# Patent

## Title
Herbicide

## 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.

## Background
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.

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 amides

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 as Cynodon 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 communis etc.; Cyperaceae, such as Carex spp.        Eleocharis spp. Cyperus spp.      Scirpus spp. etc.; dicotyledonous weeds, such as Malvaceae, e.g. Abutilon theoprasti Hibiscus spp. Sida spp.         Malva spp. etc.; Compositae, such as Ambrosia spp.     Centaurea spp. Lactuca spp.      Tussilago spp. Senecia spp.      Lapsana communis Sonchus 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 as Convolvulus spp.  Cuscuta spp. Ipomoea spp.      Jaquemontia tamnifolia etc.; Cruciferae, such as Barbarea vulgaris Arabidopsis thaliana Brassica spp.     Descurainia spp. Capsella spp.     Draba spp. Sisymbrium spp.   Coronopus didymus Thlaspi spp.      Lepidium spp. Sinapis arvensis  Raphanus spp. etc.; Geraniaceae, such as Erodium spp.      Geranium spp. etc.; Portulacaceae, such as Portulaca spp.    etc.; Primalaceae, such as Anagallis arvensis Lysimachia spp. etc.; Rubiaceae, such as Richardia spp.    Diodia spp. Gallium spp.      etc.; Scrophulariacea, such as Linaria spp.      Digitalis spp. Veronica spp.     etc.; Solanaceae, such as Physalis spp.     Nicandra spp. Solanum spp.      Datura spp. etc.; Urticaceae, such as Urtica spp. Violaceae, such as Viola spp.        etc.; Zygophyllaceae, such as Tribulus terrestris etc.; Euphorbiaceae, such as Mercurialis annua Euphorbia spp. Umbelliferae, such as Daucus carota     Ammi majus Aethusa cynapium  etc.; Chenopodiaceae, such as Chenopodium spp.  Atriplex spp. Kochia spp.       Monolepsis nuttalliana Salsola Kali      etc.; Lythraceae, such as Cuphea spp.       etc.; Oxalidaceae, such as Oxalis spp. Ranunculaceae, such as Ranunculus spp.   Adonis spp. Delphinium spp.   etc.; Papaveraceae, such as Papaver spp.      Fumaria offinicalis etc.; Onagraceae, such as Jussiacea spp.    etc.; Rosaceae, such as Alchemillia spp.  Potentilla spp. etc.; Potamogetonaceae, such as Potamogeton spp.  etc.; Najadaceae, such as Najas spp.        etc.; Equisetaceae Equisetum spp.    etc.; Marsileaceae, such as Marsilea quadrifolia etc.; Polypodiaceae, Pteridium quilinum Alismataceae, such as Alisma spp. Sagittaria sagittifolia etc. The herbicides according to the invention may be em- ployed in cereal crops such as Avena spp.          Sorghum Triticum spp.       Zea mays Hordeum spp.        Panicum miliaceum Secale spp.         Oryza spp. Saccharum offinicarum and in dicotyledon crops such as Cruciferae, 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 hirsutum Leguminosae, e.g. Medicago ssp.       Phaseolus spp. Trifolium spp.      Arachis spp. Pisum spp.          Glycine max. Chenopodiaceae, e.g. Beta vulgaris Spinacia spp. Solanaceae, e.g. Solanum spp.        Capsicum annuum Nicotiania spp. Linaceae, e.g. Linum spp. Umbelliferae, e.g. Petroselinum spp.   Apium graveolens Daucus carota Rosaceae, e.g.      Fragaria Cucurbitaceae, e.g. Cucumis spp.        Cucurbita spp. Liliaceae, e.g. Allium spp. Vitaceae, e.g. Vitis vinifera Bromeliaceae, e.g. Ananas sativus. ______________________________________

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

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           II kg/ha            0.8     1.6     0.8   1.6 ______________________________________ Crop plants: Beta vulgaris    0       0       0     0 Beta vulgaris var. conditiva 0       0       0     0 Beta vulgaris var. altissima 0       0       0     0 Triticum aestivum 0       0       0     0 Hordeum vulgare  0       0       0     0 Secale cereale   0       0       0     25 Brassica napus   0       0       0     0 Unwanted plants: Alopecurus myosuroides 95      100     75    95 Avena sterilis   75      95      30    80 Avena fatua      80      100     35    85 Lolium multiflorum 90      100     70    90 Poa annua        95      100     75    95 0 = no damage 100 = complete destruction ______________________________________

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: comparison

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       II kg/ha                0.8     0.8 ______________________________________ Crop plants: Beta vulgaris        0       0 Triticum aestivum    0       0 Unwanted plants: Alopecurus myosuroides 80      60 Avena fatua          70      35 Lolium multiflorum   80      60 0 = no damage 100 = complete destruction ______________________________________

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

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 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      III kg/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    0 Hordeum vulgare 0   0   0   0   40  60  0   0    0 Secale cereale 0   0   0   20  40  80  0   20  40 Triticum aestivum 13  23  40  47  63  75  47  47  80 Alopecurus myosuroides 66  86  96  36  61  95  0   57  70 Avena fatua    80  88  95  62  85  95  50  81  95 Bromus 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 damage 100 = complete destruction __________________________________________________________________________

In the open, separate experiments - depending on the crop plants used -- were carried out with the following active ingredients: 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. Avena fatua is unexpectedly poor. myosuroides and to II in its compatibility with barley and wheat. Active ingredient I        II       III kg/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  0 Hordeum vulgare 0  0  0   0 5  2.5 0  0  0 Triticum aestivum 10 15 15 20 30 35 0  0  0 Alopecurus myosuroides 68 67 81 53 66 87 41 50 63 Avena fatua    48 61 65 47 57 85 41 52 68 0 = no damage 100 = complete destruction __________________________________________________________________________

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.

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.

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.

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.

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.

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.

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.