GB1588934A

GB1588934A - Herbicidally active 1,3,3 - trimethyl - 6 - azabicyclo-(3,2,1) - octane - 6 - carboxylic acid esters and their manufacture and use

Info

Publication number: GB1588934A
Application number: GB30241/77A
Authority: GB
Original assignee: Schering AG
Current assignee: Bayer Pharma AG
Priority date: 1976-07-19
Filing date: 1977-07-19
Publication date: 1981-04-29
Also published as: CS192582B2; MX4852E; CH627920A5; NO147603C; SE424868B; NL7707038A; AU511783B2; IE45359B1; BE856933A; JPS5510578B2; HU178752B; GR71649B; IE45359L; NO772552L; PT66822B; AT355861B; BG28027A3; DD131070A5; TR19833A; PL103690B1

Abstract

A herbicide contains, as active substance, a novel 1,3,3-trimethyl-6-azabicyclo[3.2.1]octane-6-carboxylic ester of the formula <IMAGE> in which the substituents are defined in Claim 1. A process for the preparation of the herbicide is described.

Description

(54) HERBICIDALLY ACTIVE 1,3,3-TRIMETHYL-6 AZABICYCLO-(3,2, 1 )-OCTANE-6-CARBOXYLIC ACID ESTERS AND THEIR MANUFACTURE AND USE (71) We, SCHERING AKTIENGESELLSCHAFT, a Body Corporate organised according to the laws of the Federal Republic of Germany, of Berlin and Bergkamen, Federal Republic of Germany, do hereby declare the invention for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:- The present invention is concerned with new herbicidally active 1,3,3 trimethyl-6-azabicyclo-(3,2,l)-octane-6-carboxylic acid esters, with processes for their manufacture and also with their use.

It has already been known that alkyleneiminocarbothiolates are herbicidally active (United States Patent Specification No. 3,198,786). However, these compounds develop sufficient selective-herbicidal properties only in certain crops of useful plants, for example in rice crops for combating Echinochloa spp.

The problem upon which the present invention is based has therefore been to provide an agent of the kind in question, which has a wide spectrum of selectivity towards crop plants and a very good herbicidal action against weeds.

This problem is solved in accordance with the present invention by the compounds of the general formula I, as defined below.

The present invention accordingly provides compounds of the general formula I

in which R represents an unsubstituted or substituted aliphatic, cylcoaliphatic, aromatic or araliphatic hydrocarbon group and X and Y each represents an oxygen atom or a sulphur atom.

The compounds of the present invention are distinguished by an outstanding herbicidal action especially against monocotyledonous weeds, for example Avena, Alopecurus, Echinochloa c.g., Setaria, Digitaria, Poa, Hordeum and Triticum.

Owing to their excellent selective properties they can be used in agricultural crops, for example in cauliflower, sugar beet, seeded tomato, bush bean, soya bean, cotton and rice crops.

The compounds of the present invention can also be used in maize and sorghum, it being advantageous to admix an antidote, for example 8-naphthalic anhydride or N,N-diallyl-dichloroacetamide, with the seed grain or the spraying preparation, respectively.

A further advantage of the compounds of the present invention is that they also possess plant growth-regulating properties.

The compounds act satisfactorily even at rates of application from 1 kg of active substance per hectare, and, owing to their surprisingly wide spectrum of selectivity, they can be used without injuring crops of useful plants in quantities of up to 8 kg of active substance per hectare before sowing by incorporation in the soil; when two or more compounds of the general formula I are used the range of I to 8 kg refers of course to the total amount used of these compounds.

The present invention accordingly also provides a herbicidal preparation which comprises a compound of the general formula I, in admixture or conjunction with a suitable carrier. The preparation may of course contain one or more compounds of the general formula I.

The present invention further provides a method of protecting a living plant against weeds, wherein the area in the vicinity of the living plant is treated with a compound of the general formula I.

The present invention further provides a method of protecting a crop area against weeds and/or of regulating the growth of plants in the area, wherein the crop area is treated with a compound of the general formula I.

The present invention further provides a pack which comprises a compound of the general formula I together with instructions for its use as a herbicide and/or for regulating the growth of living plants.

The compounds of the present invention can be used either alone or in admixture with one another or with other active substances.

In this connection, depending on the purpose desired, there may be mentioned, for example, the following herbicidally active substances, which, if desired, may be added to the compounds of the present invention only immediately before use: substituted anilines, substituted aryloxy-carboxylic acids and also salts, esters and amides thereof, substituted ethers, substituted arsonic acids and also salts, esters and amides thereof, substituted benzimidazoles, substituted benzisothiazoles, substituted benzthiadiazinone dioxides, substituted benzoxazines, substituted benzoxazinones, substituted benzthiazoles, substituted benzthiadiazines, substituted biurets, substituted quinolines, substituted carbamates, substituted aliphatic carboxylic acids and also salts, esters and amides therof, substituted aromatic carboxylic acids and also salts, esters and amides thereof, substituted carbamoylalkyl-thio- or dithio-phosphates, substituted quinazolines, substituted cycloalkylamidocarbonthiolic acids and also salts, esters and amides thereof, substituted cycloalkylcarbonamido-thiazoles, substituted dicarboxylic acids and also salts, esters and amides thereof, substituted dihydrobenzofurariyl sulphonates, substituted disulphides, substituted dipyridylium salts, substituted dithiocarbamates, substituted dithiophosphoric acids and also salts, esters and amides thereof, substituted ureas, substituted hexahydro-lH-carbothioates, substituted hydantoins, substituted hydrazides, substituted hydrazonium salts, substituted isoxazolepyrimidones, substituted imidazoles, substituted isothiazolepyrimidones, substituted ketones, substituted naphthoquinones, substituted aliphatic nitriles, substituted aromatic nitriles, substituted oxadiazoles, substituted oxadiazinones, substituted oxadiazolidinediones, substituted oxadiazinediones, substituted phenols and also salts and esters thereof, substituted phosphonic acids and also salts, esters and amides thereof, substituted phosphonium chlorides, substituted phosphonalkylglycines, substituted phosphites, substituted phosphoric acids and also salts, esters and amides thereof, substituted piperidines, substituted pyrazoles, substituted pyrazolalkylcarboxylic acids and also salts, esters and amides thereof, substituted pyrazolium salts, substituted pyrazolium alkyl sulphates, substituted pyridazines, substituted pyridazones, substituted pyridine carboxylic acids and also salts, esters and amides thereof, substituted pyridines, substituted pyridine carboxylates, substituted pyridinones, substituted pyrimidones, substituted pyrolidine carboxylic acids and also salts, esters and amides thereof substituted substituted aryl sulphonic acids and also salts, esters and amides thereof, substituted styrenes, substituted tetrahydro-oxadiazinediones, substituted tetrahydromethanoindenes, substituted tetrahydro-diazole-thiones, substituted tetrahydro-thiadiazine-thiones, substituted tetrahydro-thiadiazolediones, substituted thiadiazoles, substituted aromatic thiocarboxylic acid amides, substituted thiocarboxylic acids and also salts, esters and amides thereof, substituted thiolcarbamates, substituted thiophosphoric acids and also salts, esters and amides thereof, substituted triazines, substituted triazoles, substituted uracils and substituted uretidinediones.

Furthermore, there may be used other additives, for example non-phytotoxic additives, which impart to herbicides a synergistic increase in action, for example wetting agents, emulsifiers, solvents and oily additives.

The characterized active substances or mixtures thereof are advantageously used in the form of herbicidal preparations, for example powders strewable preparations, granules, solutions, emulsions and suspensions, with the addition of liquid and/or solid vehicles or diluents, and, if desired, of surface-active agents, for example wetting, adherent, emulsifying and/or dispersing agents.

Suitable liquid carriers are, for example, water, aliphatic hydrocarbons, aromatic hydrocarbons, for example benzene, toluene and xylene, cyclohexanone, isophorone, dimethyl sulphoxide and dimethylformamide, and also mineral oil fractions.

As solid carriers there are suitable, for example, mineral earths, for example tonsil, silica gel, talcum, kaolin, attaclay, limestone and silicic acid, and vegetable products, for example meals.

As surface-active agents there may be mentioned for example, calcium lignin sulphonate, polyoxyethylenalkyl-phenyl ethers, naphthalene sulphonic acids and salts thereof, phenol sulphonic acids and salts thereof, fortnaldehyde condensates, fatty alcohol sulphates and also substituted benzene sulphonic acids and salts thereof.

The total proportion of the active substance or substances in the various herbicidal preparations may vary within wide limits. For example, the preparations may contain from 10 to 80% by weight of active compound(s), from 90 to 20% by weight of liquid or solid carrier and also, if desired, up to 20% by weight of surfaceactive agent(s).

The active compounds may be applied in the usual manner, for example with water as carrier in quantities of spray liquor from 100 to 1000 litres per hectare. It is also possible to apply the active compounds by the so-called "low volume" and "ultra-low volume" methods and also to apply them in the form of so-called microgranules.

Among the compounds of the present invention there are especially distinguished those of the general formula I given above in which R represents an alkyl group containing 1 to 7 carbon atoms, a chloralkyl group containing I to 7 carbon atoms, an alkenyl group containing~2 to 7 carbon atoms, a chloralkenyl group containing 2 to 7 carbon atoms, an alkynyl group containing 2 to 7 carbon atoms, a benzyl group, a chlorobenzyl group, a phenyl group, a naphthyl group, a chlorophenyl group, a phenyl group substituted by an alkyl group containing I to 4 carbon atoms or a phenyl group substituted by a chloralkyl group containing I to 4 carbon atoms, and X and Y each represent an oxygen or a sulphur atom.

As such groups represented by R there are preferably mentioned amongst many, for example, methyl, ethyl, 2-chlorethyl, propyl, isopropyl, allyl, 2propynyl, dichlorallyl, trichlorallyl, butyl, sec.-butyl, isobutyl, tert.-butyl, butenyl, butynyl, pentyl, isopentyl, benzyl, 4-chlorobenzyl, 2,4-dichlorobenzyl, phenyl and 4-chlorophenyl groups.

The new compounds of the general formula I may be prepared, for cxample, by the process of the present invention as defined below.

The present invention accordingly further provides a process for the manufacture of a compound of the general formula I, wherein 1,3,3-trimethyl-6 azabicyclo-(3,2,1)-octane of the formula

if desired dissolved in a solvent, (a) is reacted, if desired in the presence of an acid-binding agent, with a halogeno-formic acid ester of the general formula

in which R, X and Y have the meanings given above and Hal represents a halogen atom, or (b) is reacted in the presence of a base with a compound of the general formula X=C=Y, in which X and Y have the meanings given below, to form a salt of such a base of the general formula

in which X and Y have the meanings given above and B represents a cation derived from the base, and the salt is treated with an alkylating agent of the general formula R-Z, in which R has the meaning given above and Z represents a halogen atom, an alkyl sulphuric acid group or a toluene sulphonic acid group, or (c) is reacted with a phosgene compound of the general formula H a52C=X, in which X and Hal have the meanings given above, to form a 1,3,3-trimethyl-6 azabicyclo-(3,2, l)-octane-6-carboxylic acid halide of the general formula

in which X and Hal have the meanings given above, which is then reacted with oxygen- or thio compound of the general formula R#Y(-)B(+), in which R and Y have the meanings given above and B(+) represents a cation.

The present invention also includes within its scope a process for the manufacture of a compound of the general formula I, wherein a 1,3,3-trimethyl-6 azabicyclo-(3,2,l)-octane-6-carboxylic acid halide of the general formula shown in the definition of variant (c) of the process defined above, in which X and Hal have the meanings given above, is reacted with an oxygen- or thio-compound of the general formula R#Y(-)B(+), in which R, Y and B(+) have the meanings given above, As bases or acid-binding agents, respectively, there may be used all the usual proton acceptors. For this purpose there are suitable organic bases, for example tertiary amines, for example triethylamine or N,N-dimethylaniline, or pyridine bases and suitable inorganic bases, for example oxides, hydroxides and carbonates of alkali and alkaline earth metals. Liquid bases may serve simultaneously as solvents. An excess of the liquid starting base used may also function as acidbinding agent.

As alkylating agents there are advantageously used chlorides, bromides and iodides.

The reaction of the components may be carried out at between 0 and 1200C., but generally at room temperature.

For the synthesis of the compounds of the present invention the reactants are preferably used in approximately equimolar quantities.

Suitable reaction media are solvents inert towards the reactants, either alone or in admixture with water. Amongst many such reaction media the following may be mentioned by way of example, namely aliphatic and aromatic hydrocarbons, for example petroleum ether, cyclohexane, benzene, toluene and xylene, halogenated hydrocarbons, for example methylene chloride, chloroform, carbon tetrachloride and halogenated ethylenes, ether-like compounds, for example diethyl ether, diisopropyl ether, tetrahydrofuran and dioxan, ketones, for example acetone, methyl isobutyl ketone and isophorone, esters, for example methyl and ethyl acetate, acid amides, for example dimethylformamide and hexamethylphosphoric acid triamide, and carboxylic acid nitriles, for example acetonitrile.

Finally, the isolation of the compounds of the present invention may be carried out in a manner known per se by distilling off the solvent or extraction medium used under atmospheric or reduced pressure, optionally after treatment with acid or basic agents to remove undesired by-products. If necessary, the compounds may be distilled in vacuo for purification.

The starting compounds used for preparing the compounds of the present invention are known or can be prepared by methods known per se.

Some specific compounds of the present invention are listed in the following Table: TABLE Physical Name of the Compound Constant 1,3,3 - Trimethyl - 6 - azabicyclo - (3,2,1) - octane - 6 thiocarboxylic acid S - ethyl ester nD =1.5123 1,3,3 - Trimethyl - 6 - azabicyclo - (3,2,1) - octane - 6 dithiocarboxylic acid (2 - propenyl) ester nD =1.5810 1,3,3 - Trimethyl - 6 - azabicyclo - (3,2,1) - octane - 6 carboxylic acid methyl ester nD =1.4840 1,3,3 - Trimethyl - 6 - azabicyclo - (3,2,1) - octane - 6 thiocarboxylic acid S - methyl ester nD20=1,5172 1,3,3 - Trimethyl - 6 - azabicyclo - (3,2,1) - octane - 6 thiocarboxylic acid S - propyl ester nD =1.5090 1,3,3 - Trimethyl - 6 - azabicyclo - (3,2,1) - octane - 6 thiocarboxylic acid S - benzyl ester nD =1.5526 1,3,3 - Trimethyl - 6 - azabicyclo - (3,2,1) - octane - 6 carboxylic acid ethyl ester nD20=1.4702 1,3,3 - Trimethyl - 6 - azabicyclo - (3,2,1) - octane - 6 carboxylic acid propyl ester nD =1.4692 1,3,3 - Trimethyl - 6 - azabicyclo - (3,2,1) - octane - 6 carboxylic acid butyl ester nD =1.4612 1,3,3 - Trimethyl - 6 - azabicyclo - (3,2,1) - octane - 6 carboxylic acid isopropyl ester n20=l.4652 1,3,3 - Trimethyl - 6 - azabicyclo - (3,2,1) - octane - 6 carboxylic acid (2 - propenyl) ester nD20=1.4796 1,3,3 - Trimethyl - 6 - azabicyclo - (3,2,1) - octane - 6 carboxylic acid phenyl ester nD =1.5224 1,3,3 - Trimethyl - 6 - azabicyclo - (3,2,1) - octane - 6 thiocarboxylic acid (S - (4 - fluorophenyl)ester n20=1 .5488 1,3,3 - Trimethyl - 6 - azabicyclo - (3,2,1) - octane - 6 carboxylic acid benzyl ester nD20=1.5212 1,3,3 - Trimethyl - 6 - azabicyclo - (3,2,1) - octane - 6 carboxylic acid pentyl ester nD =1.4664 The compounds of the present invention are colourless or slightly yellow coloured oils having a slight aromatic odour, which are insoluble in water, but readily dissolve in all organic solvents, for example hydrocarbons, halogenated hydrocarbons, ethers, ketones, carboxylic acid esters, carboxylic acid am ides, carboxylic acid nitriles, alcohols, carboxylic acids, sulphoxides and many others.

The following Examples illustrate the invention. Examples 1 to 3 illustrate the manufacture of the compounds of the present invention and Examples 4 and 5 illustrate the possibilities of use of the compounds of the present invention.

Example 1 To a solution of 61.3 gms of 1,3,3 - trimethyl - 6 - azabicyclo - (3,2,1) octane in 150 ml of diisopropyl ether were slowly added dropwise, while stirring, 24.9 gms of chloro-thioformic acid S-ethyl ester at room temperature. After being stirred for one hour the reaction mixture was extracted by agitation with water, then with dilute hydrochloric acid and again with water, the organic phase was dried over magnesium sulphate, the solvent was distilled off in vacuo and finally the mixture was freed from the residual solvent in a high vacuum.

By adding sodium hydroxide solution to the first water extract the excess of starting material used was recovered.

Yield: 46.0 Gms (95.29% of the theoretical yield) of 1,3,3 - trimethyl - 6 azabicyclo - (3,2,1) - octane - 6 - thiocarboxylic acid S - ethyl ester of nD20=1.5123.

Analysis Calculated C 64.68% H 9.600/, N 5.80 Found C 64.38% H9.65% N 6.01% Example 2 Into a mixture of 34 ml of 1 ,3,3-trimethyl-6-azabicyclo-(3,2, l)-octane, 50 ml of acetonitrile and 8 gms of sodium hydroxide, dissolved in 50 ml of water, were added dropwise, while stirring, at between 10 and 15 C. 15.2 gms of carbon disulphide. To form the dithiocarbamic acid salt the mixture was stirred for a further 2 hours.

There were then added dropwise to the reaction mixture 24.5 gms of allyl bromide, and the whole was stirred for one hour for ester formation. After the addition of 500 ml of methylene chloride, the organic phase was extracted by agitation with hydrochloric acid, dried over magnesium sulphate, treated with active carbon and concentrated in a high vacuum. There remained behind 52 gms (96.4% of the theoretical yield) of 1,3,3-trimethyl-6-azabicyclo-(3,2,1)-octane-6-dithiocarboxylic acid allyl ester of nD20=1.5810.

Analysis: Calculated C 62.40 H 8.60% N 5.20% S 23.80% Found C62.23% H8.53% N5.02% S23.71% Example 3 Into a solution of 21.5 gms of 1,3,5-trimethyl-6-azabicyclo-(3,2,1)-octane-6- carboxylic acid chloride in 100 ml of acetonitrile were introduced, while stirring, 5.4 gms of sodium methylate. After being stirred for two hours, there were added to the reaction mixture of 350 ml of water, the oil that separated was extracted with chloroform, the chloroform phase was extracted by agitation with dilute hydrochloric acid, then dried over magnesium sulphate, and finally the solvent was distilled off in a high vacuum. There remained behind 19.0 gms (90.2% of the theoretical yield) of oily 1,3,5 - trimethyl - 6 - azabicyclo - (3,2,1) - octane - 6 carboxylic acid methyl ester having nD =1.4840.

Analysis: Calculated C 68.21% H 10.02% N 6.63% Found C68.23% H 10.01% N7.03% Each of the other compounds of the present invention listed in the Table above can be prepared in a manner analogous to that described in any one of Examples 1 to 3.

Example 4 In a series of tests carried out in a greenhouse the compounds of the present invention listed in the Table below were each sprayed at a rate of application of 5 kg of active substance per hectare, suspended in 500 litres of water per hectare, onto the soil before the sowing of Lolium and Setaria and worked into the soil.

Three weeks after the treatment the results thereof were evaluated, the results being expressed by a numerical scale extending from 0 to 4, the value 0 representing no action and the value 4 representing destruction of the plant.

Compound of the Present Invention Lolium Setaria 1 ,3,3-Trimethyl-6-azabicyclo-(3,2, 1)- octane-6-thiocarboxylic acid S-ethyl ester 4 4 1,3,3-Trimethyl-6-azabicyclo-(3,2,1)- octane-6-thiocarboxylic acid S-methyl ester 4 4 1 ,3,3-T;imethyl-6-azabicyclo-(3,2, 1)- octane-6-thiocarboxylic acid S-propyl ester 4 4 1,3,3-Trimethyl-6-azabicyclo-(3,2,1)- octane-6-dithiocarboxylic acid (2-propenyl) ester 4 3 1,3,3-Trimethyl-6-azabicyclo-(3,2,1)- octane-6-thiocarboxylic acid S-benzyl ester 3 0=no action 4=destruction of the plant -=not tested The following compounds have an analogous action 1,3,3 - Trimethyl - 6 - azabicyclo - (3,2,1) - octane - 6 - carboxylic acid methyl ester 1,3,3 - Trimethyl - 6 - azabicyclo - (3,2,1) - octane - 6 - carboxylic acid ethyl ester 1,3,3 - Trimethyl - 6 - azabicyclo - (3,2,1) - octane - 6 - carboxylic acid propyl ester 1,3,3 - Trimethyl - 6 - azabicyclo - (3,2,1) - octane - 6 - carboxylic acid butyl ester 1,3,3 - Trimethyl - 6 - azabicyclo - (3,2,1) - octane - 6 - carboxylic acid isopropyl ester 1,3,3 - Trimethyl - 6 - azabicyclo - (3,2,1) - octane - 6 - carboxylic acid (2 propenyl) ester 1,3,3 - Trimethyl - 6 - azabicyclo - (3,2,1) - octane - 6 - carboxylic acid phenyl ester 1,3,3 - Trimethyl - 6 - azabicyclo - (3,2,1) - octane - 6 - thiocarboxylic acid S - (4 - fluorophenyl) ester 1,3,3 - Trimethyl - 6 - azabicyclo - (3,2,1) - octane - 6 - carboxylic acid benzyl ester 1,3,3 - Trimethyl - 6 - azabicyclo - (3,2,1) - octane - 6 - carboxylic acid pentyl ester Example 5 In a series of tests carried out in a greenhouse the plants listed in the following Table were treated before their emergence with the listed agents being tested at a rate of application of 3 kg of active substance per hectare. For this purpose the agents were in each case applied uniformly, in the form of an aqueous dispersion using 500 litres per hectare, onto the soil and then incorporated into the soil. The results three weeks after the treatment show that the compound of the present invention was a better herbicidal agent than the agent used for comparison.

The results are expressed by a numerical scale extending from 0 to 10, the value 0 representing total destruction of the plant and the value 10 representing no damage.

Compound of the Present Invention 1 ,3,3-Trimethyl-6-azabicyclo-(3,2, 1)- octane-6-thiocarboxylic acid S-ethyl ester Agent for Comparison (according to United States Patent Specification No. 3,198,786) S-Ethyl-N,N-hexamethylene thiocarbamate Untreated control

c) 9 a "o E 9 S > C D e t a aot; Q a, .

YdOyldS fil .

3 10 10 10 0 0 0 0 0 0 0 0 3 0 3 10 10 10 0 0 0 3 3 0 10 10 10 10 10 10 10 10 10 10 10 0=total destruction 10=no damage WHAT WE CLAIM IS: 1. A compound of the general formula I

in which R represents an unsubstituted or substituted aliphatic, cycloaliphatic, aromatic or araliphatic hydrocarbon group and X and Y each represents an oxygen atom or a sulphur atom.

**WARNING** end of DESC field may overlap start of CLMS **.

Claims

**WARNING** start of CLMS field may overlap end of DESC **. 1,3,3 - Trimethyl - 6 - azabicyclo - (3,2,1) - octane - 6 - carboxylic acid (2 propenyl) ester 1,3,3 - Trimethyl - 6 - azabicyclo - (3,2,1) - octane - 6 - carboxylic acid phenyl ester 1,3,3 - Trimethyl - 6 - azabicyclo - (3,2,1) - octane - 6 - thiocarboxylic acid S - (4 - fluorophenyl) ester 1,3,3 - Trimethyl - 6 - azabicyclo - (3,2,1) - octane - 6 - carboxylic acid benzyl ester 1,3,3 - Trimethyl - 6 - azabicyclo - (3,2,1) - octane - 6 - carboxylic acid pentyl ester Example 5 In a series of tests carried out in a greenhouse the plants listed in the following Table were treated before their emergence with the listed agents being tested at a rate of application of 3 kg of active substance per hectare. For this purpose the agents were in each case applied uniformly, in the form of an aqueous dispersion using 500 litres per hectare, onto the soil and then incorporated into the soil. The results three weeks after the treatment show that the compound of the present invention was a better herbicidal agent than the agent used for comparison. The results are expressed by a numerical scale extending from 0 to 10, the value 0 representing total destruction of the plant and the value 10 representing no damage. Compound of the Present Invention 1 ,3,3-Trimethyl-6-azabicyclo-(3,2, 1)- octane-6-thiocarboxylic acid S-ethyl ester Agent for Comparison (according to United States Patent Specification No. 3,198,786) S-Ethyl-N,N-hexamethylene thiocarbamate Untreated control c) 9 a "o E 9 S > C D e t a aot; Q a, . YdOyldS fil . 3 10 10 10 0 0 0 0 0 0 0 0 3 0 3 10 10 10 0 0 0 3 3 0 10 10 10 10 10 10 10 10 10 10 10 0=total destruction 10=no damage WHAT WE CLAIM IS:

1. A compound of the general formula I

2. A compound as claimed in claim 1, wherein R represents an alkyl group containing 1 to 7 carbon atoms, a chloralkyl group containing 1 to 7 carbon atoms, an alkenyl group containing 2 to 7 carbon atoms, a chloralkenyl group containing 2 to 7 carbon atoms, an alkynyl group containing 2 to 7 carbon atoms, a benzyl group, a chlorobenzyl group, a phenyl group, a naphthyl group, a chlorophenyl group, a phenyl group substituted by an alkyl group containing 1 to 4 carbon atoms or a phenyl group substituted by a chloralkyl group containing 1 to 4 carbon atoms.

3. A compound as claimed in claim 2, wherein R represents a methyl, ethyl, 2chlorethyl, propyl, isopropyl, allyl, 2-propynyl, dichlorallyl, trichlorallyl, butyl, sec.-butyl, isobutyl, tert.-butyl, butenyl, butynyl, pentyl, isopentyl, benzyl, 4chlorobenzyl, 2,4-dichlorobenzyl, phenyl or 4-chlorophenyl group.

4. 1,3,3 - Trimethyl - 6 - azabicyclo - (3,2,1) - octane - 6 - thiocarboxylic acid S - ethyl ester.

5. 1,3,3 - Trimethyl - 6 - azabicyclo - (3,2,1) - octane - 6 - dithiocarboxylic acid (2 - propenyl) ester.

6. 1,3,3 - Trimethyl - 6 - azabicyclo - (3,2,1) - octane - 6 - thiocarboxylic acid S - methyl ester.

7. 1,3,3 - Trimethyl - 6 - azabicyclo - (3,2,1) - octane - 6 - thiocarboxylic acid S - propyl ester.

8. 1,3,3 - Trimethyl - 6 - azabicyclo - (3,2,1) - octane - 6 - thiocarboxylic acid S - benzyl ester.

9. 1,3,3 - Trimethyl - 6 - azabicyclo - (3,2,1) - octane - 6 - carboxylic acid methyl ester.

10. 1,3,3 - Trimethyl - 6 - azabicyclo - (3,2,1) - octane - 6 - carboxylic acid ethyl ester.

11. 1,3,3 - Trimethyl - 6 - azabicyclo - (3,2,1) - octane - 6 - carboxylic acid propyl ester.

12.1,3,3 - Trimethyl - 6 - azabicyclo - (3,2,1) - octane - 6 - carboxylic acid butyl ester.

13. 1,3,3 - Trimethyl - 6 - azabicyclo - (3,2,1) - octane - 6 - carboxylic acid isopropyl ester.

14. 1,3,3 - Trimethyl - 6 - azabicyclo - (3,2,1) - octane - 6 - carboxylic acid (2 - propenyl) ester.

15. 1,3,3 - Trimethyl - 6 - azabicyclo - (3,2,1) - octane - 6 - carboxylic acid phenyl ester.

16. 1,3,3 - Trimethyl - 6 - azabicyclo - (3,2,1) - octane - 6 - thiocarboxylic acid S - (4 - fluorophenyl) ester.

17. 1,3,3 - Trimethyl - 6 - azabicyclo - (3,2,1) - octane - 6 - carboxylic acid benzyl ester.

18. 1,3,3 - Trimethyl - 6 - azabicyclo - (3,2,1) - octane - 6 - carboxylic acid pentyl ester.

19. A process for the manufacture of a compound of the general formula I given in Claim 1, in which R, X and Y have the meanings given in Claim 1, wherein 1,3,3 - trimethyl - 6 - azabicyclo-(3,2,1)-octane of the formula

(a) is reacted with a halogeno-formic acid ester of the general formula

in which R, X and Y have the meanings given above and Hal represents a halogen atom or (b) is reacted in the presence of a base with a compound of the general formula X=C=Y, in which X and Y have the meanings given above, to form a salt of such a base of the general formula

in which X and Y have the meanings given above and B represents a cation derived from the base, and the salt is treated with an alkylating agent of the general formula R-Z, in which R has the meaning given above and Z represents a halogen atom, an alkyl sulphuric acid group or a toluene sulphonic acid group, or (c) is reacted with a phosgene compound of the general formula Hal2C=X, in which X and Hal have the meanings given above, to form a 1,3,3 - trimethyl 6 - azabicyclo - (3,2,1) - octane - 6 - carboxylic acid halide of the general formula

in which X and Hal have the meanings given above, which is then reacted with an oxygen- or thio- compound of the general formula R--Y'-'B'+', in which R and Y have the meanings given above and B'+' represents a cation.

20. A process as claimed in claim 19, wherein the 1,3,3 - trimethyl - 6 azabicyclo - (3,2,1) - octane is dissolved in a solvent.

21. A process as claimed in claim 19 or 20, wherein the reaction with the halogeno-formic acid ester is carried out in the presence of an acid-binding agent.

22. A process as claimed in claim 19, conducted substantially as described herein.

23. A process as claimed in claim 19, conducted substantially as described in Example 1 or 2 herein.

24. A process for the manufacture of a compound of the general formula I given in claim 1, in which R, X and Y have the meanings given in claim 1, wherein a 1 ,3,3-trimethyl-6-azabicyclo-(3,2, 1 )-octane-6-carboxylic acid halide of the general formula

in which X has the meaning given above and Hal represents a halogen atom, is reacted with an oxygen- or thio- compound of the general formula R#Y(-)B(+), in which R and Y have the meanings given above and B(+) represents a cation.

25. A process as claimed in claim 24, conducted substantially as described in Example 3 herein.

26. A herbicidal preparation which comprises a compound of the general formula I given in claim 1, in which R, X and Y have the meanings given in claim 1, in admixture or conjunction with a suitable carrier.

27. A herbicidal preparation which comprises a compound as claimed in claim 2 or 3, in admixture or conjunction with a suitable carrier.

28. A herbicidal preparation which comprises the compound claimed in any one of claims 4 to 9, in admixture or conjunction with a suitable carrier.

29. A herbicidal preparation which comprises the compound claimed in any one of claims 10 to 18, in admixture or conjunction with a suitable carrier.

30. A preparation as claimed in any one of claims 26 to 29, which is in the form of a powder, a strewable preparation, granules, a solution, an emulsion or a suspension.

31. A preparation as claimed in any one of claims 26 to 30, containing a single compound of the general formula I in an amount of from 10 to 80% by weight.

32. A preparation as claimed in any one of claims 26 to 30, containging two or more compounds of the general formula I in a total amount of from 10 to 80 /n by weight.

33. A preparation as claimed in any one of claims 26 to 32, containing a single surface-active agent in an amount of up to 20% by weight.

34. A preparation as claimed in any one of claims 26 to 32, containing two or more surface-active agents in a total amount of up to 20% by weight.

35. Any one of the herbicidal preparations as claimed in claim 26 and substantially as described in Example 4 herein.

36. A herbicidal preparation as claimed in claim 26 and substantially as described in Example 5 herein.

37. A method of protecting a living plant against weeds, wherein the area in the vicinity of the living plant is treated with a compound of the general formula I given in claim 1, in which R, X and Y have the meanings given in claim 1.

38. A method as claimed in claim 37, wherein the area is treated with a compound as claimed in claim 2 or 3.

39. A method as claimed in claim 37, wherein the area is treated with the compound claimed in any one of claims 4 to 9.

40. A method as claimed in claim 37, wherein the area is treated with the compound claimed in any one of claims 10 to 18.

41. A method as claimed in claim 37, wherein the area is treated with a herbicidal preparation as claimed in any one of claims 26 to 36.

42. A method as claimed in any one of claims 37 to 41, wherein a single compound of the general formula I is used for the treatment in an amount within the range of from 1 to 8 kg per hectare.

43. A method as claimed in any one of claims 37 to 41, wherein two or more compounds of the general formula I are used for the treatment in a total amount within the range of from 1 to 8 kg per hectare.

44. A method as claimed in claim 37, conducted substantially as described in Example 5 herein.

45. A method of protecting a crop area against weeds and/or of regulating the growth of plants in the area, wherein the crop area is treated with a compound of the general formula I given in claim 1, in which R, X and Y have the meanings given in claim 1.

46. A method as claimed in claim 45, wherein the crop area is treated with a compound as claimed in claim 2 or 3.

47. A method as claimed in claim 45, wherein the crop area is treated with the compound claimed in any one of claims 4 to 9.

48. A method as claimed in claim 45, wherein the crop area is treated with the compound claimed in any one of claims 10 to 18.

49. A method as claimed in claim 45, wherein the crop area is treated with a herbicidal preparation as claimed in any one of claims 26 to 36.

50. A method as claimed in any one of claims 45 to 49, wherein a single compound of the general formula I is used for the treatment in an amount within the range of from 1 to 8 kg per hectare.

51. A method as claimed in any one of claims 45 to 49, wherein two or more compounds of the general formula are used for the treatment in a total amount within the range of from 1 to 8 kg per hectare.

52. A method as claimed in any one of claims 45 to 51, wherein the crop is a cauliflower, sugar beet, seeded tomato, bush bean, soya bean, cotton or rice crop.

53. A pack which comprises a compound as claimed in any one of claims 1 to 3 together with instructions for its use as a herbicide and/or for regulating the growth of living plants.

54. A pack which comprises the compound claimed in any one of claims 4 to 9 together with instructions for its use as a herbicide and/or for regulating the growth of living plants.

55. A pack which comprises the compound claimed in any one of claims 10 to 18 together with instructions for its use as a herbicide and/or for regulating the growth of living plants.