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United States Patent [191 [11] 4,159,902 Arndt et a1. [45] Jul. 3, 1979

[54] 1,3,3-TRIMETHYL-6-AZABICYCLO-(3.2.l) Sturm et al., Chem. Abs., vol. 74: 999l0j (1971). OCI‘ANE-6- , Pellacani et al., J. Org. Chem, v01. 41, pp. 1282-1283 HERBICIDES, PROCESS FOR MAKING (1976). SAME AND COMPOSITION CONTAINING Kuehne et al., J. Org. Chem., vol. 40, pp. 1287-1291 SAME (1975). [75] Inventors: Friedrich Arndt; Ludwig Niisslein, Primaryv Examiner-Donald G. Daus both of Berlin, Fed. Rep. of Assistant Examiner-Mary C. Lee Germany . Attorney, Agent, or Firm—Michael J. Striker [73] Assignee: Schering Aktiengesellschaft, Berlin [57] ABSTRACI‘ and Bergkamen, Fed. Rep. of l,3,3-trimethyl-6-azabicyc1o-(3.2. 1)-octane-6-carboxy Germany . lic acid ester of the formula [21] Appl. No.: 819,415 [22] Filed: Jul. 26, 1977 i‘“ ' CH ——c [51] Int. C1.2 ...... C07D 209/02; AOlN 9/22 H3C\| 2 l \ cu, [52] US. Cl...... 71/95; 260/376.32; /? (EH2 h-c-v-n v _ 260/ 326.82 Hsc c1r2—c1-l’ ll ' [58] ?eld of Search ...... 260/ 326.32, 326.82; ' 71/95, 88 [56] References Cited in which R is an aliphatic hydrocarbon residue which may also be substituted, a cycloaliphatic hydrocarbon U.S. PATENT DOCUMENTS residue which may also be substituted, an aromatic 3,198,786 8/1965 hydrocarbon residue which may also be substituted or 3,344,134 9/ 1967 an araliphatic hydrocarbon residue and wherein X and 3,705,165 12/ 1972 Y are oxygen or sulphur. The compounds of the inven 3,820,974 6/1974 tion are characterized by a superior herbicidal activity 3,839,337 10/1974 in particular against monocotyl weeds. They also have 3,872,126 3/1975 excellent selective properties for agricultural plants. OTHER PUBLICATIONS The invention also embraces a process of making the Edwards et al., Chem. Abs., vol. 81: 104267f (1974). compounds of the invention and compositions in which Krow et al., Chem. Abs., vol. 81: 105237h (1974). the compounds of the invention form at least one of the Schneider, Chem. Abs., vol. 76: 143l2j (1972). active components. Snyder et al., Chem. Abs., vol. 34: 9964 (1939). Hewgill et al.; Chem. Abs., vol. 50: 7730i (1956). 18 Claims, No Drawings 4,159,902 1 , 2 DISCUSSION OF THE INVENTION AND 1,3,3-TRIMETHYL-6-AZABICY CLO-(3.2.1) PREFERRED EMBODIMENTS OCI‘ANE-6-CARBOXYLIC ACID ESTER, ~ HERBICIDES, PROCESS FOR MAKING SAME Depending on the desired purpose the following AND COMPOSITION CONTAINING SAME 5 additional herbicidal agents may for instance be used and may also be added only immediately prior to use of BACKGROUND OF THE INVENTION the compounds of the invention: The invention relates to novel 1,3,3-trimethyl-6 substituted , azabicyclo-(3.2.l)-octane-6-carboxylic acid . 10 The herbicidal activity of alkyleneimocarbothiolates substituted aryloxycarboxylic acids and their salts, es ters and , is known (U.S. Pat. No. 3,198,786). These compounds, substituted , however, have a sufficient selective-herbicidal activity substituted arsonic acids and their salts, esters and am only in specific agricultural plantations, such for in ides, stance as in rice cultures where they can be used to substituted benzimidazoles, combat Echinochloa spp. ' substituted benzisothiazoles, It is therefore an object of the present invention to substituted benzthiadiazinone dioxides, provide a compound of this type which has abroad substituted benzoxazines, selectivity as to a large number of agricultural plants substituted benzoxazinones, together with a high herbicidal activity against weeds. 20 substituted benzthiazoles, substituted benzothiadiazines, SUMMARY OF THE INVENTION substituted biurets, This object is solved by a herbicide formed by a 1,3,3 substituted quinolines, substituted , trimethyl-6-azabicyclo-(3.2.l)-octane-6-carboxylic acid 25 ester which has the formula substituted aliphatic carboxylic acids and their salts, esters and amides, substituted aromatic carboxylic acids and their salts, Cl-l / | 3 esters and amides, 2 \ substituted carbamoylalkyl-thio- or dithiophosphates. H3C\| l CH2 30 substituted quinazolines, H C /(|: | 21L _ c _ Y ._ R substituted cycloalkylamidocarbonylthiol acids and 3 CHZ——CH/ 5|‘ their salts, esters and amides, substituted cycloalkylcarbonylamido-thiazoles, in which R is an aliphatic hydrocarbon residue which 35 substituted dicarboxylic acids and their salts, esters and may also be substituted, a cycloaliphatic hydrocarbon amides, residue which may also be substituted, an aromatic substituted dihydrobenzofuranylsulfonates, substituted disul?des, hydrocarbon residue which may also be substituted or substituted dipyridylium salts, an araliphatic hydrocarbon residue and wherein X and substituted , Y are oxygen or sulphur. substituted dithiophosphoric acids and their salts, esters The compounds of the invention are characterized by and amides, a superior herbicidal activity particularly against mono- . substituted urea derivatives, cotyl weeds, for instance Avena, Alopecurus, Echino substituted hexahydro-lH-carbothioates, chloa c.g., Setaria, Digitaria, Poa, Hordeum and Triti 45 substituted hydantoines, cum. substituted hydrazides, Because of their excellent selectivity the compounds substituted hydrazonium salts, can be used in agricultural plantations, for instance in substituted isoxazolpyrimidones, ?elds where cauli?ower, sugar beets, seed-tomatoes, substituted imidazoles, bush beans, cotton and rice are grown. 50 substituted isothiazolpyrimidones, The compounds of the invention furthermore can substituted , also be used in maize and sorghum plantations in which substituted naphthoquinones, case preferably antiodotes such as S-naphthalic acid substituted aliphatic , anhydride or N,N-diallylchloroacetamide are added to substituted aromatic nitriles, the seed or to the sprayed mass of active agents. 55 substituted oxadiazoles, A further advantage of the compounds of the inven substituted oxadiazinons, substituted oxadiazolidinediones, tion is that they also have growth controlling proper substituted oxadiazinediones, ties. The compounds of the invention have a satisfac substituted phenols and their salts and esters, tory effect already in amounts starting with 1 kg of substituted phosphonic acids and their salts, esters and . active agent per about 2.5 acres of ground and because amides, of their surprisingly broad spectrum of selectivity they substituted phosphoniumchlorides, can be used in amounts up to 8 kg of active agent per substituted phosphonalkylglycines, about 2.5 acres prior to the seed by implantation in the substituted phosphites, ground without damage to the agricultural plants. 65 substituted phosphoric acids and their salts, ester and The compounds of the invention can either be used amides, alone or intermixed with each other or'in mixture with substituted piperidines, other different active agents. substituted pyrazoles, 4,159,902 3 4 substituted pyrazolalkylcarboxylic acids and their salts, water as carrier material in spray amounts of about 100 esters, and amides, to 1000 liter per 2.5 acres. An application of the agents substituted pyrazolium salts, is possible in the so-called “low-volume” and “ultra substituted pyrazoliumalkylsulfates, low-volume” process as well as in the form of so-called substituted pyridazines, microgranulates; Among the compounds of the inven substituted pyridazones substituted pyridine-carboxylic acids and their salts, tion those are particularly preferred in which in the esters and amides, above formula R is of 1 to 7 carbon atoms, chlo substituted pyridines, roalkyl of l to 7 carbon atoms, alkenyl of 2 to 7 carbon substituted pyridinecarboxylates, atoms, chloroalkenyl of 2 to 7 carbon atoms, alkinyl of substituted pyridinone, 2 to 7 carbon atoms, benzyl or chlorobenzyl, phenyl or substituted pyrimidone, naphthyl, chlorophenyl, alkylphenyl wherein the alkyl substituted pyrrolidine-carboxylic acids and their salts, moieity has 1 to 4 carbon atoms, chloroalkylphenyl ‘ esters and amides, substituted pyrrolidines, 15 wherein allyl has again 1 to 4 carbon atoms and in substituted arylsulfonic acids and their salts, esters and which compounds X and Y are oxygen or sulphur. amides, Among the radicals identi?ed as R in the proceeding substituted styrenes, paragraph the following are preferred: methyl, ethyl, substituted tetrahydro-oxadiazinediones, 2-chloroethyl, propyl, isopropyl, allyl, 2-propinyl, di-_ substituted tetrahydromethanoindenes, 20 chloroallyl, trichloroallyl, butyl, sea-butyl, isobutyl, substituted tetrahydro-diazol-thiones, tert.-butyl, butenyl, butinyl, pentyl, isopentyl, benzyl, substituted tetrahydro-thiadiazine-thiones, substituted tetrahydro-thiadiazolediones, 4-chlorobenzyl, 2,4-dichlorobenzyl, phenyl, # substituted thiadiazoles, chlorophenyl and many others. substituted aromatic thiocarboxylic acid amides, 25 The compounds which have so far not been described substituted thiocarboxylic acids and their salts, esters in the literature can be made in different ways. and amides, I. 1,3,3-trimethyl~6-azabicyclo-(3.2.l)-octane of the substituted thiolcarbamates, formula ‘ substituted thiophosphoric acids and their salts, esters and amides, 30 substituted triazines, 1”“ substituted triazoles CH2—C substituted uracils, and n 3 c I I \ CH 2 substituted urethidindiones. :C CH; | 35 csc I NH In addition other additives may also be used such as for instance nonphytotoxic additives which result in a cm-cn synergistic increase of the activity in herbicides such as wetting agents, emulsi?ers, solvents and oily additives. which may be dissolved in a solvent are reacted with The compounds of the invention or their mixtures are 40 halogenated formic acid esters of the formula preferably used in the form of powders, dusting agents, granulates, solvents, emulsions or suspensions to which may be added liquid and/or solid carrier materials or diluents and, if desired, agents which improve the wet ting, adhesion, emulsifying and/0r dispersion proper ties. which reaction may be effected in the presence of an Suitable liquid carrier materials are for instance wa acid acceptor. Hal is halogen and R, Y and X have the ter, aliphatic and aromatic hydrocarbons, such as, ben meaning as in the above formula of the ?nal compound. zene, toluene, xylene, cyclohexanone, isophorone, di methylsulfoxide, dimethylformamide, and furthermore II. l,3,3-trimethyl-6-azabicyclo-(3.2.l)-octane of the mineral oil fractions. formula Solid carrier materials are mineral earths, for in stance, tonsil, silica gel, talc, kaolin, attaclay, limestone, CH3 silicic acid and plant products, for instance ?ours. There may also be added surface active agents, for cn2—c instance, calciumlignosulfonate, polyoxyethylene alkyl H 3 c I I \ ca 2 phenylethers, naphthaline sulfonic acids and their salts, >c GB; | phenolsulfonic acids and their salts, formaldehyde con n30 | I NH densation products, fatty alcohol sulfates as well as CH2_CH substituted benzosulfonic acids and their salts. ,The amount of the active agent or agents can be .varied which may be dissolved in a solvent may also be reacted widely. The compositions may for instance contain the with a compound of the formula “ ' active agents in an amount of about 10 to 80% by weight, together with about 90 to 20% by weight of liquid or solid carrier materials and, if desired, up to 65 20% by weight of surface active agents. I The application of the agents can be effected in con ’ in the presence of a base B‘so as to form the salt of the ventional form. They may for instance be applied with base having the formula 4,159,902 6 hydrocarbons such as methylene chloride, chloroform, carbontetrachloride; halogenated ethylenes; -type compounds such as diethylether, diisopropylether, tet rahydrofuran, and dioxane, ketones, such as acetone, methylisobutylketone and isophorone; ester, such as acetic acid methyl- and ethylester; acid amides, like dimethylformamide and hexamethylphosphoric acid triamide, carboxylic acid , like acetonitrile and many others. The isolation of the compounds of the wherein the salt is treated with an alkylating agent 10 invention is effected at the end of the reaction by distill R—Z. R, Y and X have the meaning as in the above ing off the solvent or extractive agent at normal or formula, B has been identi?ed above as a base and Z is reduced pressure. If desired, the reaction product may, a halogen or alkyl- or toluene sulfphuric acid residue. prior to isolation, be treated with an acid or basic agent ' III. l,3,3-trimethyl-6-azabicyclo-(3.2.l)-octane of the in order to remove undesirable byproducts. If necessary formula the compounds can be distilled in a vacuum in order to obtain them in high purity. The following examples will further illustrate the making of the compounds of the invention.

EXAMPLEv l v 24.9 of chlorothioformic acid-S-ethylester were slowly added dropwise'at room temperature and while stirring to a solution of 61.3 g l,3,3-trimethyl-6-'azabicy clo-(3.2.l)-octane in 150 ml diisopropylether. After which may be dissolved in a solvent may be reacted stirring for one hour the reaction mixture was shaken with a phosgene compound of the formula with water, then with dilute hydrochloric acid and afterwards again with water. The organic phase was Hal2C=X so to form 1,3,3-trimeth l-6-azabicyclo-(3.2.l)-octane-6-car dried on magnesium sulfate, the solvent was distilled off boxylic acid halide of the formula 30 in a vacuum and residual solvent was ?nally removed in a high vacuum. CH3 By reacting the ?rst-obtained water extract with sodium hydroxide the excess of starting product was CH1—C recovered. _ H3C I I CH2 Yield: 46.0 g (95.29% of the theoretical value) of ): CH2 I‘ 3'5 1,3,3-trimethyl-6-azabicyclo-(3.2. l)-octane-6-thiocar H3C I —|C|—Hal boxylic acid-S-ethylester; nD2°= 1.5123. CH2—-CH Analysis: calculated: C 64.68%, H 9.60%, N 5.80%. obtained: C 64.38%, H 9.65%, N 6.01%. The thus obtained reaction product is then caused to react with an oxygen- or thio compound of the formula EXAMPLE 2 15.2 g of carbondisul?de were added dropwise while stirring at a temperature between 10° and 15° C. to a mixture of 34 ml l,3,3-trimethyl-6-azabicyclo-(3.2.1) R, S and Y in these formulae have again the meaning as octane, 50 ml acetonitrile and 8 g of sodium hydroxide in the above formula of the ?nal product and Hal indi dissolved in 50 ml water. Stirring was then continued cates a halogen or an alkyl sulphuric acid residue or a for 2 hours to obtain the dithiocarbamic acid salt. toluene residue. Thereafter 24.5 g of allylbromide were added dropwise As bases or acid acceptors in the above reactions can to the reaction mixture and stirring was continued for 1 be used all conventional proton acceptors. For this 50 hour to cause formation of the ester. After adding 500 purpose organic bases may be used, such as, tertiary ml methylene chloride the organic phase was shaken like triethylamine or N,N-dimethylaniline or a with dilute hydrochloric acid, dried on magnesium pyridine base; furthermore, suitable inorganic bases, sulfate, treated with activated carbon and concentrated such as, oxides, hydroxides and carbonates of the alkali by evaporation in a high vacuum. and alkaline-earth metals. Liquid bases can at the same time function as solvents. An excess of the employed 55 There were obtained 52 g (96.4% of the theoretical initial liquid base may form also the acid acceptor. value) of l,3,3-trimethyl-6-azabicyclo-(3.2.l)-octane-6 As alkylation agents, preferably chlorides, bromides dithiocarboxylic acid allylester; nD2°= 1.5810. and iodides are used. Analysis: calculated: C 62.40%, H 8.60%, N 5.20%, S The reaction of the individual components can be 23.80%, obtained: C 62.23%, H 8.53%, N 5.02%, S effected at a temperature between about 0° and 120° C. 60 23.71%. preferably, however, at room temperature. ‘ EXAMPLE 3 The components are preferably used in. about equi molar amounts. , 5.4 g of sodiumethylate were added while stirring to Suitable reaction media should be inert towards the a solution. .of 21.5 g of l,3,3-trimethyl-6-azabicyclo reactants as solvents, either alone or when used in mix 65 (3.2.l)-octane-6-carboxylic acid chloride in 100 ml ace ture with water. The following may be named: aliphatic tonitrile. After- stirring for 2 hours the reaction mixture and aromatic hydrocarbons, such as petroleum ether, was reacted with 350 ml water. The separated oil was cyclohexane, benzene, toluene and xylene; halogenated then» extracted with chloroform and the chloroform 4,159,902 7 8 phase was shaken with dilute hydrochloric acid fol TABLE I lowed by drying on magnesium sul?te and ?nally distill Compounds of the Invention Lolium Setaria ing off of the solvent in a high vacuum. l,3,3-trimethyl-6~azabicyclo-(3.2. 1) There were obtained 19.0 g (90.2% of the theoretical octane-6-thiocarboxylic acid-S-ethyl value) of the oily product constituted by 1,3,3-trimeth ester 4 4 l,3,3-trimethyl-6-azabicyclo-(3.2.1) yl-6-azabicyclo-(3.2.1)-octane-6-carboxylic acid meth octane-6-thiocarboxylic acid-S-methyl ylester; np2°= 1.4840. ester 4 4 Analysis: calculated: C 68.21%, H 10.02%, N 6.63%. 1,3,3-trimethyl-6-azabicyclo-(3.2. l) octane-6-thiocarboxylic acid-S-propyl obtained: C 68.23%, H 10.01%, N 7.03%. ester 4 4 In an analogous manner the following compounds of the invention were prepared. octane-?-dithiocarboxylic acid-(2 propenyl)-ester 4 3 l,3,3-trimethyl-6-azabicyclo-(3.2. l) Physical 15 octane-6-thiocarboxylic acid-S Compound constants benzylester . 3 — 1,3,3-trimethyl-6-azabicycio-(3.2. 1) AIEQBLSL?iEYJIEL octane-6-tl1iocarboxylic acid-S-methyl 1,3,3~trimethyl-6-azabicyclo4(3.2. l)—octane-6-ca.rb0xylic ester 7 n 0 = 1.5172 acid-methylester l,3,3-trimethyl-6-azabicyclo-(3.2. l) 20 1,3,3-trimethyl-6-azabicyclo-(3.2. l)-octane-6-carboxylic octane-6-thiocarboxylic acid-S-propyl acid ethylester ester npzo = 1.5090 l, 3,3-trimethyl-6-azabicyclo-(3.2. l)-octanc l,3,3-trimethyl-6~azabicyclo-(3.2.l) acid propylester I octane-6-thiocarboxylic acid-S-benzyl l,3,3-trimethyl-6‘azabicyclo-(l2.1)-octane acid butylester ester “D20 = 1.5526 25 l,3,3-trimethyl-6-azabicyclo-(3.2. l) 1, 3,3-trimethyl-6—azabicyclo-(3.2. 1)-octane-6-carboxylic octane-6-carboxylic acid-ethylester nDZO = 1.4702 acid isopropylester l, 3,3-trlmethyl-6-azabicyclo-(3.2. l)'octane-6-carboxylic I 1,3,3-trimethyl-6-azabicyclo-(3.2.l) acid-(2-propenyl)-ester octane-6~carboxylic acid-propylester 111320 = 1.4692 1,3,3-trimethyl-6-azabicyclo(3.2. l)-octane-6'carboxylic l,3,-trimethyl-6-azabicyclo-(3.2. l) acid phenylester octane-6-carboxy1ic acid-butylester npzo = 1.4612 30 l,3,3-trimethy-6-azabicyclo-(3.2. l)-octane~6-carboxylic) l,3,3-trimethyl~6—azabicyclo-(3.2. 1) acid-S-(4-lluorophenyl)-ester octane-6-carboxylic acid-isopropylester npzo = 1.4652 1,3,3-trimethy-6-azabicyclo-(3.2. l) octane-6-carboxylic acid-(Z-propenyD-ester 111,20 =0 1.4796 Analogous activity had: 1,3,3-trimethyl-6-azabicyclo'(3.2. 1) octane-6-carboxylic acid-phenylester R020 = 1.5224 35 1,3,3-trimethyl-6-azabicyclo-(3.2. l)-octane-6-carboxy 1,3,3-trimethyl-6-azabicyclo-(3.(3.2. l)~ lic acid-methylester octane-6-thiocarboxylic acid-S-(4-lluoro 1,3,3-trimethyl- 6-azabicyclo-(3.2. l)-octane-6-carboxy pheny1)ester l,3,3-trimethyl-6-azabicyclo-(3.(3.2. l) lic acid ethylester octane-6‘carb0xylic acid-benzylester npzo = 1.5212 l ,3,3-trimethyl-6-azabicyclo-(3 .2. 1)-octane-6-carboxy 1,3,3-trimethyl-6-azabicyclo-(3.2. l) lic acid propylester octane-6-carboxylic acid-pentylester npzo = 1.4664 1,3,3-trimethyl-6-azabicyclo-(3.2. l)-octane-6-carboxy lic acid butylester The compounds of the invention are colorless or 1,3,3-trimethyl-6-azabicyclo-(3.2. l)-octane-6-carboxy slightly yellowish oils which have a faint aromatic smell 45 lic acid isopropylester and which are insoluble in water but have good solubil 1,3,3-trimethyl-6-azabicyclo-(3.2. l)-octane-6-carboxy ity in all organic solvents, for instance in hydrocarbons, lic acid-(2-propenyl)-ester halogenated hydrocarbons, ethers, ketones, carboxylic 1,3,3-trimethyl-6-azabicyclo-(3.2. 1)-octane-6carboxylic acid phenylester acid esters, carboxylic acid amides, carboxylic acid l,3,3-trimethyl-6-azabicyclo-(3 .2. l)-octane-6-thiocar nitriles, alcohols, carboxylic acids, and many boxylic acid-S-(4—?uorophenyl)-ester others. 1,3,3-trimethyl-6-azabicyclo-(3.2. l)-octane-6-carboxy lic acid benzylester USES AND ACTIVITY 1,3,3~trimethyl-6-azabicyclo-(3.2. 1)-octane-6-carboxy The following examples will illustrate the application 55 lic acid pentylester of the compound of the invention and its activity. EXAMPLE 5 EXAMPLE 4 The plants listed below in Table II were treated in a The compounds listed below in Table I were applied preemergence application in a hothouse with the com in a hothouse in an amount of 5 kg of active agent per pounds listed in the Table in amounts of 3 kg of active 2.5 acres suspended in 500 liter water per 2.5 acres. The agent per about 2.5 acres. The agents were applied to application was effected by spraying the material onto the ground in a uniform manner as an aqueous disper the ground prior to seeding and working it into the sion in 500 liter per about 2.5 acres and the dispersion ground whereupon Lolium and Setaria were then 65 was subsequently worked into the ground. The results grown on the thus treated ground. Three 'weeks after obtained 3 weeks after treatment show that the com treatment the results were evaluated on a scale from pound of the invention are superior to the comparison 0: =no effect to 4=total destruction of the plants. material. > I 4,159,902 9 10 TABLE II Compound of the 3 kg/about soy- Trit- Alope- Echino- Set- Digi lnvention 2.5 acres cotton beans rice icum l-lordeum Avena curus chloa aria taria Poa l,3,3-trimethyl~6~azabicyclo (3.2. l)-octane-6-thiocarboxylic acid-S-ethylester 3 10 l0 l0 0 0 O 0 0 0 0 0 Comparison Compound (Pat. 3,198,786) Sethyl-NN-hexamethylenethio 0 3 l0 l0 l0 0 0 0 3 3 0 Untreated l0 l0 l0 l0 l0 10 10 l0 10 10 10

0 = total destruction l0 = no injury to plants 6. The compound of claim 1 which is 1,3,3-trimethyl l5 6-azabicyclo-(3.2.1)-octane-6-thiocarboxylic acid-S Without further analysis, the foregoing will so fully benzylester. reveal the gist of the present invention that others can, 7. The compound of claim 1 which is 1,3,3-trimethyl by applying current knowledge, readily adapt it for 6-azabicyclo-(3.2.l)-octane-6-carboxylic acid methyles various applications without omitting features that, ter. from the standpoint of prior art, fairly constitute essen 20 8. The compound of claim 1 which is 1,3,3-trimethyl tial characteristics of the generic or speci?c aspects of 6-azabicyclo-(3.2.l)-octane-6-carboxylic acid ethyles this invention. ter. What is claimed as new and desired to be protected 9. The compound of claim 1 which is l,3,3-trimethyl by Letters Patent is set forth in the appended claims: 6-azabicyclo-(3.2.l)-octane-6-carboxylic acid propy 1. l,3,3-trimethyl-6-azabicyclo-(3.2.1)-octane-6-car 25 lester. boxylic acid ester of the formula 10. The compound of claim 1 which is 1,3,3-trimeth yl-6-azabicyclo-(3.2.l)-octane-6~carboxylic acid buty lester. 11. The compound of claim 1 which is 1,3,3-trimeth yl-6-azabicyclo-(3.2.l)-octane-6-carboxylic acid isopro pylester. 12. The compound of claim 1 which is 1,3,3-trimeth yl-6-azabicyclo-(3.2. l)-octane-6-carboxylic acid-(2 propenyl)-ester. in which R is alkyl of l to 7 carbon atoms, chloro-alkyl 35 13. The compound of claim 1 which is 1,3,3-trimeth of l to 7 carbon atoms, alkenyl of 2 to 7 carbon atoms, yl-6-azabicyclo-(3.2.l)'octane-6~carboxylic acid chloroalkenyl of 2 to 7 carbon atoms, alkinyl of 2 to 7 phenylester. , carbon atoms, benzyl, chlorobenzyl, phenyl, naphthyl, 14. The compound of claim 1 which is 1,3,3-trimeth chlorophenyl, alkylphenyl having 1 to 4 carbon atoms yl-6-azabicyclo-(3.2.l)-octane-6~thiocarboxylic acid-S in the alkyl moiety of chloroalkylphenyl having again 1 40 (4-fluorophenyl)-ester. to 4 carbon atoms in the alkyl portion and wherein X 15. The compound of claim 1 which is 1,3,3-trimeth and Y are oxygen or sulphur. yl-6-azabicyclo-(3.2.l)-octane-6-carboxylic acid benzy 2. The compound of claim 1 which is 1,3,3-trimethyl lester. 6-azabicyclo-(3.2.l)-octane-6-thiocarboxylic acid-S 16. The compound of claim 1 which is 1,3,3-trimeth ethylester. . 45 yl-6-azabicyclo-(3.2.l)-octane-6-carboxylic acid penty 3. The compound of claim 1 which is 1,3,3-trimethyl lester. 6-azabicyclo»(3.2.l)-octane-6-dithiocarboxylic acid-2 ' 17. A herbicidal composition comprising at least one (propenyl)-ester. active agent as defined in claim 1 in an amount from 4. The compound of claim 1 which is 1,3,3-trimethyl about 10 to 80% by weight and a liquid or solid carrier 6-azabicyclo-(3.2.l)-octane-6-thiocarboxylic acid-S 50 material in an amount of about 90 to 20% by weight. methylester. 18. The composition of claim 17 which includes up to 5. The compound of claim 1 which is 1,3,3-trimethyl about 20% by weight of a surface active agent or 6-azabicyclo-(3.2.l)-octane-6-thiocarboxylic acid-S agents. propylester. 55

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