Thiol carbamates

Abstract

The new compound S-(2,3-dichloroallyl)-(2,2,4-trimethylazetidine)-1-carbothiolate, herbicides containing this compound as active ingredient, a process for controlling the growth of unwanted plants with this compound, and a process for its manufacture.

Description

The present invention relates to the new compound S-(2,3-dichloroallyl)-(2,2,4-trimethylazetidine)-1-carbothiolate, herbicides containing this compound as active ingredient, a process for controlling the growth of unwanted plants with this compounds, and a process for its manufacture.

It is known (German Laid-Open Application DOS 2,312,045) to use carbothiolates, e.g. S-(2,3,3-trichloroallyl)-(2,2,4-trimethylazetidine)-1-carbothiolate, as herbicides. However, their herbicidal action is poor.

We have now found that the compound S(2,3-dichloroally)(2,2,4-trimethylazetidine)-1-carbothiolate of the formula ##STR1## HAS A BETTER HERBICIDAL ACTION THAN THE ABOVEMENTIONED PRIOR ART COMPOUND.

The compound of the invention is prepared by reacting 2,2,4-trimethylazetidine with carbonyl sulfide and 2,3-dichloroallyl chloride in the presence of a trialkylamine. The halogen atoms of the dichloroallyl radical may be in either the cis or trans position.

EXAMPLE 1

38.6 parts (by weight) of 2,2,4-trimethylazetidine and 39.3 parts of triethylamine are added to 200 parts of dry benzene. At 0.degree. C., 23.4 parts of COS is passed into this solution. The temperature of the mixture is then allowed to rise to room temperature, and is then stirred for a further hour. At 0.degree. to +5.degree. C., a solution of 57.0 parts of 2,3-dichloroallyl chloride in 100 parts of anhydrous benzene is then dripped in. Up to completion of the reaction the mixture is stirred at room temperature; the precipitated triethylamine hydrochloride is removed, and extraction is carried out with water. After drying has been effected, the solvent is evaporated and the residue distilled in vacuo. Boiling point (0.01 mm): 111.degree.-112.degree. C.

n.sub.D.sup.25 : 1.5269 Yield: 57.0 parts of the compound of the invention.

Application may be effected for instance in the form of directly sprayable solutions, powders, 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 purpose for which the agents are being used; in any case they should ensure a fine distribution of the active ingredient.

For the preparation of solutions, emulsions, pastes and oil dispersions to be sprayed direct, mineral oil fractions of medium to high boiling points, such as kerosene or diesel oil, further coal-tar oils, etc. 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, cyclohexanol, 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 concentrates, pastes, oil dispersions or wettable powders by adding 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.

Examples of surfactants are: alkali metal, alkaline earth metal and ammonium salts of ligninsulfonic acid, naphthalenesulfonic 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 alcohol glycol ether, condensation products of sulfonated naphthalene and naphthalene derivatives with formaldehyde, condensation products of naphthalene or naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol ethers, ethoxylated isooctylphenol, ethoxylated octylphenol and ethoxylated nonylphenol, alkylphenol polyglycol ethers, tributylphenol polyglycol ethers, alkylaryl polyester alcohols, isotridecyl alcohols, fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylat polyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitol esters, lignin, sulfite waste liquors and methyl cellulose.

Powders, dusts and broadcasting agents may be prepared by mixing or grinding the active ingredients with a solid carrier.

Granules, e.g., coated, impregnated or homogeneous granules, may be prepared by bonding the active ingredients to solid carriers. Examples of solid carriers are mineral earths such as silica gel, silicic acid, silica gels, silicates, talc, kaolin, Attaclay, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground plastics, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, and ureas, and vegetable products such as grain flours, 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.

There may be added to the compositions or individual active ingredients (if desired, immediately before use (tankmix)) oils of various types, wetting agents or adherents, herbicides, fungicides, nematocides, insecticides, bactericides, trace elements, fertilizers, antifoams (e.g., silicones), growth regulators, antidotes and other herbicidally effective compounds such as

substituted anilines substituted aryloxycarboxylic acids and salts, esters and amides thereof, substituted ethers substituted arsonic acids and their salts, esters and amides substituted benzimidazoles substituted benzisothiazoles substituted benzothiadiazinone dioxides substituted benzoxazines substituted benzoxazinones substituted benzothiadiazoles substituted biurets substituted quinolines substituted carbamates substituted aliphatic carboxylic acids and their salts, esters and amides substituted aromatic carboxylic acids and their salts, esters and amides substituted carbamoylalkylthiol- or -dithiophosphates substituted quinazolines substituted cycloalkylamidocarbothiolic acids and their salts, esters and amides substituted cycloalkylcarbonamidothiazoles substituted dicarboxylic acids and their salts, esters and amides substituted dihydrobenzofuranyl sulfonates substituted disulfides substituted dipyridylium salts substituted dithiocarbamates substituted dithiophosphoric acids and their salts, esters and amides substituted ureas substituted hexahydro-1H-carbothioates substituted hydantoins substituted hydrazides substituted hydrazonium salts substituted isoxazole pyrimidones substituted imidazoles substituted isothiazole pyrimidones substituted ketones substituted naphthoquinones substituted aliphatic nitriles substituted aromatic nitriles substituted oxadiazoles substituted oxadiazinones substituted oxadiazolidine diones substituted oxadiazine diones substituted phenols and their salts and esters substituted phosphonic acids and their salts, esters and amides substituted phosphonium chlorides substituted phosphonalkyl glycines substituted phosphites substituted phosphoric acids and their salts, esters and amides substitutes piperidines substituted pyrazoles substituted pyrazole alkylcarboxylic acids and their salts, esters and amides substituted pyrazolium salts substituted pyrazolium alkyl sulfates substituted pyridazines substituted pyridazones substituted pyridine carboxylic acids and their salts, esters and amides substituted pyridines substituted pyridine carboxylates substituted pyridinones substituted pyrimidines substituted pyrimidones substituted pyrrolidine carboxylic acid and its salts, esters and amides substituted pyrrolidines substituted pyrrolidones substituted arylsulfonic acids and their salts, esters and amides substituted styrenes substituted tetrahydrooxadiazine diones substituted tetrahydroxadiazole diones substituted tetrahydromethanoindenes substituted tetrahydroxadiazole thiones substituted tetrahydrothiadiazine thiones substituted tetrahydrothiadiazole diones substituted aromatic thiocarbonylamides substituted thiocarboxylic acids and their salts, esters and amides substituted thiol carbamates substituted thioureas substituted thiophosphoric acids and their salts, esters and amides substituted triazines substituted triazoles substituted uracils, and substituted uretidine diones.

The last-mentioned herbicidal compounds may also be applied before or after the active ingredients or compositions thereof according to the invention.

These agents may be added to the herbicides according to the invention in a ratio by weight of from 1:10 to 10:1. The same applies to oils, fungicides, nematocides, insecticides, bactericides, antidotes and growth regulators.

The amount used of the agents according to the invention may vary and depends in essence on the type of effect to be achieved; it is generally from 0.1 to 15 (and more), preferably from 0.2 to 6, kg per hectare of active ingredient. The agents according to the invention may be used once or several times before or after planting, before sowing, and before, during or after emergence of the crop plants and unwanted plants.

The new compositions have a strong herbicidal action and may therefore be used as weedkillers or for controlling the growth of unwanted plants. Whether the new active ingredients are used as total or selective agents depends in essence on the amount of ingredient used per unit area.

By weeds and unwanted plant growth are meant all monocotyledonous and dicotyledonous plants which grow in loci where they are not desired.

The agents according to the invention may therefore be used for controlling for instance

______________________________________Gramineae, such asCynodon spp. Dactylis spp.Digitaria spp. Avena spp.Echinochloa spp. Bromus spp.Setaria spp. Uniola spp.Panicum spp. Poa spp.Alopecurus spp. Leptochloa spp.Lolium spp. Brachiaria spp.Sorghum spp. Eleusine spp.Agropyron spp. Cenchrus spp.Phalaris spp. Eragrostis spp.Apera spp. Phragmites communisetc.;Cyperaceae, such asCarex spp. Eleocharis spp.Cyperus spp. Scirpus spp.etc.;dicotyledonous weeds, such asMalvaceae, e.g.Abutilon theoprasti Hibiscus spp.Sida spp. Malva spp.etc.;Compositae, such asAmbrosia spp. Centaurea spp.Lactuca spp. Tussilago spp.Senecia spp. Lapsana communisSonchus spp. Tagetes spp.Xanthium spp. Erigeron spp.Iva spp. Anthemis spp.Galinsoga spp. Matricaria spp.Taraxacum spp. Artemisia spp.Chrysanthemum spp. Bidens spp.Cirsium spp. etc.;Convolvulaceae, such asConvolvulus spp. Cuscuta spp.Ipomoea spp. Jaquemontia tamnifoliaetc.;Cruciferae, such asBarbarea vulgaris Arabidopsis thalianaBrassica spp. Descurainia spp.Capsella spp. Draba spp.Sisymbrium spp. Coronopus didymusThlaspi spp. Lepidium spp.Sinapis arvensis Raphanus spp.etc.;Geraniaceae, such asErodium spp. Geranium spp.etc.;Portulacaceae, such asPortulaca spp. etc.;Primalaceae, such asAnagallis arvensis Lysimachia spp.etc.;Rubiaceae, such asRichardia spp. Diodia spp.Gallium spp. etc.;Scrophulariacea, such asLinaria spp. Digitalis spp.Veronica spp. etc.;Solanaceae, such asPhysalis spp. Nicandra spp.Solanum spp. Datura spp.etc.;Urticaceae, such asUrtica spp.Violaceae, such asViola spp. etc.;Zygophyllaceae, such asTribulus terrestris etc.;Euphorbiaceae, such asMercurialis annua Euphorbia spp.Umbelliferae, such asDaucus carota Ammi majusAethusa cynapium etc.;Chenopodiaceae, such asChenopodium spp. Atriplex spp.Kochia spp. Monolepsis nuttallianaSalsola Kali etc.;Lythraceae, such asCuphea spp. etc.;Oxalidaceae, such asOxalis spp.Ranunculaceae, such asRanunculus spp. Adonis spp.Delphinium spp. etc.;Papaveraceae, such asPapaver spp. Fumaria offinicalisetc.;Onagraceae, such asJussiacea spp. etc.;Rosaceae, such asAlchemillia spp. Potentilla spp.etc.;Potamogetonaceae, such asPotamogeton spp. etc.;Najadaceae, such asNajas spp. etc.;EquisetaceaeEquisetum spp. etc.;Marsileaceae, such asMarsilea quadrifolia etc.;Polypodiaceae,Pteridium quilinumAlismataceae, such asAlisma spp.Sagittaria sagittifoliaetc.The herbicides according to the invention may be em-ployed in cereal crops such asAvena spp. SorghumTriticum spp. Zea maysHordeum spp. Panicum miliaceumSecale spp. Oryza spp.Saccharum offinicarumand in dicotyledon crops such asCruciferae, e.g.Brassica spp. Raphanus spp.Sinapis spp. Lepidium spp.Compositae, e.g.Lactuca spp. Carthamus spp.Helianthus spp. Scorzonera spp.Malvaceae, e.g.Gossypium hirsutumLeguminosae, e.g.Medicago ssp. Phaseolus spp.Trifolium spp. Arachis spp.Pisum spp. Glycine max.Chenopodiaceae, e.g.Beta vulgarisSpinacia spp.Solanaceae, e.g.Solanum spp. Capsicum annuumNicotiania spp.Linaceae, e.g.Linum spp.Umbelliferae, e.g.Petroselinum spp. Apium graveolensDaucus carotaRosaceae, e.g. FragariaCucurbitaceae, e.g.Cucumis spp. Cucurbita spp.Liliaceae, e.g.Allium spp.Vitaceae, e.g.Vitis viniferaBromeliaceae, e.g.Ananas sativus.______________________________________

EXAMPLE 2

In the greenhouse, loamy sandy soil was filled into pots and sown with various seeds. The solid prepared in this manner was then immediately treated with

I s-(2,3-dichloroallyl)-(2,2,4-trimethylazetidine)-1-carbothiolate and, for comparison, Ii s-(2,3,3-trichloroallyl)-(2,2,4-trimethylazetidine)-1-carbothiolate. The application rates for both compounds were 0.8 and 1.6 kg/ha, each amount being dispersed or emulsified in 500 liters of water per hectare.

After 3 to 4 weeks it was ascertained that active ingredient I had a better herbicidal action than active ingredient II, combined with the same crop plant compatibility.

The results are given below:

______________________________________Active ingredient I IIkg/ha 0.8 1.6 0.8 1.6______________________________________Crop plants:Beta vulgaris 0 0 0 0Beta vulgaris var. conditiva 0 0 0 0Beta vulgaris var. altissima 0 0 0 0Triticum aestivum 0 0 0 0Hordeum vulgare 0 0 0 0Secale cereale 0 0 0 25Brassica napus 0 0 0 0Unwanted plants:Alopecurus myosuroides 95 100 75 95Avena sterilis 75 95 30 80Avena fatua 80 100 35 85Lolium multiflorum 90 100 70 90Poa annua 95 100 75 95 0 = no damage100 = complete destruction______________________________________

EXAMPLE 3

In the greenhouse, various plants were treated at a growth height of from 2 to 20 cm with 0.8 kg/ha of each of the following active ingredient, each being dispersed or emulsified in 500 liters of water per hectare:

I s-(2,3-dichloroallyl)-(2,2,4-trimethylazetidine)-1-carbothiolate and, for comparison Ii s-(2,3,3-trichloroallyl)-(2,2,4-trimethylazetidine)-1-carbothiolate.

After 2 to 3 weeks it was ascertained that active ingredient I had a better herbicidal action than II, combined with the same crop plant compatibility.

The results are given below:

______________________________________Active ingredient I IIkg/ha 0.8 0.8______________________________________Crop plants:Beta vulgaris 0 0Triticum aestivum 0 0Unwanted plants:Alopecurus myosuroides 80 60Avena fatua 70 35Lolium multiflorum 80 60 0 = no damage100 = complete destruction______________________________________

EXAMPLE 4

In the greenhouse, loamy sandy soil was filled into pots and sown with the seeds of various plants. Subsequently, the soil prepared in this manner was treated with the following amounts of the following individual active ingredients and compositions thereof as dispersions or emulsions:

Iv 1-phenyl-4-amino-5-chloropyridazone-(6) Iii o-(methylaminosulfonyl)-glycolic acid-N-isopropylanilide I s-(2,3-dichloroallyl)-(2,2,4-trimethylazetidine)-1-carbothiolate each at rates of 0.25, 0.5, 0.75, 1, 1.5, 2, 3 and 4 kg/ha; Iv + i and III + I each at rates of 0.25 + 0.75, 0.75 + 0.25, 2 + 1, 1 + 2, 1.5 + 1.5 and 2 + 2 kg/ha; Iv + i + iii at rates of 0.25 + 0.25 + 0.5, 0.25 + 0.5 + 0.25, 0.5 + 0.25 + 0.25, 0.25 + 0.25 + 1.5, 0.25 + 1.5 + 0.25 and 1.5 + 0.25 + 0.25 kg/ha.

After 4 to 5 weeks it was ascertained that at the lower application rates the compositions had a better herbicidal action than their components and the same crop plant compatibility, and at the higher application rates the compositions had better crop plant compatibility than their components.

The results are given below:

__________________________________________________________________________Active ingredient IVkg/ha 0.25 0.5 0.75 1 1.5 2 3 4__________________________________________________________________________Crop plants:Beta vulgaris 0 0 0 0 0 0 0 10Unwanted plants:Avena fatua 0 5 8 12 15 20 40 75Echinochloa crus-galli 5 6 10 13 20 32 65 75Matricaria chamomilla 15 20 30 40 60 85 100 100Active ingredient III__________________________________________________________________________Beta vulgaris 0 0 0 0 0 0 0 10Avena fatua 10 15 30 40 45 54 75 80Echinochloa crus-galli 20 25 45 70 90 100 100 100Matricaria chamomilla 5 15 25 35 55 80 90 95Active ingredient I__________________________________________________________________________Beta vulgaris 0 0 0 0 10 5 10 15Avena fatua 20 40 80 90 95 98 100 100Echinochloa crus-galli 5 10 15 20 30 40 45 50Matricaria chamomilla 0 2 5 8 10 15 20 30Active ingredient IV + Ikg/ha 0.25+ 0.75+ 2+1 1+2 1.5+ 2+2 0.75 0.25 1.5__________________________________________________________________________Beta vulgaris 0 0 0 5 0 5Avena fatua 100 95 100 100 100 100Echinochloa crus-galli 60 55 90 92 90 100Matricaria chamomilla 60 70 100 100 100 100Active ingredient III + Ikg/ha 0.25+ 0.75+ 2+1 1+2 1.5+ 2+2 0.75 0.25 1.5__________________________________________________________________________Beta vulgaris 0 0 0 5 0 5Avena fatua 100 100 100 100 100 100Echinochloa crus-galli 75 90 100 100 100 100Matricaria chamomilla 50 65 100 100 100 100Active ingredient IV + III + Ikg/ha 0.25+ 0.25+ 0.5+ 0.25+ 0.25+ 1.5+ 0.25+ 0.5+ 0.25+ 0.25+ 1.5+ 0.25+ 0.5 0.25 0.25 1.5 0.25 0.25__________________________________________________________________________Beta vulgaris 0 0 0 0 0 0Avena fatua 95 95 97 100 100 100Echinochloa crus-galli 73 75 78 100 100 100Matricaria chamomilla 60 70 62 90 100 100 0 = no damage100 = complete destruction__________________________________________________________________________

EXAMPLE 5

In the greenhouse, loamy sandy soil was filled into pots and sown separately, according to species, with the seeds of various plants. The soil prepared in this manner was then immediately treated with

I s-(2,3-dichloroallyl)-(2,2,4-trimethylazetidine)-1-carbothiolate Ii 2,3-dichloroallyl N,N-diisopropylthiolcarbamate Iii 2,2,3-trichloroallyl N,N-diisopropylthiolcarbamate, each amount of each substance being emulsified in 500 liters of water per hectare. After the soil had been sprayed, each pot was watered and covered with a transparent plastic hood. This hood was only removed after the plants had emerged. During the experiment the pots were kept moist.

The plants employed, the active ingredient concentrations and the results obtained are given in the following table.

Active ingredient I is superior to comparative compound III in its action on unwanted grasses. The compatibility of I with cereals is far better than that of II.

__________________________________________________________________________Active ingredient I II IIIkg/ha 0.4-0.5 0.8-1.0 1.5-2.0 0.4-0.5 0.8-1.0 1.5-2.0 0.4-0.5 0.8-1.0 1.5-2.0__________________________________________________________________________Beta vulgaris 0 0 6 0 0 0 0 0 0Hordeum vulgare 0 0 0 0 40 60 0 0 0Secale cereale 0 0 0 20 40 80 0 20 40Triticum aestivum 13 23 40 47 63 75 47 47 80Alopecurus myosuroides 66 86 96 36 61 95 0 57 70Avena fatua 80 88 95 62 85 95 50 81 95Bromus inermis 100 100 -- 90 95 -- 40 95 --Digitaria sanguinalis 60 90 -- 60 90 -- 0 10 --Eleusine indica 90 95 -- 50 95 -- 40 90 --Sorghum halepense 20 70 -- 10 45 -- 5 55 -- 0 = no damage100 = complete destruction__________________________________________________________________________

EXAMPLE 6

In the open, separate experiments - depending on the crop plants used -- were carried out with the following active ingredients:

I s-(2,3-dichloroallyl)-(2,2,4-trimethylazetidine)-1-carbothiolate Ii 2,3-dichloroallyl N,N-diisopropylthiolcarbamate Iii 2,2,3-trichloroallyl N,N-diisopropylthiolcarbamate each amount of each compound being emulsified in 700 liters of water per hectare. The soil, which had been prepared for sowing, was sprayed and cultivated to a depth of 5 cm within an hour to incorporate the active ingredients into the soil. Sowing followed. The soil was a sandy loam. Rainfall was normal.

The following table contains the test plants, the active ingredient application rates, and the results.

(1) The average action of all three compounds on Alopecurus myosuroides and Avena fatua is unexpectedly poor. (2) Active ingredient I is superior to III in its action on Alopecurus myosuroides and to II in its compatibility with barley and wheat. __________________________________________________________________________Active ingredient I II IIIkg/ha 1.0 1.5 2.0 1.0 1.5 2.0 1.0 1.5 2.0__________________________________________________________________________Beta vulgaris 0 0 0 -- 0 0 0 0 0Hordeum vulgare 0 0 0 0 5 2.5 0 0 0Triticum aestivum 10 15 15 20 30 35 0 0 0Alopecurus myosuroides 68 67 81 53 66 87 41 50 63Avena fatua 48 61 65 47 57 85 41 52 68 0 = no damage100 = complete destruction__________________________________________________________________________

EXAMPLE 7

90 parts by weight of compound I is mixed with 10 parts by weight of N-methyl-.alpha.-pyrrolidone. A mixture is obtained which is suitable for application in the form of very fine drops.

EXAMPLE 8

20 parts by weight of compound I 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 to 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 to 1 mole of castor oil. By pouring the soluton 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 9

20 parts by weight of compound I is dissolved in a mixture consisting of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the adduct of 7 moles of ethylene oxide to 1 mole of isooctylphenol, and 10 parts by weight of the adduct of 40 moles of ethylene oxide to 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 10

20 parts by weight of compound I is dissolved in a mixture consisting of 25 parts by weight of cyclohexanol, 65 parts by weight of a mineral oil fraction having a boiling point between 210.degree. and 280.degree. C., and 10 parts by weight of the adduct of 40 moles of ethylene oxide to 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 11

20 parts by weight of compound I is well mixed with 3 parts by weight of the sodium salt of diisobutylnaphthalene- -sulfonic acid, 17 parts by weight of the sodium salt of a ligninsulfonic 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 liquid is obtained containing 0.1% by weight of the active ingredient.

EXAMPLE 12

3 parts by weight of compound I is intimately mixed with 97 parts by weight of particulate kaolin. A dust is obtained containing 3% by weight of the active ingredient.

EXAMPLE 13

30 parts by weight of compound I 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 silical gel. A formulation of the active ingredient is obtained having good adherence.

Claims

1. S-(2,3-dichloroallyl)-(2,2,4-trimethylazetidine)-1-carbothiolate.

2. A process for controlling the growth of unwanted plants wherein the soil or the plants are treated with a herbicidally effective amount of S-(2,3-dichloroallyl)-(2,2,4-trimethylazetidine)-1-carbothiolate.