HERBICIDAL BICYCLIC 1,3-DIKETONE DERIVATIVES

Abstract: Compounds of formula (1a), (1b) or (1c) or isomeric or tautomeric forms thereof characterized in that W is hydrogen or one of the groups ( alpha ) and ( beta ); R<1>, R<2>, R<3>, R<4>, R and R'' are various substituents; and n is 1, 2, 3, 4 or 5; and herbicidal compositions or methods which include such compounds.

Description: -1- HERBICIDAL BICYCLIC 1,3-DIKETONE DERIVATIVES Th .s invention re tes to organic o.po.nds having herbicida. properties and plant growt h relating properties, to processes for the reparation o . such compounds; to mediates usefu, ,» the preparat i „ such compoun d s; to her ci d a. compositions an d processes utϋizmg suc n compounds and to p nt growth regu ting compositions an d processe utilizing such compounds. ( ■ < f i ~~>~~-~~~~-73*1" r" — . The use of certain cyclohexane-l,3-dione derivatives as grass herbicides is known in the art. Thus, for example, the compendium "Agricultural Chemicals - Book II Herbicides 1986-87 Revision" (W.T. Thomson Editor, Thomson Publications, California U.S.A.) describes the cyclohexane-l,3-dione derivatives known commercially as Alloxydim Sodium ( methyl -3-[l-( ally loxyi mi no) utyl ]-4-hydroxy-6,6-di methyl -2-oxocyclohex- 3-ene carboxylate), Cloproxydim ((E,E)-2[l-[l-[(3-chloro-2-propenyl ) oxy]imino]butyl]-5-[2-(ethylthio)propyl]-3-hydroxy-2-cyclohexen-l-one), 0 Cycloxydim (2-[l-eth oxyimi no)butyl ]-3-hydroxy-5-[2H^tetrahydrothiopyran- 3-yl]-2-cyclohexen-l-one and Sethoxydim (2-[l-(ethoxyimino)butyl]-5-[2- ethylt_io]proρyl-3-hydroxy-2-cyclo exen-1-one) as selective post-emergent ,_ herbicides. Alloxydim and Sethoxydim have been disclosed in Australian lb Patent No. 464655 and Australian Patent Application No. 35,314/78 respectively. Esters and amides of the general formula (A) (X=0 or NR°) wherein 20 R 5 =H have been claimed to show herbicidal activity (Eur. Pat. Appl. EP. 126,713 (Chemical Abstracts, 1985, 102, 112934)). 25 30 suBSTranrε^ΗEET Furthermore, compounds similar to Formula (A), but which bear an additional substituent at the C-1 position (ie R 5 = alkyl, etc) have also been claimed as herbicides (our co-pending Eur. Pat. Appl. 219,343 (Chemical Abstracts, 1987, _107_, 23Q12y)). The compounds of this co- pending patent show herbicidal activity towards grasses and are safe to broadleaved crops. A major deficiency of this class of compounds is their general toxicity towards cereal crops such as wheat and barley. Derivatives of bicyclic 1,3-diketones of Formula (B) have been claimed as herbicides : Japan Kokai 76, 80,844 (Chemical Abstracts, 1976, 85, 176958n). SUuSTΪTUTE S. We have discovered that compounds similar to Formula (B) but which bear an additional substituent at one of the bridgehead carbon atoms as shown in Formula (1) exhibit particul rly useful herbicidal activity with special selectivity for weed grasses in crops, and plant growth regulating activity. Significantly, some of these derivatives of Formula (1) also show special selectivity for weed grasses in grass crops such as wheat and barley. It should be noted that compounds of the general formula (1) wherein n=4 and R=R -hydrogen fall within a general structural class claimed as herbicides (Great Britain Patent 1 455 200 and Great Britain Patent 1 461 I SUBSTITUTE SHEET 2041 .cording,,, this mention provides a compound of formula U, „ here in _■ is sheeted from the group consisting of: . ,_.ι__kvl ■ cycloalkenyl substituted alkyl or alkenvl; alkynyl; cycloalky i , 'I' 1 " t uted cycloalkyi wherein the alkyl or cycloalky, group is subst1tuted w(t n a substituent selected from the group «~»«"' neterocycle; alkyl sulfonyl; optionally subst i tuted a cyl group; and an inorganic or organic cation . Λs selected from the group consisting of: 5 hal oalkenyl . alkynyl; haloal kynyl; R 3 1s Elected from the group consisting of: alkyl. alkenyl. alkynyl; and optionally substituted phenyl; . 0 n is 1,2,3,4,5; • „ t _ R R U are each selected independently from t The 2n substituents R,R are cβv - „ n . alkyl- alkenyl; alkynyl; haloalky group consisting of: hydrogen; alkyl, 35 SUBSTiTU " haloalkenyl; cycloalkyi; cycloalkenyl; substituted alkyl or substituted cycloalkyi wherein the alkyl or cycloalkyi group is substituted with a substituent selected from the group consisting of alkoxy, alkyl thio, oxo, acyl, alkoxycarbonyl, ketal, optionally substituted phenyl, and optionally substituted heterocycle; optionally substituted phenyl; and optionally substituted heterocycle; with the proviso that when n is 4 not all of tne eight substituents R and R 11 are hydrogen. ,4 is selected from the group consisting of: alkyl; alkenyl; alkynyl; substituted alkyl wherein the alkyl group is substituted with a substituent selected from the group consisting of alkoxy, alkylthio, optionally substituted phenyl, and optionally substituted heterocycle; optionally substituted phenyl; and optionally substituted heterocycle. In all of the above alkyl, alkenyl and alkynyl include straight- chain and branched-chain structures. In all of the above heterocycle means a mono- or polycyclic heterocyclic ring structure that contains one or more heteroatoms and may or may not be aromatic. Suitable heteroatoms are nitrogen, oxygen, and sulphur. The heterocyclic ring preferably has more than three atoms in the ring. Some examples of suitable heterocycle groups are thiophenyl, benzofuranyl, furanyl, morpholino, and pyri yl. Preferably in all of the above alkyl, alkenyl, and alkynyl mean lower alkyl, alkenyl and alkynyl. More preferably alkyl, alkoxy, alkylthio, haloalkyl, alkyl sulphonyl or substituted alkyl groups contain 1 to 6 carbon atoms and alkenyl, alkynyl, haloalkenyl, or haloalkynyl groups contain 2 to 6 carbon atoms. It should be recognized that when R is hydrogen the compounds of Formula (1) of the invention may undergo tautomerism and exist in any one of five forms as shown below. 1 CM ."TIT _' v: " ~ • l?-~~-—- (lc) (Id) All tautomeric forms are included in the scope of this invention. -8- It should be noted that when R 1 is other than hydrogen a compound of Formula ( 1) may b e obtained as a mixture with an isomeric compound of Formula (ID) where R 1 , R Z , R 3 , * R and R 11 , and n are as d efine d a b ove. These isomeric compounds of Formula (lb) are included within the scope of this invention, either pure or as mixtures with the corresponding compound of Formula (1). It should be recognized that cis and trans ring fusion is possible or bicyclic derivatives of Formula (1) and Formula ( l b) of the invent i on. Both cis and trans isomers of derivatives of Formula ( 1 ) and Formula (lb) are included in the scope of this invention. Particularly preferred choices for R 1 include hydrogen and the 5 alkali metal cations. Preferred choices for R 2 include alkyl, alkenyl and haloalkenyl. Particularly preferred choices for R 2 include ethyl, ally! and 2- and 3-chloroallyl. on Particularly preferred choices for R 3 include ethyl and n-propyl. The particularly preferred choice for n is 3. Where isomers may exist useful compositions may consist of the 35 ϊ ~j j UP * " "! ~ ~~-- ~ r~-- ~ --'- ~ ~ ' -. • - . . - < ■ <'- -_i. l--.--- isomers separately or in mixtures in any possible ratio. Specific examples of herbicidal compounds of formula (1) of the invention are the alkyl 3aH_-indene-3a-_:arboxylate derivatives (1.1-1.9) (Table 1) and methyl 3,5-dioxo-4-(l-(2- propenyl )oxyimino)butylbicyclo[4. ' 2.0]octane-l-carboxylate (1.10). TABLE 1 (1.1 - 1.9) (1.10) Compound R l J R R- ,11 20 1.1 H n-propyl allyl methyl 1.2 H ethyl 1.3 H CH 2 CH=CH 2 C1 1.4 H propargyl methyl 2 255 1.5 H allyl isopropyl 1.6 H eth l methyl methyl 1.7 H allyl II 1.8 H ethyl allyl methyl H H 3 .0_ 1.9 H n-propyl allyl methyl methyl H * Footnote: For convenience all compounds in this invention of formula (1), (6), (7) and (8) are named as 1,3-diketone tautomers 35 rather than enol -ketone tautomers. Ti ; ■ _" _. ' ■ •' S UBS» s ■ ' ' ~ "" The compounds of this invention may be prepared from 3,5- dimet oxybenzoic acid (2) by reduction with an alkali metal in l quid ammonia followed by addition of an appropriate electrophile (cf. Aust. J. Chem., 1981, _34, 675). (Reaction Scheme 1). The 1-substi tuted 3,5- dimethoxy-2,5-cyclohexadiene-l-carboxylic acid derivatives of Formula (4) thus obtained may be converted to the ester derivatives of Formula (5) by standard literature methods. By way of non-limiting example, the esters of Formula (5) may be prepared by reaction of compounds of Formula (4) with an alcohol in the presence of an acid. Also by way of non-limiting example, the esters of Formula (5) may be prepared by a three step method involving reduction of esters of 3,5-dimethoxybenzoic acid with an alkali metal in liquid ammonia followed by addition of an appropriate electrophile followed by treatment with aqueous acid (Reaction Scheme 2). ύ _. (->«_* 1 k -. t m , R 4 OH/H + Fries (6) (7) (8) 1) Reaction Scheme 1 (9) (10) (ID Reaction Scheme 2. Q We have found that the use of 1,2-dihalo-, 1,3-dihalo- and 1,4- dihaloalkanes as electrophile in the reactions shown in Reaction Schemes 5 1 and 2 provides a particularly efficaceous method of making compounds of Formula (5), wherein n = 2,3,4 and Y = halogen. Reaction of compounds of Formula (5) with lithium diisopropyl amide (cf Organic Syntheses, 1986, j54_, 68) provides the novel bicyclic 0 derivatives of Formula (6), which afford the bicyclic 1,3-diketone derivatives of Formula (7) on treatment with aqueous acid. The enol derivatives of Formula (7) may be acylated on oxygen and the enol ester intermediates thus obtained isomerized (Fries rearrangement) to give the 5 novel j acylated products of Formula (8). The ^-acylated derivatives may be reacted with 0_-substituted hydroxyl amines to afford derivatives of the general Formula (1) wherein is hydrogen. 0 Compounds of the invention of Formula (1) wherein R is not hydrogen may be prepared by standard synthetic procedures. For example, compounds Sϋ Sτi3U of the invention of Formula (1) wherein R,1 A is an inorganic or organic cation may be prepared from compounds of the invention of Formula (1) wherein 1 is hydrogen by reacting these latter compounds with an appropriate inorganic or organic base. From such reactions a mixture of isomeric compounds of Formula (1) and Formula (lb) may be obtained. Esterification of the vinylogous acid in compounds of Formula (1) wherein R is hydrogen provides further herbicidal and growth regulating derivatives; from such reactions a mixture of isomeric compounds of Formula (1) and Formula (lb) may also be obtained. Compounds of Formula (6), (7) and (8) where R ,R ,R , and n are herein Defore defined are novel. The scope of the invention includes these compounds. It should be recognized that cis and trans ring fusion is possible for the bicyclic derivatives of Formula (6), (7) and (8) of the invention. Both cis and trans isomers of derivatives of Formula (6), (7) and (8) are included in the scope of this invention. It should be recognized that tautomerization is possible for the compounds (7) of the invention and that they may exist in any one of three tautomeric forms as shown below. « - » * i j j ,. '- -. - -. ._. . . All tautomeric and cis and trans isomeric forms of compounds of Formula (7) are included in the scope of this invention. It should be recognized that the compounds (8) of the invention may undergo tautomerism and exist in any one of five forms as shown below. (8c) (8d) All tautomeric and cis and trans isomeric forms of compounds of Formula (8) are included in the scope of this invention. The compounds of Formula (1) may be applied directly to the plant (post-emergence application) or to the soil before the emergence of the plant (pre-emergence application). The compounds of Formula (1) may be used on their own to inhibit the growth of, severely damage, or kill plants but are preferably used in the form of a composition comprising a compound of the invention in admixture with an inert carrier comprising a solid or liquid diluent. Therefore, in yet a further aspect the invention provides plant growth inhibiting, plant damaging, or plant killing compositions comprising a compound of Formula (1) as hereinbefore defined and an inert carrier therefore. The compositions of the invention may comprise, in addition to one or more compounds of the invention, one or more compounds not of the invention but which possess biological activity. For example, as hereinbefore indicated the compounds of the invention are in general substantially more effective against onocotyledonous plants or grass species than against dicotyledonous plants or broad-leaved species. As a result, in certain applications the herbicidal use of the compounds of the invention alone may not be sufficient to protect a crop. Accordingly in yet a still further embodiment the invention provides a herbicidal composition comprising a mixture of at least one herbicidal compound of Formula (1) as hereinbefore defined with at least one other herbici e. Certain of the compounds of Formula (1) exhibit useful plant growth regulating activity. For example, while certain compounds of Formula (1) shown selective herbicidal activity against wild grasses in crops of cultivated plants, at some rates of application they exhibit plant growth regulating effects in said crops. Certain of the compounds of Formula (1) may be used for selective control of wild grass in graminaceous crops. Plant growth regulating effects may be manifested in a number of ways. For example, suppression of apical dominance, stimulation auxili ry bud growth, stimulation of early flowering and seed formation, enhancement of flowering and increase in seed yield, stem thickening, stem shortening and tillering. Plant growth regualting effects shown by compounds of the invention include, for example, tillering and stem shortening in crops such as wheat and barley. Accordingly in a still further aspect the invention provides a process for regulating the growth of a plant which process comprises applying to the plant, to the seed of the plant, or to the growth medium 0 of the plant, an effective amount of a compound Formula (1), as hereinbefore defined. To effect the plant growth regulating process of the present I - invention the compounds of Formula (1) may be applied directly to the " plant (post-emergence application) or to the seed or soil before the emergence of the plant (pre-emergence) application. The compounds of Formula (1) may be used on their own to regulate 0 the growth of plants but in general are preferably used in the form of a composition comprising a compound of the invention in admixture with a carrier comprising a solid or liquid diluent. Therefore, in a still further aspect the invention provides pl nt 5 growth regulating compositions comprising a compound of Formula (1) as hereinbefore defined and an inert carrier therefor. The compositions of the present invention may be in the form of solids, liquids or pastes. The compositions include both dilute 0 compositions which are ready for immediate use and concentrated compositions which may require dilution before use. Therefore, the concentration of the active ingredient in the compositions of the present _ 5 invention will vary depending on the type of formulation and whether the c- • >. ' — composition is ready for use such as, for example, a dust formulation or an aqueous emulsion or whether the composition is a concentrate such as, for example, an emulsifiable concentrate or a wettable powder, which is suitable for dilution before use. The present invention includes both types of composition, accordingly the compositions to the present invention comprise from lppm to 99% by weight of active ingredient. The solid compositions may be in the form of powders, dusts, pellets, grains, and granules wherein the active ingredient is mixed with a solid diluent. Powders and dusts may be prepared by mixing or grinding the active ingredient with a solid carrier to give a finely di ided composition. Granules, grains and pellets may be prepared by bonding the active ingredient to a solid carrier, for example, by coating or impregnating tne preformed granular solid carrier with the active ingredient or by agglomeration techniques. Examples of solid carriers include: mineral earths and clays such as, for example, kaolin, betonite, kieselguhr, Fuller's earth, Attaclay, diatomaceous earth, talc, chalk, dolomite, limestone, lime, calcium carbonate, powdered magnesia, magnesium oxide, magnesium sulfate, gypsum, calcium sulfate, pyrophllite, silicic acid, silicates and silica gels; fertilizers such as, for example, ammonium sulfate, ammonium phosphate, ammonium nitrate and urea; natural products of vegetable origin such as, for example, grain meals and flours, bark meals, wood meals, nutshell meals and cellulosic powders; and synthetic polymeric materials such as, for example, ground or powdered plastics and resins. Alternatively, the solid compositions may be in the form of dispersible or wettable dusts, powders, granules or grains wherein the active ingredient and the solid carrier are combined with one or more SUBSTITUTE SHEET surface active agents which act as wetting, emulsifying and/or dispersing agents to facilitate the dispersion of the active ingredient in liquid. Examples of surface active agents include those of the cationic, anionic and non-ionic type. Cationic surface active agents include quaternary ammonium compounds, for example, the long chain alkyl ammonium salts such as cetyltrimethylam onium bromide. Anionic surface active agents include: soaps or the alkali metal, alkaline earth metal and ammonium salts of fatty acids; the alkali metal, alkaline earth metal and ammonium salts of aryl sulfonic acids including the salts of naphthalenesulfonic acids such as butyl naphtha! enesulfom ' c acid, the di- and tri-isopropylnaphthalenesulfonic acids, the salts of the condensation products of sulfonated naphthalene and naphthalene derivatives with formaldehyde, the salts of the condensation products of sulfonated naphthalene and naphthalene derivatives with phenol and formaldehyde, and the salts of alkyl aryl benzenesulfonic acids such as dodecylbanzenesulfonic acid; the alkali metal, alkaline earth metal and ammonium salts of the long chain mono esters of sulfuric acid or alkylsulfates such as lauryl sulfate and the mono esters of sulfuric acid with fatty alcohol glycol ethers. Nonionic surface active agents include: the condensation products of ethylene oxide with fatty alcohols such as oleyl alcohol and cetyl alcohol; the condensation products of ethylene oxide with phenols and alkylphenols such as isooctylphenol, octylphenol and nonylphenol; the condensation products of ethylene oxide with castor oil; the partial esters derived from long chain fatty acids and hexitol anhydrides, for example sorbitan monolaurate, and their condensation products with ethylene oxide; ethylene oxide/prop 1ene oxide block copolymers; lauryl alcohol polyglycol ether acetal ; and the f £&.. _3£ l eci thi ns. The l iqui d composi tions may compri se a solution or di spersion of the acti ve i ngredient in a l i quid carrier optional ly contai ni ng one or more surface acti ve agents which act as wetti ng, emul si fyi ng and/or di spersi ng agents. Examples of liquid carriers include: water; mineral oil fractions such as, for example, kerosene, solvent naphtha, petroleum, coal tar oils and aromatic hydrocarbons such as, for example, paraffin, cyclohexane, toluene, the xylenes, tetrahydronaphthalene and alkylated naphthalenes; alcohols such as, for example, methanol, ethanol, propanol, isopropanol, butanol, cyclohexanol and propylene glycol ; ketones such as, for example, cyclohexanone and isophorone; and strongly polar organic solvents such as, for example, j, _-dimethylformamide, dimethyl sulfoxide, ^methylpyrrolidone and sulfolane. A preferred liquid composition comprises an aqueous suspension, dispersion or emulsion of the active ingredient which is suitable for application by spraying, atomizing or watering. Such aqueous compositions are generally prepared by mixing concentrated compositions with water. Suitable concentrated compositions include emulsion concentrates, pastes, oil dispersions, aqueous suspensions and wettable powders. The concentrates are usually required to withstand storage for prolonged periods and after such storage to be capable of dilution with water to form aqueous preparations which remain homogeneous for a sufficient time to enable them to be applied by conventional spray equipment. The concentrates conveniently contain from 20 to 99%, preferably 20 to 60%, by weight of active ingredient. Emulsions or emulsifiable concentrates of the salts are conveniently prepared by dissolving the active ingredient in an organic solvent ε s. - containing one or more surface active agents used in the formulation and the salts generated in situ by the use of the appropriate organic or inorganic base. The mode of application of the compositions of the invention will depend to a large extent on the type of composition used and the facilities available for its application. Solid compositions may be applied by dusting or any other suitable means for broadcasting or spreading the solid. Liquid compositions may be applied by spraying, atomizing, watering, introduction into the i rigation water, or any other suitable means for broadcasting or spreading the liquid. The rate of application of the compounds of the invention will depend on a number of factors including, for example, the compound chosen for use, the i entity of the plants whose growth is to be inhibited, the formulations selected for use and whether the compound is to be applied for foliage or root uptake. As a general guide, however, an application rate of from 0.005 to 20 kilograms per hectare is suitable while from 0.01 to 5.0 kilograms per hectare may be preferred. The invention is now illustrated by but in no way limited to the following examples. U -_-. « », „ , Example 1. Preparation of Compounds of Formula (6) of the Invention The general method for the preparation of compounds of the invention of formula (6) is exemplified by the detailed description of the preparation of (6.5) and (6.1). Preparation of Methyl 5-0xo-3-methoxybicyclo[4.2.03oct-3-ene-l- 10 carboxylate (6.5) (i ) Preparation of Methyl l-(2-Bromoethy1 )-3,5-dimethoxy-2,5- ,_ cyclohexadiene-1-carboxylate (11.5) by reductive alkylation of methyl i 3,5-dimeth oxybenzoate with 1,3-dibromoethane. To a stirred solution of tertiary butanol (3.22ml, 33.6mmol) and dry tetrahydrofuran (30ml) in anhydrous ammonia (c_ 200ml) under argon and 20 cooled to -78° was added sodium metal (2.00g, 87mg atom). After the sodium dissolved a solution of methyl 3,5-dimethoxybenzoate (6.55g, 33.4mmol) and tertiary butanol (3.22ml) in dry tetrahydrofuran (30ml) was added dropwise over 5 min. The mixture was stirred for 0.5h at -78° (at the 25 end of this time the solution remained deep blue), and then 1,2- dibromoethane (8.63ml, lOOmmol ) was added rapidly via syringe. The reaction mixture was stirred for 0.5h at -78°, and then the ammonia was allowed to evaporate under a stream of argon at room temperature. 30 Ammonium chloride (c_5.0g) was added and the tetrahydrofuran was evaporated in vacuo. Chloroform (100ml) was added and the mixture cooled to 0°. Water (100ml) was added and the organic phase was collected. The mm aqueous layer was extracted with chloroform (100ml). The combined SUBSTITUTE SHEET chlorofor extracts were dried and evaporated to afford crude (11.5) (9.40g, 30.8mmol, 92%) as a colourless solid H n.m.r. δ (CDC1 3 ) 4.63, s, H2 and H6; 3.67, s, C0 2 CH 3 ; 3.58, s, 2 x 0CH 3 ; 3.40-3.10, m, CH 2 Br; 2.72, s, H4, 2.4/2.18, CH 2 . Mass spectrum (Chemical Ionization (C.I): m/z 293 (C 12 H 18 81 Brθ4)) --- Infrared Spectrum Vmax (KBr): 1730(s), 1695(s), 1650(s) cπr . (ii ) Preparation of Methyl l-(2-Bromoethyl )-5-oxo-3-methoxy-3- — cyclohexene-1-carboxylate (5.5) by hydrolysis of (11.5). To a solution of the ester (11.5) (9.40g, 30.8mmol) in methanol (50ml) was added a solution of cone, sulfuric acid (3ml) in methanol (100ml). The mixture was allowed to stand for 10 min and then most of the methanol was evaporated. Chloroform (200ml) was added and the mixture cooled to 0°. The aqueous phase was neutralized by the careful addition of saturated sodium hydrogen carbonate solution. The chloroform layer was collected and the aqueous layer extracted with chloroform (100ml). The combined chloroform extracts were washed with brine (50ml), dried and evaporated to afford a pale yellow oil (8.52g). The oil was subjected to column chroma tography (silica) using light petroleum - chloroform (7:3), then chloroform, then chloroform - methanol (99:1) as eluants to give (5.5) (7.08g, 24.32mmol, 79%) as a colourless gum (Found C, 45.5; H, 5.1; Br, 27.1. requires C, 45.4; H, 5.2; Br, 27.4%). l ti n.m.r. δ (CDC1 3 ) 5.32, s, H4; 3.70, s, 2 x OCH ; 3.30, t, J6Hz, CH 2 Br; 2.94, dd, J17, 1Hz, 1H; 2.88, dd, J17, 1Hz, 1H; 2.48, d, J17 Hz, 1H; 2.32, d, J17Hz, 1H; 2.22, t, J6Hz, CH 2 . _s ii - , _. : (iii) Reaction of (5.5) with lithium diisopropyl amide To a stirred solution of diisopropyl ami ne (0.77ml, 5.49mmol) in dry tetrahydrofuran (10ml) at -78° under argon was added 2.5M n-butyllithium (2.06ml, 5.15mmol). The solution was warmed to 0° for 15 min and then recooled to -78°. A solution of the ester (5.5) (l.OOg, 3.43mmol) in dry tetrahydrofuran (20ml) was added. The reaction mixture was allowed to warm up to room temperature over 2h, and stirred for a further 7h at room temperature. The reaction was quenched by the addition of saturated ammonium chloride solution (20ml) and the mixture extracted with ethyl acetate (3 x 5ϋml). The combined organic extracts were washed with brine (20ml), dried and evaporated. The residue was subjected to radial thin layer chromatography on silica using dichloromethane and then dichloromethane/methanol (99:1) as eluents to afford (6.5) (387mg, 54%) as a colourless liquid (Found C, 62.7; H, 6.9. ^H^O^ requires C, 62.8; H, 6.7%). l n.m.r. (250MHz) δ (CDC1 3 ) 5.51, d, JlHz, H4; 3.73, s, 2 x 0CH 3 ; 3.26-3.14, m, H6; 2.90, dd, J18, 1Hz, 1 of H2; 2.47, d, ϋl8Hz, 1 of H2; 2.67-2.40, m, 2H; 2.20-1.90, m, 2H. 13 C n.m.r. δ (CDCI3) 199.1, C5; 175.8, C3; 175.2, C0 2 CH 3 ; 101.5, C4; 55.8, 0CH 3 ; 52.4, 0CH 3 ; 44.2, Cl; 43.5, C6; 33.4, C2; 29.9, C7; 23.5, C8. Mass spectrum (C.I): m/z 211 (M+l) + . Infrared spectrum ^ aχ (thin film): 1730 (s), 1650 (s), 1615 (s) cm "1 . SUBSTITUT .SHEET Preparation of Methyl 7-Qxo-5-methoxy-l,2,3,4,7,7a-hexahydro-3aH-indene- 3a-carboxyl ate (6.1). (i) Methyl l-(3-Bromopropyl )-3,5-dimethoxy-2,5-cyclohexadiene-l- carboxylate (11.1) was obtained from the reductive alkylation of methyl 3,5-dimethoxybenzoate with 1,3-dibromopropane (J.Am. Chem. Soc, 1986, 108, 5893). (ii) Preparation of Methyl l-(3-Bromopropyl )-5-oxo-3-methoxy-3- cyclohexene-1-carpoxylate (5.1) by hydrolysis of (11.1). Acid hydrolysis of (11.1) gave crude (5.1) as an oil; crystall zation from di ethyl ether/light petroleum afforded pure (5.1) in 71% yield as colourless prisms, m.p. 87-88° (Found C,47.5; H, 5.4; Br, 26.3. C 12 H 17 Br0 4 requires C, 47.2; H, 5.6; Br, 26.2%). 1 H n.m.r. δ (CDC1 3 ) 5.32, s, H4; 3.68, s, 0CH 3 ; 3.66, s, 0CH 3 ; 3.50-3.30, m, CH 2 Br; 2.95, dd, J 2,16Hz, IH; 2.88, dd, J 2,16Hz, IH; 2.43, d, Jlδriz, IH; 2.30, d, J16Hz, IH; 2.00-1.67, m, 2 x CH 2 . Mass spectrum (C.I.): m/z 307 (Cι 2 H 18 81 Br0 4 ), 305 (C 12 H 18 79 Br0 4 ). Infrared spectrum ^ aχ (thin film): 1730 (s), 1655 (s), 1605 (s) cm "1 . (i ) Reaction of (5.1) with lithium diisopropyl ami e To a stirred solution of di i sop ropy! ami ne (1.10 ml, 7.85 mmol) in dry tetrahydrofuran (20 ml) at -78° under argon was added 2.5M n- butyl! ithi urn (2.95 ml, 7.38 mmol). The solution was warmed to 0° for 15 min and then recooled to -78°. A solution of the bromo-ester (5.1) (1.50 g, 4.92 mmol) in tetrahydrofuran (20 ml) was added. The mixture was allowed to warm up to room temperature over 2h, and then quenched by the β lffisπrurE -SHEET addition of saturated ammonium chloride solution (10 ml). Work up as described for the preparation of (6.5) afforded, after crystallization from diethyl ether, the title compound (6.1) (932 mg, 84%) as colourless needles, m.p. 76-78° (Found C, 64.3; H, 7.1. C 12 H 16 0 4 requires C, 64.3; H, 7.2%). l H n.m.r. (250 MHz) δ (CDCI3) 5.30, d, J 1Hz, H6; 3.68, s, 0CH 3 ; 3.67, s, 0CH 3 ; 3.05, t, J 9Hz, H7a; 2.84, d, J 18Hz, 1 of H4; 2.46, dd, J 18, 1 Hz, 1 of H4; 2.25-2.00, m, 2H; 1.95-1.70, m, 4H. 13 C n.m.r. δ (CDC ) 199.3, C7; 175.8, C5; 175.0, CO CH ; 100.4, C6; 55.8, * 0CH 3 ; 53.3, C3a; 52.4, C7a; 52.2, 0CH 3 ; 36.2, C4; 32.9, Cl; 28.9, C3; 22.6, C2. Mass spectrum (C.I.): m/z 225 (M+l) + . Infrared spectrum ^ aχ (thin film): 1730 (s), 1650 (s), 1605 (s)cra '1 . Preparation of Isopropyl 7-0xo-5-methoxy-l,2,3,4,7,7a-hexahydro-3aH- indene-3a-carboxylate (6.2) Reductive alkyl ati on of isopropyl 3,5-dimethoxybenzoate with 1- bromo-3-chloropropane gave isopropyl l-(3-chloropropyl )-3,5-dimethoxy- 2,5-cyclohexadiene-l-carboxylate (11.2) which was hydrolyzed to isopropyl l-(3-chloropropyl )-5-oxo-3-methoxy-3-cyclohexene-l-carboxylate (5.2). Reaction of (5.2) with lithium diisopropyl amide gave (6.2) : H n.m.r. δ (CDCI3) 5.33, broad s, H6; 4.84, septet, J 6Hz, CH_(CH 3 ) 2 ; 3.67, s, 0CH 3 ; 3.20-1.60, m, 9H; 1.17, d, J 6Hz, CH(CH3) 2 . Infrared spectrum \^ aχ (thin film): 1725 (s), 1650 (s), 1615 (s) cm "1 . Preparation of Methyl 7-0xo-5-methoxy-2-methyl-l,2,3,4,5,6,7,7a- hexahydro-3aH-indene-3a-carDoxylate (6.3) Reductive alkyl ati on of methyl 3,5-dimethoxybenzoate with l-bromo-3- chloro-2-methyl propane gave methyl l-(3-chloro-2-methylpropyl )-3,5- ' SUBSTITUTE SHEET dimethoxy-2,5-cyclohexadiene-l-carboxylate (11.3) which was hydrolyzed to methyl l-( 3-chl oro-2-methyl propyl )-5-oxo-3-methoxy-3-cycl ohexene-1- carboxylate (5.3). Reaction of (5.3) with lithium diisopropyl ami e gave (6.3). n.m.r. δ (CDCL3) 5.32, broad s, H6; 3.67, 3.65, 2s, 2 x 0CH 3 ; 3.30-1.60, m, 8H; 1.05, d, J 6Hz, CH3. Preparation of Methyl 7-0xo-5-methoxy-l-methyl-l,2,3,4,7,7a-hexahydro- 3aH-indene-3a-carboxylate (6.4) Reductive alkyl ati on of methyl 3,5-dimethoxybenzoate with l-bromo-3- chlorobutane gave methyl l-( 3-chl orobutyl )-3,5-dimethoxy-2,5- cyclohexadiene-1-carboxylate (11.4) which was hydrolyzed to methyl l-(3- chlorobutyl )-5-oxo-3-meth oxy-3-cyclohexene-l-carbox late (5.4). Reaction of (5.4) with lithium d isopropyl amide gave (6.4). Example 2 The general method for the preparation of compounds of formula (7) of the invention by hydrolysis of compounds of formula (6) is exemplified by the preparation of (7.1). Methyl 5,7 -Di oxo-1 , 2, 3, , 5, 6, 7 , 7 a-octahydro-3aH-i ndene-3a-carboxyl ate (7.1) To a stirred solution of the ester (6.1) (850 mg, 3.79 mmol) in tetrahydrofuran (40 ml) was added 1M hydrochloric acid (6 ml). The mixture was stirred at room temperature for 4h. The tetrahydrofuran was evaporated and ethyl acetate (50 ml) was added to the resi ue. The organic layer was collected, and the aqueous layer extracted further with " "« "- i - ϊ '-J ' t ' U ethyl acetate (50 ml). The combined organic extracts were washed with brine (10 ml), dried and evaporated. The residue was subjected to radial thin layer chromatography on silica using dichloromethane/methanol (98:2) as eluant to afford after crystallization from acetone/di ethyl ether, (7.1) (720 mg, 90%) as a colourless solid, m.p. 110-112° (Found C, 62.9; H, 6.5. 11H14Q4 requires C, 62.8; H, 6.7%). Mass spectrum (C.I.): m/z 211 (M+l) + . Infrared spectrum (KBr): 3440 (broad, w), 2500 (broad, m), 1900 (broad, w), 1730 (s), 1540 (broad s) cm "1 . In a similar manner the following compounds were prepared: Isopropyl 5,7-ύioxo-l,2,3,4,5,6,7,7a-octahydro-3aH-indene-3a-carboxylate (7.2) was obtained as a colourless gum from the hydrolysis of (6.2). l H n.m.r. δ (CDCI3) 8.08, s, OH; 5.41, broad s, H6; 4.96, septet, J 6Hz, qUCH 3 ) 3 ; 3.30-1.60, m, 9H; 1.19, d, J 6Hz, CHtCJ^. Infrared spectrum (thin film): 3650-2400 (broad, m), 1720 (s), 1590 (s) cm "1 . Methyl 5,7-Dioxo-2-methyl-l,2,3,4,5,6,7,7a-octahydro-3aH-indene-3a- carboxylate (7.3) was obtained as a colourless gum from the hydrolysis of (6.3). 1 H n.m.r. δ (CDCI3) 10.08, s, OH; 5.45, d, J 2Jz, H6; 3.68, s, 0CH 3 ; 3.45-1.65, m, 8H; 1.08, d, J 6Hz, CH3. Methyl 5,7-Dioxo-l-methyl-l,2,3,4,5,6,7,7a-octahydro-3aH-indene-3a- carboxylate (7.4) was obtained as a colourless gum from the hydrolysis of (6.4). Methyl 3,5-Dioxobicyclo[4.2.03octane-l-carboxylate (7.5) was obtained from the hydrolysis of (6.5). 1 H n.m.r. δ (CDC1 3 ) 10.28, broad s, OH; SUBSTITUTE SHEET 5.65, s, H4; 3.77, s, 0CH 3 ; 3.52-3.20, m, H5a; 3.00-1.90, m, 6H. Infrared spectrum ^ ax (thin film): 3700-2300 (broad, m), 1730 (s), 1590 (s) cm "1 . Example 3 The general method for the preparation of compounds of formula (8) of the i vention by acylation of compounds of formula (7) is exemplified by the preparation of (8.1). 10 Methyl 6-Butyry 1 -5,7 -di oxo-1 , , 3, , 5, 6, 7 , 7 a-octahydro-3aH-i ndene-3a- carboxylate (8.1) A stirred solution of the ester (7.1) (2.07 g, 9.85 mmol) and 4- 15 dimethyl ami nopyri ine (236 mg, 1.93 mmol) in tri ethyl ami ne (2.75 ml, 19.7 mmol) and butyric anhydride (3.23 ml, 19.7 mmol) was heated under argon at 80° for lh. After this time methanol (2 ml) was added and the mixture 20 heated a further 5 min. The mixture was cooled and dissolved in a mixture of diethyl ether (150 ml) and 3M hydrochloric acid (40 ml). The ether layer was collected and the aqueous phase further extracted with ether (50 ml). The combined ether extracts were washed with brine (40 " ml), dried and evaporated. The excess butyric acid was removed by distillation (2 Torr, pot temperature 80°) and the pot residue was subjected to radial thin layer chromatography on silica using dichloromethane/light petroleum (3:2) to afford (8.1) (1.27 g, 46%) as a 30 pale yellow oil. (Found C, 64.4; H, 7.2. Cι 5 H 20 0 5 requires C, 64.3; H, 7.2%). 1 H n.m.r. (250MHz) (Compound (8.1) is completely enolized in CDC1 3 ; two enol tautomers were observed) 3.68, s, C0 2 CH 3 ; 3.33, t, J 9Hz, H7a (major tautomer, ca 60% of mixture); 3.13, t, J 9Hz, H7a (minor 35 — c.ϊ ι~-~~- tautomer); 3.05-1.70, m, 10H; 1.61, hextet, J 7.5Hz, CH3CH2; 0.93, t, J 7.5Hz, CH_3CH 2 . Mass spectrum (C.I.): m/z 281 (M+l) + . Infrared spectrum \^ aχ (thin film): 1730 (s), 1670 (s) cm '1 . In a similar manner the following compounds were prepared. Isopropyl 6-Butyry1-5,7-dioxo-l,2,3,4, 5,6,7,7a-octahydro-3aH-indene-3a- carboxylate (8.2) was obtained as an oil from the reaction of (7.2) with butyric anhydride. 1 H n.m.r. δ (CDC! 3) 18.17, s, OH; 4.96, septet, J 6Hz, 0CH_(CH 3 ) 2 ; 3.45-1.40, m, 13H; 1.18, d, J 6Hz, CW{Z\Y-) 2 ; 0.95, t, J 7Hz, CH3. Infrared spectrum jnaχ (thin film): 1725 (s), 1665 (s) cm "1 . Methyl 6-Butyryl-5,7-dioxo-2-methyl-l,2,3,4,5,6,7,7a-octahydro-3aH- i ndene-3a-carboxyl ate (8.3) was obtained as an oil from the reaction of (7.3) with butyric anhydride. l H n.m.r. δ (CDCI3) 18.05, s, OH; 3.67, s, 0CH 3 ; 3.62-1.38, m, 12H; 1.18-0.85, m, 2 x CH3. Infrared spectrum ^ ax (thin film): 1730 (s), 1665 (s) cm "1 . Methyl 5,7-Dioxo-6-propionyl-l,2,3,4,5,6,7,7a-octahydro-3aH-indene-3a- carboxylate (8.4) was obtained as an oil from the reaction of (7.1) with 1 propanoic anhydride. Hi n.m.r. δ (C1DCI3) 18.06, s, OH; 3.65, s, 0CH 3 ; 3.50-1.60, m, 11H; 1.11, t, J 7Hz, CH3. Infrared spectrum ^ aχ (thin film) 1730 (s), 1660 (s) cm '1 . Methyl 6-Butyryl-5,7-dioxo-l-methyl-l,2,3,4,5,6,7,7a-octahydro-3aH- indene-3a-carboxylate (8.5) was obtained as an oil from the reaction of (7.4) with butyric anhydride. l H n.m.r. δ (CDC1 3 ) 18.17, s, OH; 3.65, s, 0CH 3 ; 3.50-1.35, m, 12H; 1.35-0.80, m, 2 x CH3. c ~ ~ ~~~ —-—- • — • - ------ Methyl 4-Butyryl-3,5-dioxobicyc1o[4.2.03octane-l-carboxylate (8.6) was obtained as an oil from the reaction of (7.5) with butyric anhydride 1 H n.m.r. s (00013) 18.0 and 17.8, 2s, 2 x OH (two enol tautomers were observed); 3.77, s, 0CH 3 ; 3.70-1.40, m, 11H; 1.00, t, J 7Hz, CH3. Infrared spectrum tø aχ (thin film) 1730 (s), 1665 (s) cm "1 . Example 4 The general method for the preparation of compounds of formula (1) of the invention by reaction of compounds of formula (8) with hydroxyl ami ne derivatives is exemplified by the preparation of (1.1). Methyl 5,7-Dioxo-6-(l-(2-propenyl)oxyimino)butyl-l,2,3,4,5,6,7,7a- octahydro-3aH-i ndene-3a-carboxyl ate (1.1) A solution of (8.1) (391 mg, 1.40 mmol) and __-{2- propenyl ) hydroxyl am ne hydrochloride (347 mg, 2.80 mmol) in ethanol (20 ml) and pyridine (3 ml) was stirred at room temperature for 2 days. The solvents were evaporated and di ethyl ether (100 ml) was added to the residue followed by 1M hydrochloric acid (10 ml). The ether layer was collected, washed with brine (20 ml) and dried. The ether extract was ~ ~ evaporated and the residue subjected to radial thin layer chromatography using dichloromethane as the eluant to afford (1.1) (324 mg, 69%) as a pale yellow oil (Found C, 64.6; H, 7.3; N, 4.3. Cι 8 H 25 0 5 requires C, 64.5; H, 7.5; N, 4.2%). 1 H n.m.r. δ (CDC ) 13.3, broad s, OH; 6.20- 0 J 5.70, m, IH; 5.50-5.18, m, 2H; 4.50, d, J 6Hz, C=N0CH 2 ; 3.66, s, 0CH 3 ; 3.38-3.12, , H7a; 3.03-2.78, m, CH 2 C= 0; 2.88, 2.50, ABq, J 17 Hz, H4; 2.50-1.30, m, 8H 0.93, t, J 6Hz, CH 3 . Mass spectrum (C.I.): m/z 336 (M+l) + . ^ ax (thin film): 2600 (broad, w), 1730 (s), 1655 (s), 1600 (s) cm " . In a similar manner the following compounds were prepared: Methyl 5,7-Dioxo-6-(l-ethoxyimino)butyl-l,2,3,4,5,6,7,7a-octahydro-3aH- indene-3a-carboxyl te (1.2) was obtained from the reaction of (8.1) with 0-ethyl hydroxyl ami ne. HCl.iH n.m.r. δ (CDCI3) 14.8, broad s, OH; 4.10, q, " " 6Hz, 0CH 2 CH 3 ; 3.66, s, 0CH 3 ; 3.45-3.05, m, H7a; 3.05-1.30, m, 12H; 1.32, t, J 6riz, 0CH 2 CH 3 ; 0.95, t, J 6Hz, CH3. Mass spectrum (C.I.): m/z 324 (M+l) + . (thin film): 1730 (s), 1660 (s), 1600 (s) cm "1 . Methyl 5,7-Dioxo-6-(l-(2-(3-ch1oro)propeny1 )oxyimino)butyl- l,2,3,4,5,6,7,7a-octahydro-3aH-indene-3a-carboxylate (1.3) was obtained from the reaction of (8.1) with _-( 2-( 3-chl o o ) propenyl ) hydroxyl ami ne hydrochloride. l n.m.r. δ (CDCL3) 11.4, very broad s, OH; 6.43-5.84, m, 2H; 4.75 and 4.50, 2d, J 6Hz, (E and Z isomers are present); 3.67, s, 0CH ; 3.45-3.05, m, H7a; 3.00-1.25, m, 12H; 0.92, t, J 7Hz, CH3. Methyl 5,7-Dioxo-6-(l-(2-propyny1 )oxyimino)butyl-l,2,3,4,5,6,7,7a- octahydro-3aH-indene-3a-carboxylate (1.4) was obtained as a yellow oil from the reaction of (8.1) with 0_-(2-proρynyl ) hydroxyl ami ne hydrochloride. 1 H n.m.r. δ (CDCI3) 12.2, very broad s, OH; 4.60, d, J 2Hz, 2H; 3.67, s, 0CH 3 ; 3.25, broad t, J 8Hz, H7a; 3.00-1.30, m, 13H; 0.91, t, J 8Hz, CH 3 . w * -' •' I ik < fc ~ ;.. J Isopropyl 5,7-Dioxo-6-(l-(2-propenyl )oxyimino)butyl-l,2,3,4,5,6,7,7a- octahydro-3aH-indene-3a-carboxyl te (1.5) was obtained as a yellow oil from the reaction of (8.2) with _0_-(2-propenyl ) hydroxyl ami ne hydrochloride. 1 H n.m.r. δ (CDC1 3 ) 14.3, very broad s, OH; 6.20-5.75, m, IH; 5.44-5.16, m, 2H; 4.97, heptet, J 6Hz, CH_(CH 3 ) 2 ; 4.50, d, J 6Hz, OCH^CH^Hg; 3.37-3.13, m, H7a; 3.00-1.37, , 12H; 1.18, d, J 7Hz, CH(Cl3) 2 ; 0.92, d, J 7Hz, CH3. Infrared spectrum ^ aχ (thin film): 1720 (s), 1655 (s), 1600 (s) cm -1 0 Methyl 5,7-Dioxo-6-(l-ethoxyimino)butyl-2-methyl-l,2,3,4,5,6,7,7a- octahydro-3aH-indene-3a-carboxylate (1.6) was obtained as a yellow oil i ιr o. from the reaction of (8.3) with — 0-ethyl ydroxyl ami ne hydrochloride. H n.m.r. δ (CDC1 3 ) 14.0, very broad s, OH; 4.08, q, J 7Hz, OCH2CH3; 3.66, s, 0CH 3 ; 3.34, m, H7a; 3.10-1.43, m, 11H; 1.30, t, J7Hz, OCHgCH^; 1.13- 0.80, m, 2 x CH 3 . Infrared spectrum (thin film): 1730 (s), 1660 20 (s), 1605 (s) cm "1 . Methyl 5,7-Dioxo-6-(l-(2-propenyl ) oxyimi no) butyl -2-methyl - l,2,3,4,5,6,7,7a-octahydro-3aH-indene-3a-carboxylate (1.7) was obtained 25 as a yellow oil from the reaction of (8.3) with j)_-(2- propenyl) hydroxyl ami ne hydrochloride. 1 H n.m.r. δ (CDCL3) 14.8, broad s, OH; 6.24-5.68, m, IH; 5.45-5.16, , 2H; 4.50, d, J 5Hz, 3.63, s, OCH ; 3.47-3.15, m, H7a; 3.10-1.23, m, 11H; 1.20-0.75, m, 2 x CH . 30 Infrared spectrum ^ ax (thin film): 1730 (s), 1660 (s), 1600 (s) cm " 1 1 . SUBSTITUTE SHEET Methyl 5,7-Dioxo-6-( l-(2-propeny1 )oxyimino)propy1-l,2,3,4,5,6,7,7a- octahydro-3aH-indene-3a-carboxy1ate (1.8) was obtained as an oil from the reaction of (8.4) with _p_-(2-propenyl ) hydroxyl ami ne hydrochloride. 1 H n.m.r. δ (CDC1 3 ) 12.8, broad s, OH; 6.20-5.70, m, IH; 5.47-5.13, m, 2H; 4.51, d, J6Hz, 3.63, s, 0CH 3 ; 3.40-3.07, m, H7a; 3.04-1.50, , 10H; 1.10, t, J 7Hz, CH3. Infrared spectrum ^ aχ (thin film): 1730 (s), 1660 (s), 1600 (s) cm "1 . Methyl 5,7-ϋioxo-6-(l-(2-proρenyl )oxyimino)bυtyl-l-methy1- l,2,3,4,5,6,7,7a-octahydro-3aH-idene-3a-carboxylate (1.9) was obtained as an oil from the reaction of (8.5) with ϋ_-(2-proρenyl ) hydroxyl ami ne hydrochloride. l n.m.r. δ (CDC1 3 ) 14.30, broad s, OH; 6.18-5.70, m, IH, 5.45-5.05, m, 2H; 4.45, d, J 6Hz, CH^CH^; 3.61, s, 0CH 3 ; 3.45-1.14, m, 12H; 0.97, t, J 7Hz, CH 3 ; 0.90, t, J 7Hz, CH3. Infrared spectrum ^ aχ (thin film): 1730 (s), 1660 (s), 1600 (s) cm "1 . Methyl 3,5-Dioxo-4-(l-(2-propenyl ) oxyimi no) butyl bicyclo[4. .0. ]octane-l- carboxylate (1.10) was obtained as an oil from the reaction of (8.6) with _0-(2-propenyl ) hydroxyl ami ne hydrochloride. H n.m.r. δ (CUCI3) 6.05- 5.85, m, IH; 5.40-5.20, m, 2H; 4.52, d, J 6Hz, 3.73, s, 0CH 3 ; 3.45-3.35, , IH; 2.95-2.30, , 6H; 2.15-1.95, m, 2H; 1.65-1.50, m, 2H; 0.97, t, J 7Hz, CH3. } ™ & T -3i ~ ~ Exa ple 5 The post-emergence herbicidal activities of the compounds (1.1-1.10) of the invention were assessed by the following procedure. Seeds of the following weed species were planted in both post and preemergence tests: Common Name Code Species crabgrass CRB Digitaria sanguinalis giant foxtail GFX Setaria faberi barnyardgrass BYG Echinochloa crus-galli wild oats IO Avena fatua cheatgrass CHT Bromus secalinus Seeds of the following crop species were planted in both pre and post emergence tests: wheat WHT Triticum aestivum corn CRN Zea mays barley BAR Hordeum vulgare soybean SBN Glycine max rice RCE Oryza sativa grain sorghum S0R Sorghum bicolor sugarbeet SBT Beta vulgaris cotton COT Gossypium hi sutum ! C .Ϊ:7. Ϊ ; P "Ϊ" S: Postemergence Procedure The species listed above were planted in Sassafras sandy loam soil (pH 6.5 and 1.0% organic matter) and sprayed postemergence with the rates given in Table 3 with the test sample dissolved in a nonphytotoxic solvent. Plants were grown 8-12 days prior to treatment. Treated and control plants were maintained in the greenhouse for 14 to 16 days before ratings were taken. Numerical Response Ratings All treated plants were compared to controls and visually rated for response to chemical treatment. Response ratings are based on a scale of 0 to 10, where 0 = no effect and 10 = complete control. The results are shown for compounds (1.1-1.10) in Table 2. 8U_ _&mBTE:SH t c~ o. Table 2. Post-emergence Herbicidal Activity of Compounds (1.1-1.10) - o ^ . ∞ < Compound Rate CRB GFX BYG WIO CHT WHT CRN BAR SBN RCE kg/ha (1.1) 0.4 9 9 10 9 6 0 9 5 0 9 0.1 7 7 9 8 0 0 8 0 0 8 (1.2) 0.4 9 9 10 9 9 0 8 5 0 9 7 0.1 4 6 9 3 0 0 2 0 0 7 0 I (1.3) 0.4 6 6 9 3 0 0 5 0 0 4 m 0 I 0.1 2 0 9 0 0 0 0 0 0 0 0 (1.4) 0.4 9 9 9 9 0 0 7 3 0 7 7 0.1 3 2 9 2 0 0 0 0 0 0 0 (1.5) 0.4 3 4 9 6 0 0 8 0 0 0 1 0.1 0 0 6 0 0 0 5 0 0 0 0 (1.6) 0.4 8 9 10 7 7 0 9 7 0 9 9 o 0.1 6 7 10 2 0 0 5 2 0 6 9 Ox I m r. β o σ. 00 < Dm Table 2 continued. Compound Rate CRB GFX BYG WIO CHT WHT CRN BAR SBN RCE SOR SBT COT kg/ha (1.7) 0.4 9 9 10 9 2 1 9 7 0 9 10 0 0 1 0.1 7 8 9 3 0 0 9 0 0 5 - 0 0 ro (1.8) 0.4 9 9 10 6 0 1 9 6 0 8 10 0 0 0.1 6 7 8 0 0 0 5 0 0 3 - 0 0 (1.9) (1.10) 0.4 7 6 9 0 0 3 8 4 0 9 7 0 0 0.1 0 0 7 0 0 0 0 0 0 0 0 0 0 Ti¬ es a- ∞ Example 6 The pre-emergence herbicidal activities of the compounds of the invention were assessed by the following procedure. The test species used are as described in Example 5. Pre-emergence Procedure The species listed above were planted in Sassafras sandy loam soil (pH 6.5 with 1.0% organic matter) and treated at rates given in Table 3 with the test chemical dissolved in a nonphytotoxfc solvent. Plants were grown in the green house for 14 to 16 days before ratings were taken. Numerical Response Ratings All treated plants were compared to controls and visually rated for response to chemical treatment. Response ratings are based on a scale of 0 to 10, where 0 = no effect and 10 = complete control. The results are shown for the compounds (1.1-1.10) in Table 3. r. r. o © 00 P Table 3. Pre-emergence Herbicidal Activity of Compounds (1.1-1.10) < Compound Rate CRB GFX BYG WIO CHT WHT CRN BAR SBN RCE SOR SBT COT kg/ha (1.1) 0.4 9 9 3 3 0 2 8 3 0 8 5 0 0 0.1 3 2 0 0 0 0 5 0 0 0 2 0 0 I σ> (1.2) 0.4 0 5 9 3 4 0 5 6 0 4 5 0 0 ro I 0.1 0 3 3 0 0 0 0 0 0 0 0 0 0 (1.3) 0.4 7 6 6 0 0 0 0 0 0 5 0 0 0 0.1 0 0 0 0 0 0 0 0 0 0 0 0 0 (1.4) 0.4 9 5 9 0 0 0 0 3 0 2 3 0 0 0.1 0 0 0 0 0 0 0 0 0 0 0 0 0 (1.5) 0.4 0 0 0 0 0 0 0 0 0 0 0 0 0 0.1 0 0 0 0 0 0 0 0 0 0 0 0 0 T © r. oo (1.6) 0.4 7 2 10 0 8 0 3 0 0 7 6 0 0 O 0.1 3 2 5 6 3 0 0 0 0 0 0 0 0 kg/ha (1.7) 0.4 2 3 8 5 0 0 6 0 0 2 3 0 0 0.1 0 0 2 0 0 0 0 0 0 0 0 0 0 o (1.8) 0.4 3 3 3 5 0 0 3 1 0 3 5 0 0 I 0.1 0 0 0 0 0 0 0 0 0 0 0 0 0 (1.9) (1.10) 0.4 0 0 3 0 0 0 0 0 0 0 0 0 0 0.1 0 0 0 0 0 0 0 0 0 0 0 0 0 f o oo I Exa ple 6 Compounds (12.1-12.4) (Table 4) which fall within a structural class claimed as herbicides by Great Britain Patents 1 455200 and 1 461 170 have been prepared and tested for herbicide activity exactly as described in Examples 4 and 5. The post- and pre-emergence herbicide activity of these compounds is shown in Tables 5 and 6. Table 4 Compound 0 12.1 ethyl 12.2 allyl 12.3 CH 2 CH=CHC1 12.4 propargyl 5 0 -WBSTΠ Π:E - i-»LS*-*<^£_&S'^_?%jg, t~) r o. * o». o 00- Table 5 D Post-emergence Herbicidal Activity of Compounds (12.1-12.4) e p. Compound Rate CRB GFX BYG WIO CHT WHT CRN BAR SBN RCE SOR SBT COT kg/ha 12.1 0.4 8 8 6 0 0 3 9 0 0 9 5 0 0 0.1 2 5 2 0 0 0 3 0 0 2 0 0 0 12.2 0.4 9 9 7 0 0 0 9 0 0 8 7 6 0 0.1 0 6 6 0 0 0 3 0 0 1 0 0 0 12.3 0.4 7 8 10 0 3 0 9 0 0 9 4 0 0 0.1 5 4 9 0 0 0 5 0 0 2 0 0 0 12.4 0.4 7 8 9 0 0 0 5 0 0 2 0 4 0 0.1 2 0 0 0 0 0 0 0 0 0 0 0 0 © oo r- ~ © © g Table 6. Pre-emergence Herbicidal Activity of Compounds (12.1-12.4) < Compound Rate CRB GFX BYG WIO CHT WHT CRN BAR SBN RCE SOR SBT COT kg/ha 12.1 o.4 - - - - - - - - - - - - - 0.1 0 2 0 0 0 0 0 0 0 0 0 0 0 12.2 0.4 0 5 2 0 0 0 0 0 0 2 0 0 0 ro 0.1 0 0 0 0 0 0 0 0 0 0 0 0 0 12.3 0.4 0 6 4 0 0 0 0 0 0 0 0 0 0 0.1 0 4 2 0 0 0 0 0 0 0 0 0 0 12.4 0.4 0 6 2 0 0 0 0 0 0 0 0 0 0 0.1 0 0 0 0 0 0 0 0 0 0 . 0 0 0 rt © oo Comparison of post-emergence herbicide activity of (12.1-12.4) with the lower homologues (1.1-1.4) which are claimed in this patent application shows that, in general, compounds (12.1-12.4) are less active. Furthermore, unlike compounds (1.1-1.4), compounds (12.1- 12.4) show _no_ selectivity towards wild oats in wheat and barley.

Claims: CLAIMS A compound of formula (la) , " (lb) or (lc) or an isomeric or tautomeric form thereof: characterised in that 0 R 2 0N II W is hydrogen or one of the groups R - ■ Cc-- and R 3 J -C n- ; R 1 is selected from the group consisting of: hydrogen, alkyl; alkenyl; alkynyl; cycloalkyi; cycloalkenyl; substituted alkyl or substituted cycloalkyi wherein the alkyl or cycloalkyi group is substituted with a substituent selected from the group consisting of alkyoxy, alkylthio, optionally substituted phenyl, optionally substituted heterocycle; optionally substituted phenyl; optionally substituted heterocycle; alkyl sulphonyl; optionally substituted benzene sulphonyl; an acyl group; and an inorganic or organic cation; R 2 is selected from the group consisting of: alkyl; alkenyl; haloalkenyl; alkynyl; and haloalkynyl; R 3 is selected from the group consisting of : alkyl; alkenyl; alkynyl; and optionally substituted phenyl; n is 1, 2 , 3 , 4 or 5 ; R and R" are each selected independently from the group consisting of: hydrogen; alkyl; alkenyl; alkynyl; haloalkyl; haloalkenyl; cycloalkyi; cycloalkenyl; substituted alkyl or substituted cycloalkyi wherein the alkyl or cycloalkyi group is substituted with a substituent selected from the group consisting of alkoxy, alkylthio, oxo, acyl, alkoxycarbonyl, ketal, optionally substituted phenyl, and optionally substituted heterocycle; optionally substituted phenyl; and optionally substituted heterocycle; with the proviso that when n is 4 then not all of the eight substituents R and R" are hydrogen; R A is selected from the group consisting of: alkyl; alkenyl; alkynyl; substituted alkyl wherein the alkyl group is substituted with a substituent selected from the group consisting of alkoxy, alkylthio, optionally substituted phenyl, and optionally substituted heterocycle; optionally substituted phenyl; and optionally substituted heterocycle; 2. A compound of formula (1) or an isomeric or tautomeric form thereof: - 47 - wherein R 1 , R 2 , R 3 , R 4 , R, R" and n are as defined in Claim 1. 3 - A compound of Formula (lb) or an isomeric or tautomeric form thereof. wherein R 1 , R , R J , R , R, R" and n are as defined in Claim 1, 4. A compound as claimed in any one of Claims 1 to 3 , characterised in that any heterocylic ring contains more than three atoms. 5. A compound as claimed in Claim 4 characterised in that the heterocyclic ring is selected from the group consisting of thiophenyl, benzofuranyl, furanyl, morpholino, and pyridyl. 6. A compound as claimed in any one of Claims 1 to 5, characterised in that any alkyl, alkoxy, alkylthio, haloalkyl, alkyl sulphonyl or substituted alkyl groups contain from 1 to 6 carbon atoms and any alkenyl, haloalkenyl, or haloalkynyl groups contain from 2 to 6 carbon atoms. 7. A compound as claimed in any one of Claims 1 to 6, characterised in that R 1 is hydrogen or an alkali metal cation. 8. A compound as claimed in any one of Claims 1 to 7, characterised in that R 2 is alkyl, alkenyl or haloalkenyl. 9. A compound as claimed in Claim 8, characterised in that R 2 is ethyl, allyl or 2- or 3-chlorallyl. 10. A compound as claimed in any one of Claims 1 to 9, characterised in that R 3 is ethyl, or n-propyl. 11. A compound as claimed in any one of Claims 1 to 10, characterised in that n is 3. 12. A compound as claimed in Claim 1, selected from the group consisting of: methyl 5-oxo-3-methoxybicyclo[4.2.0]oct-3-ene-l- carboxylate; methyl 7-oxo-5-methoxy-1,2,3,4,7,7a-hexahydro-3aH-indene- 3a-carboxylate; isopropyl 7-oxo-5-methoxy-1,2,3,4,7,7a-hexahydro-3aH- indene-3a-carboxylate; methyl 7-oxo-5-methoxy-2-methyl-l,2,3,4,7,7a-hexahydro- 3aH-indene-3a-carboxylate; and methyl 7-oxo-5-methoxy-l-methyl-l,2,3,4,7,7a-hexahydro- 3aH-indene-3a-carboxylate. 13. A compound as claimed in Claim 1, selected from the group consisting of: methyl 5,7-dioxo-l,2,3,4,5,6,7,7a-octahydro-3aH-indene-3a- carboxylate; isopropyl 5,7-dioxo-l,2,3,4,5,6,7,7a-octahydro-3aH-indene- 3a-carboxylate; methyl 5,7-dioxo-2-methyl-l,2,3,4,5,6,7,7a-octahydro-3aH- indene-3a-carboxylate; methyl 5,7-dioxo-l-methyl-l,2,3,4,5,6,7,7a-octahydro-3aH- indene-3a-carboxylate; and methyl 3,5-dioxobicyclo[4.2.0]octane-1-carboxylate. 14. A compound as claimed in Claim 1, selected from the group consisting of: methyl 6-butyryl-5,7-dioxo-1,2,3,4,5,6,7,7a-octahydro-3aH- indene-3a-carboxylate; isopropyl 6-butyryl-5,7-dioxo-1,2,3,4,5,6,7,7a-octahydro- 3aH-indene-3a-carboxylate; methyl 6~butyryl-5,7-dioxo-2-methyl-l,2,3,4,5,6,7,7a- octahydro-3aH-indene-3a-carboxylate; methyl 5,7-dioxo-6-propionyl-1,2,3,4,5,6,7,7a-octahydro- 3aH-indene-3a-carboxylate; methyl 6-butyryl-5,7-dioxo-l-methyl-l,2,3,4,5,6,7,7a- octahydro-3aH-indene-3a-carboxylate; and methyl 4-butyryl-3,5-dioxobicyclo[4.2.0]octane-1- carboxylate. 15. A compound as claimed in Claim 1, selected from the group consisting of: methyl 5,7-dioxo-6-(1-(2-propenyl)oxyimino)butyl- 1,2,3,4,5,6,7,7a-octahydro-3aH-indene-3a-carboxylate; methyl 5,7-dioxo-6-(l-ethoxyimino)butyl-l,2,3,4,5,6,7, 7a- octahydro-3aH-indene-3a-carboxylate; methyl 5,7-dioxo-6-(1-(2-(3-chloro)propenyl)oxyimino)- butyl-1,2,3,4,5,6,7,7a-octahydro-3aH-indene-3a- carboxylate; methyl 5,7-dioxo-6-(1-(2-propynyl)oxyimino)butyl- 1,2,3,4,5,6,7,7a-octahydro-3aH-indene-3a-carboxylate; isopropyl 5,7-dioxo-6-(1-(2-propenyl)oxyimino)butyl- 1,2,3,4,5,6,7,7a-octahydro-3aH-indene-3a-carboxylate; methyl 5,7-dioxo-6-(1-ethoxyimino)butyl-2-methy1- 1,2,3,4,5,6,7,7a-octahydro-3aH-indene-3a-carboxylate; methyl 5,7-dioxo-6-(1-(2-propenyl)oxyimino)butyl-2-methyl- 1,2,3,4,5,6,7,7a-octahydro-3aH-indene-3a-carboxylate; methyl 5,7-dioxo-6-(1-(2-propenyl)oxyimino)propyl- 1,2,3,4,5,6,7,7a-octahydro-3aH-indene-3a-carboxylate; methyl 5,7-dioxo-6-(1-(2-propenyl)oxyimino)butyl-l-methyl- 1,2,3,4,5,6,7,7a-octahydro-3aH-indene-3a-carboxylate; and me hyl 3,5-dioxo-4-(1-(2-propenyl)oxyimino)butyl- bicyclo[4.2.0]octane-1-carboxylate. 16. A method for preparing a compound of Formula (1) or (lb) as stated in Claim 2 or Claim 3 respectively, characterised in that a compound of Formula (8) wherein R , R 4 , R, R ,r and n are as stated in Claim 1, is reacted with an 0-substituted hydroxylamine of the formula R 2 0NH 2 wherein R 2 is as stated in Claim 1, thereby to produce a compound of formula (1) or (lb) wherein R 1 is hydrogen; and thereafter, if desired, the thus obtained compound is converted to a compound of formula (1) and/or (lb) , wherein R 1 is other than hydrogen by standard and appropriate synthetic procedure. 17. A method for preparing a compound of formula (8), as stated in Claim 16, characterised in that a compound of Formula (7) wherein R*, R, R" and n are as defined in Claim 1, is 0- acylated with an acyl group of the formula R 3 C0- and isomerized by the Fries rearrangement. 18. A method for preparing a compound of Formula (7) as stated in Claim 17, characterised in that a compound of Formula (6) wherein R A , R, R" and n are as defined in Claim 1 and Alk is a lower alkyl group, is treated with aqueous acid. 19. A method for preparing a compound of Formula (6) as stated in Claim 18, characterised in that a compound of Formula (5) is reacted with lithium disopropylamide. 20. A method for preparing a compound of Formula (5) as stated in Claim 19, characterised in that a 3,5-dialkoxybenzoic acid is reduced with an alkali metal in liquid ammonia followed by addition of an appropriate electrophile to give a 1-substituted 3,5-dimethoxy-2,5-cyclohexadiene-l-carboxylic acid derivative of Formula (4) and the compound of Formula (4) is esterified to give the required compound of Formula (5) . 21. A method for preparing a compound of Formula (5) as stated in Claim 19, characterised in that an alkyl 3,5-dialkoxybenzoic acid is reduced with an alkali metal in liquid ammonia followed by addition of an appropriate electrophile, then acid hydrolysis, to give the required compound of Formula (5) . 22. A plant growth inhibiting, plant damaging or plant killing composition comprising a compound of Formula (1) or (b) as defined in Claim 2 or Claim 3, and an inert carrier therefor. 23. A method for regulating the growth of a plant which process comprises applying to the plant, to the seed of the plant, or to the growth medium of the plant, an effective amount of a compound of Formula (1) or (la) as defined in Claim 2 or Claim 3.

Inventors: LIEPA ANDRIS JURIS, WINZENBERG KEVIN NORMAN, LIEPA, ANDRIS, JURIS, WINZENBERG, KEVIN, NORMAN
Applicants: DUNLENA PTY LTD, DUNLENA PTY. LIMITED
Application year: 1989
Main classification: C07C69
IPC codes: A01N37, C07C251