IL45023A - Carbothiolates and thiocarbothiolates of alkyl-hexahydro-1hazepines their preparation and their use as herbicides - Google Patents

Abstract

1465112 Azepine carbothiolates BASF AG 28 June 1974 [30 June 1973] 28753/74 Heading C2C [Also in Division A5] Novel compounds of formula where X is O or S, R<SP>1</SP> n is Et or 2 or 3 radicals independently selected from Et and Me, and R<SP>2</SP> is hydrocarbyl optionally substituted by halogen, OH, CN, alkoxy and/or nitro, any nitro groups being attached to a benzene ring, are prepared by reacting a thiol chloroformate ester with an alkyl hexahydro-IH-azepine, by reacting an alkyl hexahydro-1H-azepine acyl chloride with a mercaptan or by reacting an alkyl hexahydro - 1H - azepine -1 - carbodithioate salt with an organic halide. Sodium 2,3 - dimethyl - hexahydro - 1H - azepine-1-carbodithioate is prepared by reacting CS 2 with 2,3-dimethylhexamethylenimine in the presence of NaOH. The novel compounds are used as herbicides. [GB1465112A]

Description

45023/2 Garbothiolstes and thlocarbothiolates of allr.yl-hexahydro-lH-azepines , their preparation and their use as herbicides BASF Aktiengesellschaft C. 3130 45023/2 The present invention relates to new and valuable carbothiolates and thiocarbathiolates of 1-H-hexahydro-azepines, herbicides containing them, and their use as herbicides.

It is known (British 995,316) to use S-ethylhexahydro-lH-azepine-l-carbothiolate for controlling unwanted plants in crops such as barley, wheat and rice. However, its action is poor.

We have now found that carbothiolates and thiocarbothiolates of alkyl-lH-hexahydroazepines of the formula where X is oxygen or sulfur, R1 is methyl or ethyl, n is 2 or 3 and may also denote the integer 1 when R^" is ethyl, ' 2 and R is a lower alkyl or alkenyl radical which is unsubstituted 2 or mono- or polysubstituted by halogen, or R is a benzyl or phenethyl radical optionally substituted with halogen, have a better herbicidal action than the prior art compound. The compounds of the invention have better crop plant compatibility and a better herbicidal action on various unwanted plants than S-ethylhexahydro-lH-azepine-l-carbothiolate. 45023/2 The active ingredients may be prepared by reacting a thiol chloroformate with an alkyl-substituted lH-azepine. They may also be produced by allowing substituted IH-azepines, in the form of 0 the corresponding N-acyl chlorides, to react with mercaptans. The preparation of IH-azepines is disclosed for instance in Heterocyclic Compounds (R.C. Elderfield), 224, 1967, German 738,448, and Tetrahedron Letters, 791, 1970. It is possible to obtain 2, 3- dimethylhexamethylenimine for instance by Schmidt reaction from the · corresponding ketone, followed by reduction.

Boiling point (72 mm): 91° to 93°C. 2, 7-dimethylhexamethylenimine is accessible by reductive cyclic zation of the corresponding diamine.

Boiling point (27 mm): 70°C.

EXAMPLE 1 Preparation of S- (n-propyl) - (2 , 3-dimethyl-lH-hexahydroazepine) -1- carbothiolate At 20°C, 104 parts (by weight) of thio-n-propyl chloroformate t is dripped into 9.50 parts of 2, 3-dimethyl-lH-azepine and 7.60 parts of triethylamine in 60 parts of benzene. After one hour the amine hydrochloride is suction filtered and the filtrate washed with water. After drying, concentration is carried out in vacuo and the residue distilled off. There is obtained 13.6 parts of S- (n-propyl )-; I , ( 2, 3-dimethyl-lH-azepine)-l-carbothiolate. The compound has the following structural formula: boiling point (0.01 123° to 126°C S-CH2-CH2-CH2 i' The following carbothiolates may be obtained in the same manner:, I ' boiling 1 point (mm) S-ethyl- (2 , 3-dimethyl-lH-hexahydroazepine) -1- ' carbothiolate (0.01) : 92 °C S-benzyl- (2 , 3-dimethyl-lH-hexahydroazepine) -1- carbothiolate (0.01): 138°C S- (p-chlorobenzyl) - (.2 , 3-dimethyl-lH-hexahydro- azepine) -1-carbothiolate (0.01): 171°C. S-benzyl (2 , 7-dimethyl-lH-hexahydroazepine) -1- carbothiolate (0.01) : 142-150°C S-propyl- (trimethyl-lH-hexahydroazepine) -1- •carbothiolate+) (0.01) : 100-103°C S-methyl- (trimethyl-lH-hexahydroazepine) -1- carbothiolate+) (0.01): 100-103°C S-benzyl- (trimethyl-lH-hexahydroazepine) -1- carbothiolate+) (0.01) : 149-150°C +) ' 1:1 isomer mixture of 3 , 5 , 5-trimethyl and 3,3, 5-trimethyl-lH-hexahydroazepine carbothiolates S- (p-chlorobenzyl) - (4-ethyl-lH-hexahydro- azepine) -1-carbothiolate (0.01): 169°C S-benzyl- ( 4-ethyl-lH-hexahydroazepine) -1- carbothiolate (0.01) : 157°C S-ethyl- (4-ethyl-lH-hexahydroazepine) -1- carbothiolate (0.01): 95-99°C S-benzyl- (3 , 6-dimethyl-lH-hexahydroazepine) - ° boiling * point (mm) S-propyl- (3,6-dimethyl-lH-hexahydro-azepine) -l-carbothiolate (0.01) : llO°C S- (I,l-dichloro-2-methylallyl) - (3,6· dimethyl-lH-hexahydroazepine) -1-carbothiolate (0.01) : 147»C S-methy1- (3 ,6-dimethyl-lH-hexahydrO' azepine) -l-carbothiolate (0.01) : 90eC S-ethyl-(3 ,6-dimethyl-lH-hexahydro-azepine) -l-carbothiolate (0.01) : 95°C S-phenylethyl-(2 ,3-dimethyl-lH-hexahydroazepine) -1-carbothiolate (0.01): 152-256°C S-phenylethyl-(2 ,7-dimethyl-lH-hexahydroazepine) -l-carbothiolate EXAMPLE 2 Preparation of S-benzyl- (2 , 3-dimethyl-lH-hexahydroazepine) - 1-thiocarbothiolate At 10°C, 7.8 parts of carbon disulfide is dripped into 12.7 parts of 2,2-dimethylhexamethylenimine and 4 parts of sodium hydroxide dissolved in 30 parts of water.

Suction filtration is carried out after about 3 minutes and the salt washed with ether. 29.3 parts of the salt is then dissolved in 100 parts of alcohol and reacted at 40°C with 17.1 parts of benzyl bromide.

After about 2 hours the solvent is removed in vacuo, water is added to the residue, and the organic phase is separated, dried and distilled.

The compound has the following structural formula: oiling point (0.01 mm): 168° to 170°C The following compounds may be obtained in the same^ manner: S-benzyl- (2 , 3-dimethyl-lH-hexahydro-azepine) -1-thiocarbothiolate b.p. (O.Ol) : 168-170°C S-methyl- ( 2 , 3-dimethyl-lH-hexahydro-azepine) -1-thiocarbothiolate b.p. (0.01): 110-114°C S-ethyl- ( 2 , 3-dimethyl-lH-hexahydro-azepine) -1-thiocarbothiolate b.p. (0.01) : 117°C S-benzyl- ( 2 , 7-dimethyl-lH-hexahydro-azepine) -1-thiocarbothiolate The new compositions have a strong herbicidal action and may O.Z. 29,951 unwanted plants. Whether the 'new active ingredients are used ar^ 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 monocotyledon-ous and dicotyledonous plants which grow in loci where they are not desired.

The agents according to the invention may therefore he used for controlling for instance Gramineae, such as Cynodon spp. Dactylis spp.

Digitaria spp. Avena spp.

Echinochloa spp. Bromus spp.

Setaria spp. Unlola 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. Phragmitres communis etc; Cyperaeeae, such as Carex spp. Eleocharis Cyperus spp. Scirpus spp etc.; dicotyledonous weeds, such as Malvaceae, e.g.

Abutilon theoprasti Hibiscus spp.

Sida spp. Malva spp. etc.; o.z. 29,951 Lactuca spp. Tussilago spp.

Senecio 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. ΘtC 0 Geraniaceae, such as Erodium spp. Geranium spp. etc . ; Portulacaceae, such as Portulaca spp. etc.; Primulaceae, such as Anagallis arvensis Lysimachia spp. etc. ; Rubiaceae, such as O.Z. 29,951 Scrophulariaceae, such as Linaria spp. Digitalis spp.

Veronica spp.

Solanaceae, such as Physalis sppD Nicandra spp.

Solanum spp. Datura spp. etc Urticaceae, such as Urtica spp.

Violaceae, such as Viola spp.

Zygophyllaceae, such as Tribulus terrestis Euphorbiaceae, such as Mercurialis annua Euphorbia spp.

Umbelliferae, such as Daucus carota Ammi majus Aethusa cynapium etc. ; Commelinaeae, such as Commelina spp, etc . ; Labiatae, such as Lamium spp. Galeopsis spp. etc.; Leguminosae, such as Medicago spp. Sesbania exaltata Trifolium spp. Cassia spp.

Vicia spp. Lathyrus spp. etc.; Plantaginaceae, such as Plantago spp. etc. ; O.Z. 29,951 Aizoaceae, such as Molluga verticillata Amaranthaceae, such as Amaranthus spp.

Boraginaceae, such as Amsinckia spp0 Anchusa spp.

Myostis spp. Lithospermum spp.

Q t C e Caryophyllaceae, such as Stellaria spp. Silene spp.

Spergula spp, Cerastium spp.

Saponaria spp. Agrostemma githago Scleranthus annuus Q t C f Chenopodiaceae, such as Chenopodium spp. Atriplex spp. ochia spp. Monolepsis nuttalliana Salsola Kali Lythraceae, such as Cuphea spp.

Oxalidaceae, such as Oxalis spp.

Ranunculaceae, such as Ranunculus spp. Adonis spp.

Delphinium spp. Θt C e Papaveraceae, such as Papaver spp. Pumaria officinalis etc. ,· Onagraceae, such as Jussiaea spp. etc Rosaceae, such as o.z. 29,951 Potamogetonaceae, such as Potamogeton spp. 61C « Najadaceae, such as Najas spp. etc. ; Marsileaceae, such as Marsilea quadrifolia etc.

The new active ingredients may he used in cereal crops such as Avena spp. Sorghum Triticum spp. Zea mays.

Hordeum spp. Panicum miliaceum Secale spp. Oryza spp. and in dicotyledon crops such 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 spp. Phaseolus spp.

Trifolium spp. Arachis spp.

Pisum spp. Glycine max.

Chenopodiacea, e.g.

Beta vulgaris Spinacia spp.

Solanaceae, e.g.

Solanum- -spp. Capsicum annuum o.z. 29,951 Umbelliferae, e.g.

Petroselinum spp. Aplum graveolens Daucus carota Rosaceae, e.g. Fragaria Cucurbitaceae, e.g.

Cucumls spp. Cucurbita spp.

Liliaceae, e.g.

Allium spp.

Vitaceae, e.g.

Vitis vinifera Bromeliaceae, e.g.

Ananas sa ivus 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 form of application depends entirely on the purpose for which the agents are being used; in any case it 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 point, such as kerosene or diesel oil, further coal-tar oils, etc. and oils of vegetable or mineral 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, chloro-benzene, isophorone, etc., and strongly polar solvents such as di-methylformamide, dimethyl sulfoxide, N-methylpyrrolidone, water, etc. are suitable. o.z. 29,951 prepare emulsions, pastes and oil dispersions such or dissolved in an oil or solvent may he 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, polyoxy-ethylene octylphenol ethers, ethoxylated 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 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, O.Z. 29,951 plastics, fertilizers such as ammonium sulfate, ammonium 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, 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 arid 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 quiiiolines 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 O.Z. 29,951 substituted oycloalkylcarbonamidothiazoles 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-lH-carbothioates substituted hydantoins substituted hydraz'ides 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 o.z. 29,951 substituted pyrazole alkylcarboxylic acids and their salts, est.ars •and amides substituted pyrazolium salts substituted pyrazolium alkyl sulfates substituted pyridazines substituted pyridine carboxylic acids and their salts, esters and amides substituted pyridines substituted pyridine carboxylates substituted pyridinones substitutedr 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 O.Z. 2.9,951 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, antiodotes and growth regulators.

The agents according to the invention may be used once or several times before or after planting, before sowing, pre- and postemergence, or during emergence of the crop plants and weeds.

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 or more kg, preferably from 0.2 to 6 kg of active ingredient per hectare.

EXAMPLE 3 In the greenhouse, loamy sandy soil was filled into pots and sown with various seeds. The soil prepared in this manner was then immediately treated with 3 kg per hectare of compounds I to VI and for comparison, VII and X, each compound being dispersed or emulsified in 500 liters of water per hectare. After 3 to 4 weeks it was ascertained that active ingredients I to VI had better crop plant compatibility and a better herbicidal action on several unwanted plants than compounds VII and X.

I : O.Z. 29,9.51 VII : X: Active ingredient I II III IV V VI VII X kg/ha 3 Crop plants: Brassica napus 0 0 0 0 0 0 20 0 Gylcine spida σ 0 0 0 0 0 0 0 Zea mays 0 0 0 0 0 0 20 10 Gossypium hirsutum 0 0 0 0 0 0 35 5 Beta vulgaris 0 0 0 0 0 0 3 15 Unwanted- plants: Lolium multiflorum 100 100 100 100 80 100 65 70 Lolium perenne 100 100 100 100 80 100 70 72 Echinochlora crus galli 8o 100 100 100 100 100 90 90 Digitaria sanguinalls 8o 100 100 100 100 100 95 95 o .z . 29, 951 EXAMPLE 4 « · In the greenhouse, various plants were treated with 3 k per hectare of compounds I to VI and, for comparison, compound VII, each compound being emulsified or dispersed in 500 liters of water per hectare.

After 3 to 4 weeks it was ascertained that active ingredients I to VI have better crop plant compatibility and a better herbicidal action than compound VII.

Crop plants: Brassica napus 0 0 0 0 0 0 0 Glycine hispida 0 0 0 0 0 0 0 Zea mays 0 0 0 0 0 0 0 Gossypium hirsutum 0 0 0 0 0 0 0 Beta vulgaris 0 0 0 0 0 0 ' 0 Unwanted plants: Lolium multiflorum 100 100 100 60 60 60 30 Lolium perenne 100 100 100 65 65 60 30 Echinochloa crus galli 60 100 80 80 80 80 50 Digitaria sanguinalis 65 100 80 85 85 85 4 Setaria viridis 60 100 80 85 85 85 45 Poa trivialis 100 100 100 70 75 75 20 Poa annua 100 100 100 70 75 75 10 0 = no damage 100= complete destruction The action of compounds VIII and IX corresponds to that of compounds I to VI.

EXAMPLE o „z . 29, 951 suitable for application in the form of very fine drops.

EXAMPLE 6 20 parts by weight of compound III 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 0 moles of ethylene oxide to 1 mole of castor oil. By pouring the solution into 100, 000 parts by weight of water and uniformly distri-buting it therein, an aqueous dispersion is obtained containing 0.02$ by weight of the active ingredient.

EXAMPLE 7 20 parts by weight of compound IV is dissolved in a mixture consisting of ^0 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 0 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 8 20 parts by weight of compound V is dissolved in a mixture con-sisting of 25 parts by weight of cyclohexanol, 65 parts by weight of a mineral oil fraction having a boiling point between 210° and 280°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 9 O.Z. 29,951 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 10 2 parts by weight of compound II is intimately mixed with 97 parts by weight of particulate kaolin. A dust is obtained containing 5 ~ % by weight of the active ingredient.

EXAMPLE 11 JO parts by weight of compound III 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. -19-

Claims (14)

CLAIMS :

1. Carbothiolates and thiocarbothiolates of alkyl-substituted 1-H-hexahydroazepines of the formula where X is oxygen or sulfur, R is methyl or ethyl, n is 2 or 3 and may also denote the integer 1 when R"" is ethyl, 2 lower and R is an alkyl or alkenyl radical which is unsubstituted 2 or mono- or polysubstituted by halogen, or R is a benzyl or phenethyl radical optionally substituted with halogen.

2. S- (n-propyl) - (2 , 3-dimethyl-lH-hexahydroazepine) -1-carbothiolate. i

3. S-ethyl- (2 ,3-dimethyl-lH-hexahydroazepine) -1- | i carbothiolate. i I

4. S-benzyl- (2 , 3-dimethyl-lH-hexahydroazepine) -1- i carbothiolate. 1

5. S- (p-chlorobenzyl) - (2 , 3-dimethyl-lH-hexahydro-azepine) -1-carbothiolate.

6. S-benzyl- (2 , 7-dimethyl-lH-hexahydroaaepine) -1-carbothiolate .

7. S- (n-propyl) - (trimethyl-lH-hexahydroazepine) -1-carbothiolate .

8. S-methyl- (trimethyl-lH-hexahydroazepine) -1-carbothiolate.

9. S-benzyl- (trimethyl-lHrhexahydroazepine) -1-carbothiolate .

10. A compound of formula I in Claim 1, substantially as described herein, with reference to the Examples.

11. A process for producing a compound of formula I in Claim 1 wherein a thiol chloroformate is reacted with an alkyl-substituted lH-hexahydroazepine, or a substituted IH-hexahydroazepine-N-acyl chloride is reacted with a mercaptan.

12. A herbicide! composition containing a compound of formula I in Claim 1.

13. A herbicidal composition containing a solid or liquid carrier and a compound of formula I in Claim 1.

14. A process for controlling the growth of unwanted plants wherein the plants or the soil are treated with a compound of formula I i Claim 1 alone or in admixture with a solid or liquid carrier. PC:dn