DE2312045A1 - CARBOTHIOLATES - Google Patents

Description

Badische Anilin- & Soda-Fabrik AG

Our reference: O.Z. 29 752 Sws / Wil 6700 Ludwigshafen, 7.3-1973

Carbothiolate

The present invention relates to new valuable carbothiolates of azetidines, herbicides containing them and the control unwanted vegetation with these compounds.

It is known to use S-ethyl hexahydro- lH-azepine-1-carbothiolate Control unwanted plants to use in crops of crops such as barley, wheat and rice. Its effect is however bad

It has been found that carbothiolates of azetidines of the formula

\ .NCSR ²

It

in the

R ^{1 is} an alkyl radical (methyl, ethyl),

η O to 4,

X oxygen or sulfur and

ρ
R is an aliphatic radical (methyl, ethyl, propyl, iso-propyl, butyl, sec-butyl, tert-butyl, allyl, propargyl, Butynyl, isobutynyl, β-hydroxyethyl, β-chloroethyl, dichloroallyl, trichloroallyl, 2-methyl-3-dichloroallyl, β-cyanoethyl, β-methoxyalkyl) or the remainder of the formula

means in which R ^{1 is} halogen (fluorine, chlorine, bromine, iodine) or nitro, cyano, alkoxy, methoxy, ethoxy or alkyl (methyl, ethyl), m, 0, 1 or 2 and nv, 0 to 4, and if m _{2 is} greater than 1, R ¹ denotes identical or different substituents, they have a good herbicidal effect. You own the same

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and often better herbicidal action, better plant tolerance as the well-known S-ethyl-hexahydro-1H-azepine-learbothiolate ο

The preparation of the active ingredients can be carried out in such a way that a chloroformic acid thioester with an optionally substituted azetidine is implemented. Likewise, you can produce the active ingredients if you have azetidines in the form of the corresponding Lets N-carboxylic acid chlorides react with mercaptans »

The preparation of the azetidines is known from the literature.

example 1

Preparation of S-ethyl- (2,2,4-trimethyl-azetidine) -l-carbothiolate

To a mixture of 4.95 parts (parts by weight) of 2,2,4-trimethyl-azetidine and 6 parts of triethylamine in 50 parts by weight Benzene is added dropwise at from 50 to 40 ° C. 6.25 parts of chloroformic acid thioethyl ester to"

After an hour, the triethylamine hydrochloride is filtered off with suction and the filtrate was washed with water. After drying, it is concentrated in vacuo and the residue is distilled off.

6.70 parts of S-ethyl- (2,2,4-trimethyl-azetidine) -1-carbothiolate are obtained. The compound has the following structural formula:

The following Make connections:

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S-methyl- (2,2,4-trimethyl-azetidine) -1-carbothiolate, ^Κ Ρ · Ο, Ο5 ^{: 7} ° ^C

S-propyl (2,2,4-trimethyl-azetidine) -1-carbothiolate, K _P o _{0 05} : 81 ° C

S-iso-propyl- (2,2,4-trimethyl-azetidin) -1-carbothiolate, ^Kp * ^{0.01: 67 to 71} ° ^C

S-sec-butyl (2,2,4-trimethyl-azetidin) -1-carbothiolate, ^{Kp '0.01: 75 to 80} ° ^C

S-Trichlorallyl- (2,2,4-trimethyl-azetidin) -1-carbothiolate, Kp _OjO1. 130 ⁰ C

S-Benzyl- (2,2,4-trimethyl-azetidine) -1-carbothiolate, bp _{Q Q1} '. 135 ° C S- (p-chlorobenzyl) - (2,2,4-trimethyl-azetidine) -1-carbothiolate, b.p. ₀₅ : 154 ° C

S-Benzyl- (3,3-dimethyl-azetidine) -1-carbothiolate, bp _{Q Q1} '. 128 ⁰ C S- (ß-phenylethyl) - (2,2,4-trimethyl-azetidine) -1-carbothiolate,

^Kp * o, or ^{5 J} 20 * ⁱ - » ⁵ - ' ^yö S- (β-phenylethyl) - (3,3-dimethyl-azetidine) -1-carbothiolate ^{Kp #} 0.01 ^{: 1} ^ ^{0 to 1} ^ ⁰ C, n ₂₀ : 1.5996 S-benzyl- (2,2,4-trimethyl-azetidine) -1-thiolcarbothiolate, Kpo _nm : 160 ° C, n _{O (} -: 1.6026 S-propyl- (2, 2,4-trimethyl-azetidine) -1-thiolcarbothiolate, b.p. _{0 01} ί 10O ⁰ C, n ₂₅ : 1.5540 S-benzyl-azetidine-1-carbothiolate, S-ethyl-azetidine-1-carbothiolate, S-propyl-azetidine-1-carbothiolate, Si-propyl-azetidine-1-carbothiolate, S-benzyl- (2-methyl-azetidine) -1-carbothiolate, S-butyl- (2,2,4-trimethyl-azetidine ) -1-carbothiolate, ^{Κρ0.01 : 90 to 95} ° ^{Cj n} 20 ^{: 1Λ8} ? 5 '

The application takes place in the form of directly sprayable solutions, Powders, suspensions or dispersions, emulsions, oil dispersions, Pastes, aqueous solutions if the compounds are soluble, dusts, grit, granules. The application forms depend entirely on the intended use; in any case, they should have the finest possible distribution of those according to the invention Ensure active ingredients.

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For the production of directly sprayable solutions, emulsions, Pastes and oil dispersions come from medium oil fractions to a high boiling point, such as kerosene or diesel oil, also coal tar oils, etc., as well as oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, for example methanol, ethanol, propanol, butanol, chloroform, Carbon tetrachloride, benzene, toluene, xylene, cyclohexanol, cyclohexanone, chlorobenzene, paraffin, tetrahydronaphthalene, alkylated Naphthalenes, isophorone, etc., strongly polar solvents such as. B. dimethylformamide, dimethyl sulfoxide, etc., into consideration.

Aqueous application forms can be made from emulsion concentrates, Pastes or wettable powders (wettable powders), oil dispersions can be prepared by adding water. For production of Emulsions, pastes or oil dispersions can use the substances as such or dissolved in an oil or solvent Wetting agents, adhesives, dispersants or emulsifiers can be homogenized in water. Wetting agents, adhesives, dispersants or emulsifiers and possibly Solvent or oil-based concentrates are produced, which are suitable for dilution with water.

The following surface-active substances should be mentioned:

Alkali, alkaline earth, ammonium salts of lignin sulfonic acid, naphthalene sulfonic acids, Phenolsulfonic acids, alkylarylsulfonates, alkyl sulfates, Alkyl sulfonates, alkali and alkaline earth salts of dibutylnaphthalene sulfonic acid, lauryl ether sulfate, fatty alcohol sulfates, Fatty acid alkali and alkaline earth salts, salts of sulfated hexadecanols, heptadecanols, octadecanols, salts of sulfated Petroleum alcohol glycol ethers, condensation products of sulfonated! Naphthalene and naphthalene derivatives with formaldehyde, condensation products of naphthalene or naphthalene sulfonic acids with Phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated Isooctylphenol, -. Octylphenol, - Nonylphenol, Alkylphenolpolyglykoläther, Tributylphenyl polyglycol ethers, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ether, Ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitol esters, lignin, sulphite waste liquors and methyl cellulose.

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Powder and dust can be produced by mixing or grinding together the active substances with a solid carrier. The powders have e.g. B. e.ine grain size of 0.02 to 0.04 mm (air classified) having a BET surface area of 200 m ² / g with particles in the size of 10 "^ to 10 ~ ² mm. Dusts have z. B. a Grain size up to approx. 0.1 mm or wind-sighted with a BET surface area of 200 m / g with particles in the size of 10 ^ to 10 mm.

Litter can be spread by mixing or grinding together the active substances are produced with a solid carrier. B. a grain size of about 0.075 to 0.2 mm.

Granules (e.g. coating, impregnation and homogeneous granules) can be produced by binding the active ingredients to solid carriers. The grain size is z. B. 0.01 to 5 mm »

Solid carriers are e.g. B. Mineral earths such as Tonsil, silica gel, Silicas, silica gels, silicates, talc, kaolin, Attaelay, limestone, lime, chalk, bolus, LÖ * ß, clay, dolomite, diatomaceous earth, Calcium and magnesium sulfate, magnesium oxide, ground plastics, fertilizers, such as. B. ammonium sulfate, ammonium phosphate, Ammonium nitrate, ureas and vegetable products such as cereal flours, tree bark, wood and nut shell flour, cellulose powder and other solid carriers »

The herbicidal mixtures or individual products can include oils of various types, fungicides, nematocides, insecticides, bactericides, trace elements, fertilizers, antifoams (e.g. silicones), growth regulators, antidotes or other herbicidally active compounds, such as. B. substituted alkylsulfonyloxycarboxamides, substituted alkylamidosulfonyloxycarboxamides, substituted amidosulfonyloxycarboxamides, substituted alkyl- or amidosulfonyloxycarboxycloalkylamides,
substituted anilines,

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substituted aryloxycarboxylic acids and their salts, esters and amides,

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 carbamoylalkyl thiol or dithiophosphates, substituted quinazolines,

substituted Cycloalkylamidocarbonthiolsäuren and their Salts, esters and amides,

substituted cycloalkylcarbonamido-thiazoles, substituted dicarboxylic acids and salts, esters and amides, substituted dihydrobenzofuranyl sulfonates, substituted disulfides,

substituted dipyridylium salts,

substituted dithiocarbamates,

substituted dithiophosphoric acids and their salts, esters or amides,

substituted ureas,

substituted hexahydro-1-H-earbothioates, substituted hydantoins, ■

substituted hydrazides,

substituted hydrazonium salts

substituted isooxazole pyrimidones,

substituted imidazoles,

substituted isothiazole pyrimidones,

substituted ketones,

substituted haphtoehinones,

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substituted aliphatic ^ nitriles, substituted aromatic nitriles, substituted oxadiazoles, substituted oxadiazinones, substituted oxadiazolidinediones, substituted oxadiazinediones, substituted phenols and their salts and esters, substituted phosphonic acids and their salts, esters and amides, substituted phosphonium chloride, substituted phosphonoalkylglyzines, substituted phosphites,

substituted phosphoric acids and their salts, esters and amides, substituted piperidines, substituted pyrazoles,

substituted pyrazole alkyl carboxylic acids and their salts, esters and amides,

substituted pyrazolium salts, substituted pyrazolium alkyl sulfates, substituted pyridazines, substituted pyridazones, substituted pyridinearboxylic acids and their salts, esters and Amides,

substituted pyridines,

substituted pyridine arboxylates, substituted pyridinones, substituted pyrimidines, substituted pyrimidones, substituted pyrrolidinecarboxylic acids and their salts, esters and amides,

substituted pyrrolidines, substituted pyrrolidones, substituted arylsulfonic acids and their salts, esters and Amides,

substituted styrenes,

substituted tetrahydro-oxadiazinediones, substituted tetrahydro-oxadiazoldiones, substituted tetrahydromethanoindenes substituted tetrahydro-oxadiazolthiones, substituted tetrahydro-thiadiazinthiones,

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substituted tetrahydro-thiadiazoldiones, '

substituted aromatic thiocarboxamides, substituted thiocarboxylic acids and their salts, esters and amides, substituted thiocarbamates,

substituted thioureas,

substituted thiophosphoric acids and their salts, esters and Amides,

substituted triazines,

substituted triazoles,

substituted uracils,

substituted uretidinediones,

are added and / or the same individually beforehand, at the same time and / or applied afterwards.

These agents can be admixed with the herbicides according to the invention in a ratio of 1:10 to 10: 1. The same goes for for oils. Fungicides, nematocides, insecticides, bactericides, trace elements, Fertilizers, anti-foaming agents and growth regulators.

The agents according to the invention can, inter alia, in the before or Post-planting procedures, pre-sowing procedures, pre-emergence procedures, Post-emergence process, ULV process, granulate and scattering processes, Procedure during emergence, single or multiple use procedures and tank mix method (for mixtures) used will"

The new active ingredients have a strong herbicidal effect and can therefore be used as weed killers or for control unwanted vegetation can be used. Whether the new active ingredients act as total or selective agents, depends mainly on the amount of active ingredient per unit area away.

All are under weeds or unwanted vegetation monocotyledonous and dicotyledonous plants to understand those in places grow up where they are not wanted.

For example, with the agents according to the invention Gramineae, how

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23-2045

Cynodon spp.

Digitaria spp.

Echinochloa spp.

Setaria spp.

Panicum spp.

Alopecurus spp.

LoIium spp.

Sorghum spp.

Agropyron spp.

Phalaris spp.

Apera spp.
Cyperaceae, such as Carex spp _o

Cyperus spp.

and others

dicotyledonous weeds, such as Malvaceae, such as _o

Abutilon theoprasti Sida sppο

and other,
Compostiae such as Ambrosia spp.

Lactuca spp.

Senecia spp.

Sonchus spp.

Xanthium spp.

Iva spp.

Galinsoga spp.

Taraxacum spp.

Chrysanthemum spp.

Cirisum spp. Convolvulaceae, like Convolvulus spp.

Ipomoea spp.

and other,
Cruciferae such as Barbarea vulgaris Brassica spp.

Capsella spp.

Dactylis spp. Avena spp. Bromus spp. Uniola spp. Poa spp. Leptochloa spp. Brachiaria spp. Eleusine spp. Cenchrus spp. Eragrostis spp. and other,

Eleocharis spp. Scirpus spp.

Hibiscus spp. Malva spp.

Centaurea spp. Tussilago spp. Lapsana communis Tagetes spp. Erigeron spp. Anthemis spp. Matricaria spp. Artemisia spp. Bidens spp. and other,

Cuscuta spp. Jaquemontia tamnifolia

Arabidopsis thaliana Descurainia spp. Draba spp.

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Sisymbrium spp.

ThIaspi spp »Sinapis arvensis

and others, Geraniaceae such as Erodium spp.

• and others, Portulacaeeae, such as

Portulaca spp » Primulaceae such as Anagallis arvensis

and others, Rubiaceae, such as Richardia spp =

Galium spp »Scrophulariaceae, such as Linaria spp ₀

Veronica spp »Solanaceae, such as Physalis spp» Solarium spp.

and others, such as Urticaceae. Urtica sppo Violaceae, like

Viola sppο Zygophyllaceae, like

Tribulus terrestis Euphorbiaceae, like

Mercurialis annua Umbelliferae, such as Daucus carota

Aethusa cynapium CommeHnaeae, like

Commelina spp, Labiatae, such as Lamium spp »

and others, Leguminosae, such as Coronopus didymus Lepidium spp. Raphanus spp.

Geranium spp.

and others, Lysimachia spp,

Diodia spp. and other,

Digitalis spp. and other,

Nicandra spp. Datura spp.

and others, and others, Euphorbia spp,

Ammi majus and others, and others, Galeopsis spp "

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Medieago spp "Trifolium spp" Vieia sppο

and others, such as Plantaginaceae

Plantago spp. Polygonaceae, such as Polygonum spp "

Rumex spp »Aizoaeeae, such as

Mollugo verticillata, like Amaranthaceae

Amaranthus sppα Boraginaceae, such as Amsinckia spp " Myostis sppο

and others .. Caryophyllaeeae such as Stellaria spp.

Spergula spp _o Saponaria spp.

Scleranthus annuus Chenopodiaceae, such as Chenopodium spp " Kochia spp.

Salsola Kali Lythraceae, such as

• Cuphea spp _o Oxalidaceae, such as

Oxalis spp. Ranunculaceae, like Ranunculus spp.

Delphinium spp. Papaveraceae such as Papaver spp.

and others, Onagraceae, like

Jussiaea spp. Rosaceae, like

Sesbania exaltata Cassia spp. Lathyrus spp.

and other,

Fagopyrum spp. and other,

and others, and others,

Anchusa spp. Lithospermum spp.

Silene spp. Cerastium spp. Agrostemma pallida and other,

Atriplex spp. Monolepsis nuttalliana and others,

and other,

Adonis spp. and other,

Pumaria officinalis

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Alchemillia spp. Potentilla spp.

and other,
Potamogetonaceae, such as

Potamogeton spp. and other,

Najadaceae, like

Najas όρρ «and others,

Marsileaceae, like

Marsilea quadrifolia and others to be fought "

The agents according to the invention can vary in the amount used. The amount used depends mainly on the type the desired effect.

The application rate is generally between 0.1 and 15 or more kg of active ingredient per hectare.

The new funds can be used in cereal crops, such as

Avena spp. Sorghum

Triticum spp. Zea mays

Hordeum spp »Panicum miliaceum

Seeale spp. 'Oryza spp. and in cultures of dicotyledons such as Cruciferae, e.g. B.

Brassica spp. Raphanus spp.

Sinapis spp. Lepidium spp. Composistae, e.g. B ₀

Lactuca spp _o Carthamus spp.

Helianthus spp. Scorzonera spp. Malvaceae, such as _o Gossypium hirsutum Leguminosae, such "B.

Medicago spp. Phaseolus spp.

Trifolium spp. Arachis spp.

Pisum sppο Glycine Max Chenopodiaceae, e.g. B.

Beta vulgaris

Spinacia spp "

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Capsicum annuum

Apium graveolens Fragaria

Cucurbita spp.

Solanaceae, ζ. B.

Solanura spp.

Nieotiania spp. Linaceae, e.g. B.

Linum spp. Umbelliferae, e.g. B.

Petroselinum spp

Daucus carοta Rosaceae, e.g. B. Cucurbitaceae, e.g. B.

Cucumis spp. Liliaeeae, for example _o

A11ium spp. Vitaceae, for example

Vitis vinifera Bromeliaceae e.g. B.

Ananas sativus can be applied.

Example 2

Experimental pots with a loamy sandy soil were used in the greenhouse filled and sown with various seeds. Immediately afterwards, the treatment with the active ingredients I, II, IV, V, VI and VII compared to the known active ingredient III, each dispersed or emulsified in 500 liters of water per hectare. The application rate was 1 kg / ha in each case.

During the trial period, the plants received a high amount of rainfall. After 4 weeks it was found that the Active ingredients I, II, IV, V, VI and VII are better tolerated on the crop plants and showed a better herbicidal action than the active ingredient III.

Active ingredient I:

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Active ingredient II:

Active ingredient III: (comparative agent)

Active ingredient IV:

Active ingredient V:

Active ingredient VI:

Active ingredient VII:

CB

Cl _ri

NCS-CH ₀ -C = C ^ ",

CH ^,

N-C-S-CH-

The test results can be seen from Table 1.

Active ingredient kg / ha

Tabel ι ■ III ■ IV V VI VII I. II 1 1 1 1 1 1 1 10 0 0 0 Ό 0 0 5 0 0 0 0 en) 0 0

Useful plants:

Brassica napus (rapeseed) Triticura aestivum (wheat)

40983 7 /

Ο · ξ *

Active ingredient
kg / ha I.
1 II
1 III
1 IV
1 V.
1 VI
1 VII
1 ■ unwanted plants: Echinochloa crus galli
(Chicken millet) 100 90 4o 95 90 45 80 Lolium multiflorum
(Italian ryegrass) 100 100 20th 100 95 80 85 LoIium perenne
(English ryegrass) 100 100 20th 95 90 80 90 Avena fatua
(Wild oats) 60 80 0 6o 55 40 70 Poa annua
(annual bluegrass) 100 100 30th 100 85 85 100 Poa trivialis
(common bluegrass) 100 100 30th 95 85 85 95

0 = without damage
100 = total damage

Example 3

Different plants were grown at a height of 3 to 15 cm with the active ingredients I, II, IV, V, VI and VII compared to the known active ingredient III in each case dispersed or emulsified in 500 liters of water per hectare treated.

The application rate was 1 kg / ha of active substance in each case. During the trial period, the plants received a high amount of rainfall. After 4 weeks it was found that the active ingredients I, II, IV, V, VI and VII are better tolerated by the Cultivated plants with the same herbicidal action showed as the active ingredient III.

Active ingredient
kg / ha

Tabel 2 II III IV V VI VII I. 1 1 1 1 1 1 1 0 10 0 0 0 0 0 0 5 0 0 0 0 ») 0

Useful plants:
Brassica napus (rapeseed)
Triticum aestivum (wheat) 0

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- Active ingredient
kg / ha 16 - II
1 III
1 IV
1 o.z. 29 752 VI-
1 VII
1 unwanted plants: 2312045 Echinochloa crus galli
(Chicken millet) I.
1 90 40 95 V.
1 60 90 LoIium multiflorum
(Italian ryegrass) 100 20th 95 70 90 Lolium perenne
(English ryegrass) 100 100 20th 90 90 70 85 Avena fatua (Plughoat) 100 80 0 50 90 40 50 Poa annua
(annual bluegrass) 100 100 30th 95 85 70 90 Poa trivialis
(common bluegrass) 60 100 30th 90 ^ 5 65 85 100 90 100 90

0 = without damage
100 = total damage

Example 4

90 parts by weight of compound I are mixed with 10 parts by weight of N-methyl - «.- pyrrolidone and a solution is obtained which is suitable for use in the form of the smallest drops is suitable.

Example 5

20 parts by weight of compound II are in a mixture dissolved that from 80 parts by weight of xylene, 10 parts by weight of the adduct of 8 to 10 moles of ethylene oxide with 1 mole oleic acid-N-monoethanolamide, 5 parts by weight of the calcium salt Dodecylbenzenesulfonic acid and 5 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil. By pouring the solution into 100,000 parts by weight and finely distributing it Water gives an aqueous dispersion which contains 0.02 percent by weight of the active ingredient.

Example 6.

20 parts by weight of compound I are dissolved in a mixture that of 40 parts by weight of cyclohexanone, 30 parts by weight

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Isobutanol, 20 parts by weight of the adduct of 7 moles of ethylene oxide with 1 mole of isooctylphenol and 10 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil is made by pouring in and finely distributing the Solution in 100,000 parts by weight of water gives an aqueous dispersion which contains 0.02 percent by weight of the active ingredient.

Example 7

20 parts by weight of compound II are in a mixture dissolved, which consists of 25 parts by weight of cyclohexanol, 65 parts by weight of a mineral oil fraction with a boiling point of 210 to 280 ° C and 10 parts by weight of the adduct of 40 moles Ethylene oxide consists of 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and finely distributing it an aqueous dispersion is obtained which contains 0.02 percent by weight of the active ingredient.

Example 8

20 parts by weight of the active ingredient I with 3 parts by weight the sodium salt of diisobutylnaphthalene-a-sulfonic acid, 17 parts by weight of the sodium salt of a lignosulfonic acid from a sulphite waste liquor and 60 parts by weight of powdered Silica gel mixed well and ground in a hammer mill, By finely distributing the mixture in 20,000 parts by weight of water, a spray mixture containing 0.1 percent by weight is obtained contains the active ingredient,

Example 9

25 parts by weight of compound II are 97 parts by weight finely divided kaolin intimately mixed «This gives a dust containing 5% by weight of the active ingredient.

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Example 10

30 parts by weight of compound I are powdery with a mixture of 92 parts by weight! Silica gel and
8 parts by weight of paraffin oil on the surface of this
Silica gel was sprayed on, mixed intimately. In this way, a preparation of the active ingredient with good adhesion is obtained "

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Claims (19)

Claims 1. Carbothiolate of the formula in which R is an alkyl radical, η O to 4, X is oxygen or 2
Sulfur and R denotes an aliphatic radical which is optionally substituted one or more times by halogen, the hydroxyl group, the alkoxy group or the cyano group 2
is, or R is the remainder - (CH ₂ ) means, where R ^! Halogen or nitro, cyano, alkoxy or alkyl denotes nu 0, 1 or 2 and m ₂ 0 to 4 and if nu is greater than 1, R ¹ denotes identical or different substituents. 2ο S- (p-chlorobenzyl) - (2,2,4-trimethyl-azetidine) -1-carbothiolate. 3. S-Benzyl- (2,2,4-trimethyl-azetidine) ~ 1-carbothiolate. 4. S-methyl- (2,2,4-trimethyl-azetidine) -1-carbothiolate. 5. S-sec-Butyl- (2,2,4-trimethyl-azetidine) -1-carbothiolate. 6. S-iso-propyl- (2,2,4-trimethyl-azetidine) -1-carbothiolate. 7. S-trichloroallyl (2,2,4-trimetbyl-azetidine) -1-carbothiolate. 8. S-n-propyl (2,2,4-trimethyl-azetidine) -1-carbothiolate. 9. S-Benzyl (3,3-dimethyl-azetidine) -1-carbothiolate. 10. S- (β-phenylethyl) - (2,2,4-trimethyl-azetidine) -1-carbothiolate. 11. S-ethyl- (2,2,4-trimethyl-azetidine) -1-carbothiolate. 12ο S-Benzyl- (2,2,4-trimethyl-azetidine) -l-thiocarbothiolate. 13. S-propyl (2,2,4-trimethyl-azetidine) -l-thiocarbothiolate. 14. S- (β-phenylethyl) - (3,3-dimethyl-azetidine) -1-carbothiolate. 15. S-Benzyl-azetidine-1-carbothiolate, 16. S-A * ethyl azetidine-1-carbothiolate. 17. S-propyl azetidine-1-carbothiolate. 18. S-i-propyl-azetidine-1-carbothiolate. 19. S-Benzyl- (2-methyl-azetidine) -1-carbothiolate. 409837 / 103Λ / ²⁰ - 20 - O.Z. 29 20o herbicide containing an azetidine carbothiolate accordingly Claim 1. 21 ο Use of an azetidine carbothiolate accordingly Claim 1 as a herbicide. Badische Anilin- & Soda-Fabrik AG 409837 / 103A