,4-dif'luorophenyl)-3-methyl-5-imino-imidazolidin-2-one, 1-(3-chloro-4-fluorophenyl)-3-methyl-5-imino-imidazolidin-2-one, 1-(3,4-dichlorophenyl)-3-methyl-5-imino-imidazolidin-2-one, 1-(3,5-dichlorophenyl)-3-methyl-5-imino-imidazolidin-2-one, 1-(3-bromo-4-chlorophenyl)-3-methyl-5-imino-imidazolidin-2-one, 1-(3-chloro-4-methylphenyl)-3-methyl-5-imino-imidazolidin-2-one, 1-(3-chloro-4-methoxyphenyl)-3-methyl-5-imino-imidazolidin--2-one, 1-(3-chloro-4-methylthiophenyl)-3-methyl-5-imino-imidazolidin-~0 -2-one, 1-(3-trifluoromethyl-4-chlorophenyl)-3-methyl-5-imino-imidazolidin--2-one, 1-(3-chloro-4-ethoxyphenyl)-~-methyl-5-imino-imidazolidin-2-one, 1-(3-nitro-4-methylphenyl)-3-methyl-5-imino-imidazolidin-2-one, 1-(3,5-dichloro-4-methoxyphenyl)-3-methyl-5-imino-imidazolidin--2-one, 1-(3-chloro-4-methoxy-5-bromophenyl)-3-methyl-5-imino-imidazolidin--2-one.
m e novel active ingredients of the formula I may be obtained 2C by reacting for instance aromatic isocyanates of the formula R3 II, where R1, R2 and R3 have the above meanings, with methylamino-acetonitrile (CH3NHCH2CN), in the presence or absence of aromatic -- 3 ~

1148~6~ o. z . 0050/034008 hydrocarbons, chlorinated aliphatic and aromatic hydrocarbons, ethers, e.g., diethyl and dibutyl ether, dioxane and tetrahydro-furan, or ketones, e.g., acetone and methyl ethyl ketone, as diluents, and in the presence or absence of a basic catalyst, e.g., triethylarnine, N-methylpiperidine and N,N-dimethylcyclohexyl-amine. The same compound of the formula I is also obtained if for instance an aromatic isocyanate of the formula II, if desired dissolved in a water-immiscible organic solvent, is reacted with an aqueous solution of methylaminoacetonitrile hydrochloride, if ~0 desired in the presence of a 1.1- to 2-molar excess (based on the hydrochloride) of sodium hydroxide, sodium carbonate, potassium hydroxide, potassium carbonate, triethylamine or pyridine.
The above reactions are carried out at from about -10 to +80C, preferably from 0 to 40C.
The 1-aryl-3-methyl-3-cyanomethylureas of the formula ~ NH-CO-N III, where R1, R2 and R3 have the above meanings, which probably occur as intermediates, spontaneously cyclize to give the novel com-pounds of the formula I.
The isocyanates of the formula II used as starting materials are known or may readily be prepared by conventional methods.
The starting compound methylaminoacetonitrile may be produced by the process described in German Laid-Open Application ~E-CS 2,503,5Q2.

~148164 o . z . 0050/034008 The novel compounds of the formula I are colorless crystalline products which are readily soluble in ethyl acetate, acetone, ethanol, tetrahydrofuran, methylene chloride, chloroform, dimethyl sulfoxide~ dimethylformamide and N-methylpyrrolidone.
The following experiments illustrate the manufacture of the active ingredients.
EXAMPLE

~ b' Cl NH

0.2 g of triethylamine is added to a solution of 3.5 g (0.05 mole) of methylaminoacetonitrile in 50 ml of anhydrous toluene;
subsequently, a solution of 9.4 g tO.05 mole) of 3,4-dichloro-phenyl isocyanate in 50 ml of anhydrous toluene is dripped in at from 10 to 15C. The mixture is stirred overnight and the pre-cipitate is filtered, washed with 50 ml of toluene and 50 ml of petroleum ether, and dried. There is obtained 12 g (93% of theory) 2C of 1-(3,4-dichlorophenyl)-3-methyl-5-imino-imidazolidin-2-one as white crystals which analyze pure; m.p.: 158-161C. (Active ingredient no. 1).

o (~
Cl H

At 10C, 50 ml of methylene chloride and a solution of 7 g of sodium hydroxide in 20 ml of water are added to a solution of 114816~ o.z. 0050/034008 18.6 g (0.175 mole) of methylaminoacetonitrile hydrochloride in 70 ml of water. At 10 to 15C, a solution of 20.5 g (0.15 mole) of o-chlorophenyl isocyanate in 100 ml of anhydrous methylene chloride is dripped into the thoroughly stirred mixture. After

3 hours' stirring at room temperature, the organic phase is separated, washed twice, each time with 75 ml of water, and con-centrated. m e residue is dissolved with 75 ml of petroleum ether, filtered, and washed ~rith petroleum ether. There is obtained 31.2 g (92% of theory, based on isocyanate used) of 1-(2-chlorophenyl)--3-methyl-5-imino-imidazolidin-2-one as white crystals; m.p.:
138-141C. (Active ingredient no. 2).
The compounds in the following table are prepared analogously:

o.z. ooso/034008 ~O t O O O 0 5 t~ 5 C~ ~ o a:~ o U~ C-- ~ ~ Cq ~ --~ ~I ~ ,0~ ,0~ 0~

C.)~ ~ ~ I Cl~
æ~ ~, -- I c, 0~ C

o C-~ -C~ ~ I
I ~
V
~ I

., _ ~ ~ S S -- ~ ~ S S ~ S
a~
a rl ~ ~ ~ U~ ~ C~ CO O~ O 1 ~U ~ 5 l~
E~ ¢-rl 1148~6~
0 . Z . 0050/034008 ~ ' ~, .C~ O O ~O 5 d? u~ 5~ ~ e-- ,0~
C'I I I I I I I I ~ I
5 ~ O ~ 5 ~ O t~

~ V ~
(~ 3 ~ X ~ ~

O a~ I I
III U~IOO
~ ~ t<~
_ ~ _ ~ X
~ l 1~ 5 _ S 5 5 S S 5 5, 5 S

~ I O ~ ~1 c~ v a~ z c~ c~
C) ~a ~1 r~ ~ . ~ ~ ~ O ~ N ~ ~
bO ~ ~ ~1 ~--I N N t~J N N N N
C~ ~ O

~1481t;4 o.z. oo50/034008 The active ingredients may be applied for instance in the form of directly sprayable solutions, powders, suspensions (in-cluding high-percentage aqueous, oily or other suspensions), dispersions, emulsions, oil dispersions, pastes, dusts, broadcasting agents, or granules by spraying, atomizing, dusting, broadcasting or watering. The forms of application depend entirely on the pur-pose for which the agents are being used.
For the preparation of solutions, emulsions, pastes and oil dispersions to be sprayed direct, mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, further coal-tar oils, and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons such as benzene, toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes and their derivatives such as methanol, ethanol, propanol, butanol, chloroform, carbon tetrachloride, cyclo-hexanol, cyclohexanone, chlorobenzene, isophorone, etc., and strongly polar solvents such as dimethylformamide, dimethyl-sulfoxide, N-methylpyrrolidone, water, etc. are suitable.
Aqueous formulations may be prepared from emulsion con-2C centrates, pastes, oil dispersions or wettable powders byadding water. To prepare emulsions, pastes and oil dispersions the ingredients as such or dissolved in an oil or solvent may be homogenized in water by means of wetting or dispersing agents, adherents or emulsifiers. Concentrates which are suitable for dilution with water may be prepared from active ingredient, wetting agent, adherent, emulsifying or dispersing agent and possibly solvent or oil.

_ g _ ~8~ o. z . oo50/0~4008 Examples of surfactants are: alkali metal, alkaline earth metal and ammonium salts of ligninsulfonic acid, naphthalene-sulfonic acids, phenolsulfonic acids, alkylaryl sulfonates, alkyl sulfates, and alkyl sulfonates, alkali metal and alkaline earth metal salts of dibutylnaphthalenesulfonic acid, lauryl ether sulfate, fatty alcohol sulfates, alkali metal and alkaline earth metal salts of fatty acids, salts of sulfated hexadecanols, heptadecanols, and octadecanols, salts of sulfated fatty alco-hol glycol ethers, condensation products of sulfonated naphtha-}O lene and naphthalene derivatives with formaldehyde, condensation products of naphthalene or naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol ethers, ethoxyl-ated isooctylphenol, ethoxylated octylphenol and ethoxylated nonylphenol, alkylphenol polyglycol ethers, tributylphenyl polyglycol ethers, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxy-propylene, lauryl alcohol polyglycol ether acetal, sorbitol esters, lignin, sul~ite waste liquors and methyl cellulose.
2C Powders, dusts and broadcasting agents may be prepared by mixing or grinding the active ingredients with a solia carrier.
Granules, e.g., coated, impregnated or homogeneous gra-nules, may be prepared by bonding the active ingredients to solid carriers. Examples of solid carriers are mineral earths such as silicic acid, silica gels, silicates, talc, kaolin, Attaclay, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, mag-~4~64 O.z. 0050/034oo~
nesium oxide, ground plastics, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, and ureas, and vegetable products such as grain ,lours, bark meal, wood meal, and nutshell meal, cellulosic powders, etc.
The formulations contain from 0.1 to 95, and preferably 0.5 to 90, % by weight of active ingredient.
The active ingredients are applied to the plants or soil for example by watering, broadcasting, dusting, spraying or atomizing, or by introducing them into the irrigation water.
} The influence of various representatives of the compounds according to the invention on the growth of unwanted plants com-pared with prior art active ingredients is demonstrated in the following greenhouse experiments.
The vessels employed were plastic flowerpots having a volume of 300 cm3, and which were filled with a sandy loam containing about 1.5% humus. The seeds of the test plants (cf. Table 1) were sown shallow, and separately, according to species. For the preemergence treatment, the active ingredients were applied to the surface of the soil immediately after the seeds had been sown.
2C The compounds were emulsified or suspended in water as ~ehicle, and sprayed through finely distributing nozzles. After the agents had been applied, the vessels were lightly sprinkler-irrigated to induce germination and growth and to activate the chemical agents. Transparent plastic covers were then placed on the vessels until the plants had taken root. The cover ensured uniform germination of the plants, insofar as this was not impaired by the chemicals.

~ ~8~ o.z . oo50/034008 For the postemergence treatment, the plants were first grown in the vessels to a height of from 3 to 10 cm, depending on growth form, before being treated. No cover was placed on the vessels.
The pots were set up in the greenhouse - species from warmer areas at from 25 to 40C, and species from moderate climates at 15 to 30C. The experiments were run for from 3 to 6 weeks.
During this period, the plants were tended and their reactions to the various treatments assessed. The following tables contain the compounds investigated, the application rates in kg/ha of active ingredient, and the plants used for the tests. The scale used for assessment was 0 to 100, 0 denoting no damage or normal emergence, and 100 denoting nonemergence or complete destruction Or at least the visible plant parts.
The following tables demonstrate the selective~herbicidal action of the compounds according to the invention. Some of the new compounds open up possibilities of use in crops in which the prlor art active ingredients from this class of compounds cannot be employed because they are insufficiently tolerated. The com-pounds according to the invention may be applied either pre- or 2C postemergence, but preferably preemergence, whereas the prior art compounds are best when applied postemergence. The agents may be applied to the site before the unwanted plants have germinated from seed or sprouted from vegetative plant parts, or they are applied to the leaves of the unwanted and crop plants. A further application technique is to spray the active ingredients with the aid of spraying equipment in such a way that the leaves of sensitive crop plants are if possible not hit; the acti~e ingredients 11~816~ o.z. 0050/034008 reach the soil or unwanted plants growing below the crop plants (post-directed, lay-by treatment). Depending on the season and growth stage, application rates are from 0.1 to 15 and more kg Of active ingredient per hectare, the higher rates being suitable for total elimination of vegetation.
In view of the many application methods possible, the agents according to the invention, or mixtures containing them, may be used in addition to the crop plants listed in the tables in a large number of other crops for eliminating unwanted growth.
~0 The following crop plants are given by way of example:
Botanical name Common name Allium cepa onions Ananas comosus pineapples Arachis hypogaea peanuts (groundnuts) Asparagus o~ficinalis asparagus Avena sativa oats Beta vulgaris spp. altissima sugarbeets Beta vulgaris spp. rapa fodder beets Beta vulgaris spp. esculenta table beets, red beets 2C Brassica napus var. napus rape Brassica napus var. napobrassica Brassica napus var. rapa turnips Brassica rapa var. silvestris Camellia sinensis tea plants Carthamus tinctorius safflower Carya illinoinensis pecan trees Citrus limon lemons ~1~8164 o.z. 0050/034008 Botanical name Common name .
Citrus maxima grapefruits Citrus reticulata Citrus sinensis orange trees Coffea arabica (Coffea canephora, Coffea liberica) coffee plants Cucumis melo melons Cucumis sativus cucumbers Cynodon dactylon Bermudagrass in turf and lawns 10 Daucus carota carrots Elais guineensis oil palms Fragaria vesca . strawberries Glycine max soybeans Gossypium hirsutum (Gossypium arboreum cotton Gossypium herbaceum Gossypium vitifolium) Helianthus annuus sunflowers Helianthus tuberosus Hevea brasiliensis rubber plants Hordeum vulgare barley Humulus lupulus hops Ipomoea batatas sweet potatoes Juglans regia walnut trees Lactuca sativa lettuce Lens culinaris lentils Linum usitatissimum flax Lycopersicon lycopersicum tomatoes Malus spp. apple trees ~ 8~6~ o. z . 0050/034008 Botanical name Common name Manihot esculenta cassava Medicago ~;ativa alfalfa ~lucerne) Mentha piperita peppermint Musa spp. banana plants Nicothiana tabacum tobacco (N. rustica) Olea europaea olive trees Oryza sativa rice Panicum miliaceum Phaseolus lunatus limabeans Phaseolus mungo mungbeans Phaseolus vulgaris snapbeans, green beans, dry beans Pennisetum glaucum Petroselinum crispum parsley spp. tuberosum Picea abies Norway spruce Abies alba fir trees Pinus spp. pine trees 2C Pisum sativum English peas Prunus avium cherry trees Prunus domestica plum trees Prunus dulcis almond trees Prunus persica peach trees Pyrus communis . pear trees Ribes sylvestre redcurrants Ribes uva-crispa ~4~16~ o.z. oo50/034008 Botanical name Common name Ricinus communis Saccharum officinarum sugar cane Secale cereale rye Sesamum indicum sesame Solanum tuberosum Irish potatoes Sorghum bicolor (s. vulgare) grain sorghum Sorghum dochna Spinacia oleracea spinach 10 Theobroma cacao cacao plants Trifolium pratense red clover Triticum aestivum wheat Vaccinium corymbosum blueberries Vaccinium vitis-idaea cranberries Vicia faba tick beans Vigna sinensis (V. unguiculata) cow peas Vitis vinifera grapes Zea mays Indian corn, sweet corn, maize The new 5-imino-imidazolidin-2-ones may be mixed and applied 2C with each other and together with numerous representatives of other herbicidal or growth-regulating active ingredient groups.
Examples of suitable mixture components are diazines, N-phenyl-carbamates, thiolcarbamates, diurethanes, halocarboxylic acids, phenoxy fatty acids, triazines, amides, ureas, diphenyl ethers, triazinones, uracils, benzofuran derivatives, etc. Such combinations broaden the spectrum of action and sometimes synergistic effects are achieved. A number of active ingredients which, when combined 1148~6~ o.z. 0050/034008 with the new compounds, give mixtures useful for widely varyingapplications are given below by way of example. Postemergence herbicides are a particular enrichment because they act via the ~oliage, whereas the compounds according to the invention excel via the 80il.
5-amino-4-chloro-2-phenyl-3(2H)-pyridazinone 5-amino-4-bromo-2-phenyl-3(2H)-pyridazinone 5-amino-4-chloro-2-cyclohexyl-3(2H)-pyridazinone 5-amino-4-bromo-2-cyclohexyl-3(2H)-pyridazinone 5-methylamino-4-chloro-2-(3-trifluoromethylphenyl)-3(2H)--pyridazinone 5-methylamino-4-chloro-2-(3-~,~,B,~-tetrafluoroethoxyphenyl)--3(2H)-pyridazinone 5-dimethylamino-4-chloro-2-phenyl-3(2H)-pyridazinone

4,5-dimethoxy-2-phenyl-3(2H)-pyridazinone 4,5-dimethoxy-2-cyclohexyl-3(2H)-pyridazinone 4,5-dimethoxy-2-(3-trifluoromethylphenyl)-3(2H)-pyridazinone

5-methoxy-4-chloro-2-(3-trifluoromethylphenyl)-3(2H)-pyridazinone 2C 5-amino-4-bromo-2(3-methylphenyl)-3(2H)-pyridazinone 3-(1-methylethyl)-lH-2,1,3-benzothiadiazin-4(3H)-one-2,2-dioxide and salts 3-(1-methylethyl)-8-chloro-lH-2,1,3-benzothiadiazin-4(3H)-one--2,2-dioxide and salts 3-(1-methylethyl)-8-fluoro-lH-2,1,3-benzothiadiazin-4(3H)-one--2,2-dioxide and salts 114816~ o.z. oo50/034008 3-(1-methylethyl)-8-methyl-lH-2,1,3 benzothiadiazin-4(3H)-one--2,2-dioxide and salts l-methoxymethyl-3-(1-methylethyl)-2,1,3-benzothiadiazin-4(3H)--one-2,2-dioxide l-methoxymethyl-8-chloro-3-(1-methylethyl)-2,1,3-benzothia-diazin-4t3H)-one-2,2-dioxide l-methoxymethyl-8-fluoro-3-(1-methylethyl)-2,1,3-benzothiadiazin--4(3H)-one-2,2-dioxide l-cyano-8-chloro-3-(1-methylethyl)-2,1,3-benzothiadiazin-4(3H)--one-2,2-dioxide l-cyano-8-fluoro-3-(1-methylethyl)-2,1,3-benzothiadiazin-4(3H)--one-2,2-dioxide l-cyano-8-methyl-3-(1-methylethyl)-2,1,3-benzothiadiazin-4(3H)--one-2,2-dioxide l-cyano-3-(1-methylethyl)-2,1,3-benzothiadiazin-4(3H)-one-2,2--dioxide l-azidomethyl-3-(1-methylethyl)-2,1,3-benzothiadiazin-4t3H)--one-2,2-dioxide 3-(1-methylethyl)-lH-pyridino-~3,2-e]-2,1,3-thiadiazin-(4)-one-2C -2,2-dioxide N-(l-ethylpropyl)-2,6-dinitro-3,4-dimethylaniline N-(l-methylethyl)-N-ethyl-2,6-dinitro-4-trifluoromethylaniline N-n-propyl-N-~-chloroethyl-2,6-dinitro-4-trifluoromethyl-aniline N-n-propyl-N-cyclopropylmethyl-2,6-dinitro-4-trifluoromethyl-aniline 1~48~64 o . z . ooso/034008 N-bis-(n-propyl)-2,6-dinitro-3-amino-4-trifluoromethylaniline N-bis-(n-propyl)-2,6-dinitro-4-methylaniline N-bis-(n-propyl)-2,6-dinitro-4-methylsulfonylaniline W-bis-(n-propyl)-2,6-dinitro-4-aminosulfonylaniline bis-(~-chloroethyl)-2,6-dinitro-4-methylaniline N-ethyl-N-(2-methylallyl)-2,6-dinitro-4-trifluoromethylaniline 3,4-dichlorobenzyl N-methylcarbamate 2,6-di-tert.butyl-4-methylphenyl N-methylcarbamate isopropyl N-phenylcarbamate 3-methoxyprop-2-yl N-3-fluorophenylcarbamate isopropyl N-3-chlorophenylcarbamate but-1-yn-3-yl N-3-chlorophenylcarbamate 4-chlorobut-2-yn-1-yl N-3-chlorophenylcarbamate methyl N-3,4-dichlorophenylcarbamate methyl N-(4-aminobenzenesulfonyl)-carbamate 0-(N-phenylcarbamoyl)-propanone oxime N-ethyl-2-(phenylcarbamoyl)-oxypropionic acid amide 3'-N-isopropylcarbamoyloxypropionanilide ethyl-N-(3-(N'-phenylcarbamoyloxy)-phenyl)-carbamate methyl-N-(3-(N'-methyl-N'-phenylcarbamoyloxy)-phenyl)-carbamate isopropyl-N-(3-(N'-ethyl-N'-phenylcarbamoyloxy)-phenyl)--carbamate methyl-N-(3-(N'-3-methylphenylcarbamoyloxy)-phenyl)-carbamate methyl-N-(3-(N'-4-fluorophenylcarbamoyloxy)-phenyl)-carbamate methyl-N-(3-(N'-3-chloro-4-fluorophenylcarbamoyloxy)-phenyl)--carbamate ~4B~ o o z . oo50/034008 ethyl-N-[3-N'-(3-chloro-4-fluorophenylcarbamoxyloxy)-phenyl]--carbamate ethyl-N-~3-N'-(3,4-difluorophenylcarbamoyloxy)-phenyl]-carbamate methyl-N-C3-(N'-3,4-difluorophenylcarbamoyloxy)-phenyl]-carbamate methyl N-3-(4'-fluorophenoxycarbonylamino)-phenylcarbamate ethyl N-3-(2'-methylphenoxycarbonylamino)-phenylcarbamate methyl N-3-(4'-fluorophenoxycarbonylamino)-phenylthiolcarbamate methyl N-3-(2',4',5'-trimethylphenoxycarbonylamino)-phenylthiol-~0 carbamatemethyl N-3-(phenoxycarbonylamino)-phenylthiolcarbamate p-chlorobenzyl N,N-diethylthiolcarbamate ethyl N,N-di-n-propylthiolcarbamate n-propyl N,N-di-n-propylthiolcarbamate 2,3-dichloroallyl N,N-dii~opropylthiolcarbamate 2,3,3-trichloroallyl N,N-diisopropylthiolcarbamate 3-methyl-5-isoxazolylmethyl N,N-diisopropylthiolcarbamate 3-ethyl-5-isoxazolylmethyl N,N-diisopropylthiolcarbamate 2C ethyl N,N-di-sec.-butylthiolcarbamate benzyl N,N-di-sec.-butylthiolcarbamate ethyl N-ethyl-N-cyclohexylthiolcarbamate ethyl N-ethyl-N-bicyclo-t2.1.1]-heptylthiolcarbamate S-(2,3-dichloroallyl)-(2,2,4-trimethylazetidine)-1-carbothiolate S-(2,3,3-trichloroallyl)-(2,2,4-trimethylazetidine)-1-carbothiolate S-ethylhexahydro-1-H-azepine-1-carbothiolate S-benzyl-(3-methylhexahydro-1-H-azepine-1)-carbothiolate ~48~64 o.z. oo50/034008 S-benzyl-~2,3-dimethylhexahydro-1-H-azepine-1)-carbothiolate S-ethyl-(3-methylhexahydro-1-H-azepine-1)-carbothiolate n-propyl N-ethyl-N-n-butylthiolcarbamate 2-chloroallyl N,N-dimethyldithiocarbamate N-methyldithiocarbamic acid, sodium salt trichloroacetic acid, sodium salt ~-dichloropropionic acid, sodium salt ~-dichlorobutyric acid, sodium salt ~ -tetrafluoropropionic acid, sodium salt ~-methyl~ -dichloropropionic acid, sodium salt methyl~-chloro-~-(4-chlorophenyl)-propionate methyl~,B-dichloro-~-phenylpropionate benzamido oxyacetic acid 2,3,5-triiodobenzoic acid (salts, esters, amides) 2,3,6-trichlorobenzoic acid (salts, esters, amides) 2,3,5,6-tetrachlorobenzoic acid (salts, esters, amides) 2-methoxy-3,6-dichlorobenzoic acid (salts, esters, amides) 2-methoxy-3,5,6-trichlorobenzoic acid (salts, esters, amides) 2C 3-amino-2,5,6-trichlorobenzoic acid (salts, esters, amides) O,S-dimethyltetrachlorothioterephthalate dimethyl-2,3,5,6-tetrachloroterephthalate disodium 3,6-endoxohexahydrophthalate 4-amino-3,5,6-trichloropicolinic acid (salts) ethyl 2-cyano-3-(N-methyl-N-phenyl)-aminoacrylate isobutyl 2-[4-(4'-chlorophenoxy)-phenoxy]-propionate methyl 2-[4-(2',4'-dichlorophenoxy)-phenoxy]-propionate . 1148~6~ o . z . 0050/034008 methyl 2-[4-(4'-trifluoromethylphenoxy)-phenoxy]-propionate 2-[4-(2'-chloro-4'-trifluorophenoxy)-phenoxy]-propionic acid, sodium salt 2-~4-(3',5'-dichloropyridyl-2-oxy)-phenoxy]-propionic acid, sodium salt ethyl 2-(N-benzoyl-3,4-dichlorophenylamino)-propionate methyl 2-(N-benzoyl-3-chloro-4-fluorophenylamino)-propionate isopropyl 2-(N-benzoyl-3-chloro-4-fluorophenylamino)-propionate 2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine 2-chloro-4-ethylamino-6-(amino-2'-propionitrile)-1,3,5-triazine 2-chloro-4-ethylamino-6-(2-methoxypropyl)-2-amino-1,3,5--triazine 2-chloro-4-ethylamino-6-butyn-1-yl-2-amino-1,3~5-triazine 2-chloro-4,6-bisethylamino-1,3,5-triazine 2-chloro-4,6-bisisopropylamino-1,3,5-triazine 2-chloro-4-isopropylamino-6-cyclopropylamino-1,3,5-triazine 2C 2-azido-4-methylamino-6-isopropylamino-1,3,5-triazine 2-methylthio-4-ethylamino-6-isopropylamino-1,3,5-triazine 2-methylthio-4-ethylamino-6-tert.butylamino-1,3,5-triazine 2-methylthio-4,6-bisethylamino-1,3,5-triazine 2-methylthio-4,6-bisisopropylamino-1,3,5-triazine 2-methoxy-4-ethylamino-6-isopropylamino-1,3,5-triazine 2-methoxy-4,6-bisethylamino-1,3,5-triazine 1~81~ o . z . 0050/034008 2-methoxy-4,6-bisisopropylamino-1,3,5-triazine 4-amino-6-tert.butyl-3-methylthio-4,5-dihydro-1,2,4-triazin-5-one 4-amino-6-phenyl-3-methyl-4,5-dihydro-1,2,4-triazin-5-one 4-isobut;ylidenamino-6-tert.butyl-3-methylthio-4,5-dihydro-1,2,4--triazin-5-one 1-methyl-3-cyclohexyl-6-dimethylamino-1,3,5-triazin-2,4-dione 3-tert.butyl-5-chloro-6-methyluracil 3-tert.butyl-5-bromo-6-methyluracil 3-isopropyl-5-bromo-6-methyluracil 3-sec~butyl-5-bromo-6-methyluracil 3-(2-tetrahydropyranyl)-5-chloro-6-methyluracil 3-(2-tetrahydropyranyl)-5,6-trimethyleneuracil 3-cyclohexyl-5,6-trimethyleneuracil 2-methyl-4-(3'-trifluoromethylphenyl)-tetrahydro-1,2,4-oxa-diazine-3,5-dione 2-methyl-4-(4'-fluorophenyl)-tetrahydro-1,2,4-oxadiazine-3,5--dione 2C 3-amino-1,2,4-triazole 1-allyloxy-1-(4-bromophenyl)-2-[1',2',4'-triazolyl-(1')]--ethane (salts) 1-(4-chlorophenoxy)-3,3-dimethyl-1-(lH-1,2,3-triazol-1-yl)--butan-2-one N,N-diallylchloroacetamide N-isopropyl-2-chloroacetanilide N-(but-1-yn-3-yl)-2-chloroacetanilide ~ 8~6~ o.z. 0050/034008 2-methyl-6-ethyl-N-propargyl-2-chloroacetanilide 2-methyl-6-ethyl-N-ethoxymethyl-2-chloroacetanilide 2-methyl-6-ethyl-N-(2-methoxy-1-methylethyl)-2-chloroacetanilide 2-methyl-6-ethyl-N-(isopropoxycarbonylethyl)-2-chloroacetanilide 2-methyl-6-ethyl-N-(4-methoxypyrazol-1-yl-methyl)-2-chloro--acetanilide 2-methyl-6-ethyl-N-(pyrazol-1-yl-methyl)-2-chloroacetanilide 2,6-dimethyl-N-(pyrazon-1-yl-methyl)-2-chloroacetanilide 2,6-dimethyl-N-(4-methylpyrazol-1-yl-methyl)-2-chloro-acetanilide 2,6-dimethyl-N-(1,2,4-triazol-1-yl-methyl)-2-chloroacetanilide 2,6-dimethyl-N-(3,5-dimethylpyrazol-1-yl-methyl)-2-chloro-acetanilide 2,6-dimethyl-N-(1,3-dioxolan-2-yl-methyl)-2-chloroacetanilide 2,6-dimethyl-N-(2-methoxyethyl)-2-chloroacetanilide 2,6-dimethyl-N-isobutoxymethyl-2-chloroacetanilide 2,6-diethyl-N-methoxymethyl-2-chloroacetanilide 2,6-diethyl-N-n-butoxymethyl-2-chloroacetanilide 2,6-diethyl-N-ethoxycarbonylmethyl-2-chloroacetanilide 2,3,6-trimethyl-N-(pyrazol-1-yl-methyl)-2-chloroacetanilide 2C 2,3-dimethyl-N-isopropyl-2-chloroacetanilide 2,6-diethyl-N-(propoxyethyl)-2-chloroacetanilide) 2-(2-methyl-4-chlorophenoxy-N-methoxyacetamide 2-(~naphthoxy)-N,N-diethylpropionamide 2,2-diphenyl-N,N-dimethylacetamide ~(3,4,5-tribromopyrazol-1-yl)-N,N-dimethylpropionamide N-(1,1-dimethylpropynyl)-3,5-dichlorobenzamide ~1~816~
O.Z. 0050/034008 N-l-naphthylphthalamic acid propionic acid 3,4-dichloroanilide cyclopropanecarboxylic acid 3,4-dichloroanilide methacrylic acid 3,4-dichloroanilide 2-methylpentanecarboxylic acid 3,4-dichloroanilide N-2,4-dimethyl-5-(trifluoromethyl)-sulfonylaminophenylacetamide N-4-methyl-5-(trifluoromethyl)-sulfonylaminophenylacetamide 2-propionylamino-4-methyl-5-chlorothiazole 0-(methylsulfonyl)-glycolic acid N-ethoxymethyl-2,6-dimethyl-~0 anilide 0-(methylaminosulfonyl)-glycolic acid N-isopropylanilide 0-(isopropylaminosulfonyl)-glycolic acid N-but-l-yn-3-yl-anilide 0-(methylaminosulfonyl)-glycolic acid hexamethyleneamide 2,6-dichlorothiobenzamide 2,6-dichlorobenzonitrile 3,5-dibromo-4-hydroxybenzonitrile (salts) 3,5-diiodo-4-hydroxybenzonitrile (salts) 3,5-dibromo-4-hydroxy-0-2,4-dinitrophenylbenzaldoxime (salts) 3,5-dibromo-4-hydroxy-0-2-cyano-4-nitrophenylbenzaldoxime 2C (salts) pentachlorophenol, sodium salt 2,4-dichlorophenyl-4'-nitrophenyl ether 2,4,6-trichlorophenyl-4'-nitrophenyl ether 2-fluoro-4,6-dichlorophenyl-4'-nitrophenyl ether 2-chloro-4-trifluoromethylphenyl-4'-nitrophenyl ether 2,4'-dinitro-4-trifluoromethyl-diphenyl ether 2,4-dichlorophenyl-3'-methoxy-4'-nitro-phenyl ether ~1~8~6~
o. z . ooso/034008 2-chloro-4-trifluoromethylphenyl-3'-ethoxy-4'-nitro-phenyl ether 2-chloro-4-trifluoromethylphenyl-3'-carboxy-4'-nitro-phenyl ether (salts) 2,4-dichlorophenyl-3'-methoxycarbonyl-4'-nitro-phenyl ether 2-(3,4-dichlorophenyl)-4-methyl-1,2,4-oxadiazolidine-3,5-dione 2-(3-tert.butylcarbamoyloxyphenyl)-4-methyl-1,2,4-oxadiazolidine--3,5-dione 2-(3-isopropylcarbamoyloxyphenyl)-4-methyl-1,2,4-oxadiazolidine--3,5-dione 2-phenyl-3,1-benzoxazinone-(4) (4-bromophenyl)-3,4,5,9,10-pentaazatetracyclo-[5,4,1,02'6'0,8'11]--dodeca-3,9-diene 2-ethoxy-2,3-dihydro-3,3-dimethyl-5-benzofuranylmethane sulfonate 2-ethoxy-2,3-dihydro-3,3-dimethyl-5-benzofuranyldimethylamino-sulfate 2-ethoxy-2,3-dihydro-3,3-dimethyl-5-benzofuranyl-(N-methyl-N--acetyl)-aminosulfonate 3,4-dichloro-1,2-benzisothiazole 2C N-4-chlorophenyl-allylsuccinimide 2-methyl-4,6-dinitrophenol (salts, esters) 2-sec.butyl-4,6-dinitrophenol (salts, esters) 2-sec.butyl-4,6-dinitrophenol acetate 2-tert.butyl-4~6-dinitrophenol acetate 2-tert.butyl-4,6-dinitrophenol (salts) 2-tert.butyl-5-methyl-4,6-dinitrophenol (salts) 2-tert.butyl-5-methyl-4,6-dinitrophenol acetate 0.2. 0050/034008 2-sec.amyl-4,6-dinitrophenol (salts, esters) 1-( , -dimethylbenzyl)-3-(4-methylphenyl)-urea l-phenyl-3-(2-methylcyclohexyl)-urea l phenyl-l-~enzoyl-3,3-dimethylurea 1-(4-chlorophenyl)-1-benzoyl-3,3-dimethylurea 1-(4-chlorophenyl)-3,3-dimethylurea 1-(4-chlorophenyl)-3-methyl-3-but-1-yn-3-yl-urea 1-(3,4-dichlorophenyl)-3,3-dimethylurea 1-(3,4-dichlorophenyl)-1-benzoyl-3,3-dimethylurea 1-(3,4-dichlorophenyl)-3-methyl-3-n.butylurea 1-(4-isopropylphenyl)-3,3-dimethylurea 1-(3-trifluoromethylphenyl)-3,3-dimethylurea -tetrafluoroethoxyphenyl)-3,3-dimethylurea 1-(3-tert.butylcarbamoyloxyphenyl)-3,3-dimethylurea 1-(3-chloro-4-methylphenyl)-3,3-dimethylurea 1-(3-chloro-4-methoxyphenyl)-3,3-dimethylurea 1-(3,5-dichloro-4-methoxyphenyl)-3,3-dimethylurea 1-[4-(4'-chlorophenoxy)-phenyl]-3,3-dimethylurea 2C 1-~4-(4'-methoxyphenoxy)-phenyl]-3,3-dimethylurea l-cyclooctyl-3,3-dimethylurea l-(hexahydro-4,7-methanoindan-5-yl)-3,3-dimethylurea 1-[1- or 2-(3a,4,5,7,7a-hexahydro)-4,7-methanoindanyl]-3,3-di-methylurea 1-(4-fluorophenyl)-3-carboxymethoxy-3-methylurea l-phenyl-3-methyl-3-methoxyurea 1-(4-chlorophenyl)-3-methyl-3-methoxyurea ~ 81~ o. z . 0050/034008 1-(4-bromophenyl)-3-methyl-3-methoxyurea 1-(3,4-dichlorophenyl)-3-methyl-3-methoxyurea 1-(3-chloro-4-bromophenyl)-3-methyl-3-methoxyurea 1-(3-chloro-4-isopropylphenyl)-3-methyl-3-methoxyurea 1-(3-chloro-4-methoxyphenyl)-3-methyl-3-methoxyurea 1-(3-tert.butylphenyl)-3-methyl-3-methoxyurea 1-(2-benzthiazolyl)-1,3-dimethylurea 1-(2-benzthiazolyl)-3-methylurea 1-(5-trifluoromethyl-1,3,4-thiadiazolyl)-1,3-dimethylurea imidazolidin-2-one-1-carboxylic acid isobutylamide 1,2-dimethyl-3,5-diphenylpyrazolium-methylsulfate 1,2,4-trimethyl-3,5-diphenylpyrazolium-methylsulfate 1,2-dimethyl-4-bromo-3,5-diphenylpyrazolium-methylsulfate 1,3-dimethyl-4-(3,4-dichlorobenzoyl)-5-(4-methylphenylsulfonyloxy)-~pyrazole 2,3,5-trichloropyridinol-(4) 1-methyl-3-phenyl-5-(3'-trifluoromethylphenyl)-pyridone-(4) 1-methyl-4-phenylpyridinium chloride 1,1-dimethylpyridinium chloride 2C 3-phenyl-4-hydroxy-6-chloropyridazine 1,1'-dimethyl-4,4'-dipyridylium-di(methylsulfate) 1,1'-di-(3,5-dimethylmorpholine-carbonylmethyl)-4,4'-dipyridylium dichloride 1,1'-ethylene-2,2'-dipyridylium dibromide 3-[1-(N-ethoxyamino)-propylidene]-6-ethyl-3,4-dihydro-2H-pyran--2,4-dione ~148~L64 O.Z. 005~/034008 3-[1-(N-allyloxyamino)-propylidene]-6-ethyl-3,4-dihydro-2H-pyran--2,4-dione 2-[1-(N-allyloxyamino)-propylidene]-5,5-dimethylcyclohexane-1,3--dione (salts) 2-~1-(N-allyloxyamino-butylidene]-5,5-dimethylcyclohexane-1,3--dione (salts) 2-[1-~N-allyloxyamino-butylidene]-5,5-dimethyl-4-methoxycarbonyl--cyclohexane-1,3-dione (salts) 2-chlorophenoxyacetic acid (salts, esters, amides) 10 4-chlorophenoxyacetic acid (salts, esters, amides) 2,4-dichlorophenoxyacetic acid (salts, esters, amides) 2,4,5-trichlorophenoxyacetic acid (salts, esters, amides) 2-methyl-4-chlorophenoxyacetic acid (salts, esters, amides) 3,5,6-trichloro-2-pyridinyl-oxyacetic acid (salts, esters, amides) methyl ~-naphthoxyacetate 2-(2-methylphenoxy)-propionic acid (salts, esters, amides) 2-(4-chlorophenoxy)-propionic acid (salts, esters, amides) 2C 2-(2,4-dichlorophenoxy)-propionic acid (salts, esters, amides) 2-(2,4,5-trichlorophenoxy)-propionic acid (salts, esters, amides) 2-(2-methyl-4-chlorophenoxy)-propionic acid (salts, esters, amides) 4-(2,4-dichlorophenoxy)-butyric acid (salts, esters, amides) 4-(2-methyl-4-chlorophenoxy)-butyric acid (salts, esters, amides) cyclohexyl-3-(2,4-dichlorophenoxy)-acrylate 9-hydroxyfluorenecarboxylic acid-(9) (salts, esters) 2,3,6-trichlorophenylacetic acid (salts, esters) 11~8~6~
o . z . ooso/034008 4-chloro-2-oxobenzothiazolin-3-yl-acetic acid (salts, esters) gibelleric acid (salts) di~odium methylarsonate monosodium salt of methylarsonic acid N-phosphonomethyl-glycine (salts) N,N-bis-(phosphonomethyl)-glycine (salts) 2-chloroethyl 2-chloroethanephosphonate ammonium-ethyl-carbamoyl-phosphonate di-n-butyl-l-n-butylamino-cyclohexyl-phosphonate trithiobutylphosphite 0,0-diisopropyl-5-(2-benzosulfonylaminoethyl)-phosphorodithionate 2,3-dihydro-5,6-dimethyl-1,4-dithiin-1,1,4,4-tetraoxide 5-tert.butyl-3-(2,4-dichloro-5-isopropoxyphenyl)-1,3,4-oxa-diazolone-(2) 4,5-dichloro-2-trifluoromethylbenzimidazole ( 9 alts) 1,2,3,6-tetrahydropyridazine-3,6-dione (salts) succinic acid mono-N-dimethylhydrazide (salts) (2-chloroethyl)-trimethylammonium chloride (2-methyl-4-phenylsulfonyl)-trifluoromethanesulfone anilide 2C 1,1-dimethyl-4,6-diisopropyl-5-indanyl ethyl ketone sodium chlorate ammonium thiocyanate calcium cyanamide 2-chloro-4-trifluoromethyl-3'-ethoxycarbonyl-4'-nitrophenyl ether 1-(4-benzyloxyphenyl)-3-methyl-3-methoxyurea 2-[1-(2,5-dimethylphenyl)-ethylsulfonyl]-pyridine-N-oxide.

~81~ o. z . oo50/034008 It may also be useful to apply the mixtures according to the invention, either alone or in combination ~Jith other herbicides, in admixture with other crop protection agents, e.g., agents for combating pests or phytophatogenic fungi or bacteria. The com-pounds may also be mixed with solutions of mineral matters used to remedy nutritional or trace element deficiencies. Wetting agents, spreader-stickers, oils of various types and oil con-centrates, and antifoams may be added to the individual active ingredients or mixtures thereof.
10 Table 1 - List of plant names Botanical name Common name Amaranthus retroflexus redroot pigweed Arachis hypogaea peanuts (groundnuts) Beta vulgaris sugarbeets Centaura cyanus cornflower Chrysanthemum segetum corn marigold Datura stramonium Jimsonweed Echinochloa crus galli barnyardgrass Glycine max soybeans 2C Ipomoea spp. morningglory Lolium multiflorum annual ryegrass Matricaria spp. chamomile Nicandra physaloides apple-of-Peru Sesbania exaltata hemp sesbania (coffeeweed) Sinapis alba white mustard Sorghum bicolor sorghum ~81~
O.Z. 0050~034008 Solanum nigrum black nightshade Stellaria media chickweed Triticum aestivum wheat Table 2 Selective control of unwanted plants in various crops; preemergence treatment in the greenhouse Test plantsActive ingredientComparative agent No. 11 (prior art) 2 kg of active ~ h ~ -C~2-CH=C~2 ingredient per ha ~
NH C~3 Beta vulgaris 0 Glycine max 0 Sorghum bicolor 0 20 Amaranthus retroflexus100 90 Chrysanthemum segetum 95 100 Echinochloa crus galli 89 0 2C Sesbania exaltata 100 40 Sinapis alba 89 70 Solanum nigrum 100 90 0 = no damage 100 = plants destroyed What is worthy of note is that the prior art compound causes damage to the crop plant sorghum and has no, or only a poor, action on the unwanted plants Echinochloa and Sesbania.

~48~64 o.z . oo50/034008 Table 3 Selective control of unwanted plants; preemergence treatment in the greenhouse Active ingredient no. 10 ~est plants Damage 1.0 kg/ha 2.0 kg/ha Arachis hypogaea 0 10 Sorghum bicolor 0 5 Amaranthus retroflexus 90 100 Chrysanthemum segetum 85 100 Datura stramonium 100 100 Sesbania exaltata 98 98 0 = no damage 100 - nonemergence or plants completely destroyed ~ 8164 o.z. 0050/034008 Table 4 Selective control o~ unwanted plants in cereals and sorghum;
preemergence treatment in the greenhou,se Active ingredient no. 9 Test plants Damage 0.5 k /ha g Sorghum bicolor 0 Triticum aestivum 5 10 Amaranthus retroflexus 79 Matricaria spp. 98 Nicandra physaloides 100 Sesbania exaltata 80 Solanum nigrum 80 Stellaria media 100 ~ 816~ o . z . 0050/034008 Table 5 Selective herbicidal action; preemergence treatment in the greenhouse ~ "
Cl NH C2H5 Active ingredient no. 1 Comparative agent (prior art) Test plants Damage at 0.5 kg/ha 10 Arachis hypogaea 8 0 Beta vulgaris 0 Amaranthus retroflexus 97 40 Chrysanthemum segetum 85 0 Datura stramonium 100 0 Solanum nigrum 100 70 -0 = no damage 100 = nonemergence or plants destroyed ~481~4 O.Z. 0050/034008 Table 6 Herbicidal action Or new compounds; pre- and postemergence t,reatment in the grreenhouse Test plants and damage at 3.0 kg/ha Preemergence Postemergence Active in- Lolium Sinapis Echinochloa Ipo.moea Centaurea gredient no. multiflorum alba crus galli spp. cyanus

6 80 100 9 5 ` 90 100

7 90 100 80 - 100

8 90 100 80 - 100 19 100 i00 90 90 100 23 _ 95 100 90 98 26 _. 70 70 80 100 0 = no damage 100 = nonemergence or plants destroyed ~1~8~
0 . Z . 0050~034008 E XAMP LE A
90 parts by weight of compound 1 is mixed with 10 parts by weight of N-methyl-drpyrrolidone. A mixture is obtained whicn is 3uitable for application in the form of very fine drops.
EXAMPLE B
20 parts by weight of compound 2 is dissolved in a mixture consisting of 80 parts by weight of xylene, 10 parts by weight of the adduct of 8 to 10 moles of ethylene oxide with 1 mole of oleic acid-N-monoethanolamide, 5 parts by weight of the calcium salt of dodecylbenzenesulfonic acid, and 5 parts by weight of the adduct of 40 moles of ethylene oxide with 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and uniformly distributing it therein, an aqueous dis-persion is obtained containing 0.02~ by weight of the active ingredient.
EXAMPLE C
20 parts by weight of compound 3 is dissolved in a mix-ture consisting of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the 2C adduct of 7 moles of ethylene oxide with 1 mole of isooctyl-phenol, and 10 parts by weight of the adduct of 40 moles of ethyIene oxide with 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and finely distributing it therein, an aqueous dispersion is obtained containing 0.02%
by weight of the active ingredient.
EXAMPLE D
20 parts by weight of compound 1 is dissolved in a mix-- 37 ~

6~
o . z . ooso/034008 ture consisting of 25 parts by weight of cyclohexanol, 65 parts by weight of a mineral oil fraction having a boiling point between 210 and 280C, and 10 parts by weight of the adduct of 40 moles of ethylene oxide with 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and uniformly distributing it therein, an aqueous dispersion is obtained containing 0.02% by weight of the active ingredient.
EXAMPLE E
20 parts by weight of compound 2 is well mixed with ~ 3 parts by weight of the sodium salt of diisobutylnaphthalene--~rsulfonic acid, 17 parts by weight of the sodium salt of a lignin-sulfonic acid obtained from a sulfite waste liquor, and 60 parts by weight of powdered silica gel, and triturated in a hammer mill. By uniformly distributing the mixture in 20,000 parts by weight of water, a spray liquor is obtained containing 0.1% by weight of the active ingredient.
EXAMPLE F
3 parts by weight of compound 3 is intimately mixed with 97 parts by weight of particulate kaolin. A dust is obtained 2C containing 3% by weight of the active ingredient.
EXAMPLE G
30 parts by weight of compound 4 is intimately mixed with a mixture consisting of 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil which has been sprayed onto the surface of this silica gel. A formulation of the active ingredient is obtained having good adherence.

. ~4816~ o. z . 0050/034008 EXAMPLE H
40 parts by weight of compound 1 is intimately mixed with 10 parts of the sodium salt of a phenolsulfonic acid-urea-form-aldehyde condensate, 2 parts of silica gel and 48 parts of water. Dilution in 100,000 parts by weight of water gives an aqueous dispersion containing 0.04 wt% of active ingredient.
EXAMPLE I
20 parts of compound 2 is intimately mixed with 2 parts of the calcium salt of dodecylbenzenesulfonic acid, 8 parts of a fatty alcohol polyglycol ether, 2 parts of the sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate and 68 parts of a paraffinic mineral oil. A stable oily dispersion is obtained.

~ 39 -

Claims (3)

O.Z. 0050/034008 The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. A 5-imino-imidazolidin-2-one of the formula , where R1, R2 and R3 are identical or different and each denotes hydrogen, halogen, unsubstituted or halogen-substituted alkyl, alkoxy or alkylthio, each of from 1 to 4 carbon atoms, cyano or nitro.

2. A process for combating unwanted plant growth, wherein the plants or the soil are treated with a 5-imino-imidazolidin-2--ones of the formula , where R1, R2 and R3 are identical or different and each denotes hydrogen, halogen, unsubstituted or halogen-substituted alkyl, alkoxy or alkylthio, each of from 1 to 4 carbon atoms, cyano or nitro.

3. A 5-imino-imidazolidin-2-one selected from the group con-sisting of 1-(2-fluorophenyl)-3-methyl-5-imino-imidazolidin-2-one, 1-(4-isopropylphenyl)-3-methyl-5-imino-imidazolidin-2-one, 1-[3-O.Z. 0050/034008 -(1,1,2,2-tetrafluoroethoxy)-phenyl]-3-methyl-5-imino-imidazolidin--2-one, 1-(3,4-dichlorophenyl)-3-methyl-5-imino-imidazolidin-2--one and 1-(3,4-difluorophenyl)-3-methyl-5-imino-imidazolidin-2--one.