HERBICIDAL PYRONES

Abstract: Compounds of the general formula (2) and isomeric and/or tautomeric forms thereof, characterized in that R<1> is hydrogen, optionally substituted alkyl, alkenyl, alkynyl, optionally substituted cycloalkyl, cycloalkenyl, optionally substituted phenyl, optionally substituted heterocycle, alkyl sulphony, optionally substituted benzene sulphonyl, an acyl group, or a cation; R<2> is optionally substituted alkyl, alkenyl, optionally substituted cycloalkyl, cycloalkenyl, haloalkenyl, alkynyl, haloalkynyl, optionally substituted phenyl, or optionally substituted heterocycle; R<3> is alkyl, haloalkyl, alkenyl, cycloalkyl, cycloalkenyl, alkynyl, or optionally substituted phenyl; R<4> is alkynyl, haloalkenyl, optionally substituted cycloalkyl, cycloalkenyl, substituted alkyl or optionally substituted heterocycle; R<5> is optionally substituted alkyl, alkenyl, alkynyl haloalkenyl, optionally substituted cycloalkyl, cycloalkenyl or optionally substituted heterocycle; or R<4> and R<5> together with the carbon to which they are attached form a optionally substituted heterocyclic or carbocyclic ring. Intermediates for the production of (2) are also disclosed. The compounds of formula (2) have herbicidal and plant growth regulating properties.

Description: "HERBICIDAL PYRONES" This invention relates to organic compounds having herbicidal properties and plant growth regulating properties, to processes for the preparation of such compounds; to intermediates useful in the preparation of such compounds; to herbicidal compositions and processes utilizing such compounds and to plant growth regulating compositions and processes utilizing such compounds. The use of certain cyclohexane-1 ,3-dione derivatives as grass herbicides is known in the art. Thus, for example, the compendium "Agricultural Chemicals - Book II Herbicides 1986- 87 Revision" ( .T. Thomson Editor, Thomson Publications, SUBSTITUTE SHEET California U.S.A.) describes the cyclohexane-I ,3-dione derivatives known commercially as Alloxydim Sodium (methyl-3- [ l-(allyloxyimlno)butyl]-4-hydroxy-6 ,6-dimethyl-2- oxocyclohex-3-ene carboxylate), Cloproxydim ((E,E)-2 [ l-[ 1- [(3-chloro-2-proρenyl)oxy]iminoJbutyl]-5-[2- (ethylthio)propyl]-3-hydroxy-2-cyclohexen-l-one) , Cycloxydim (2-[ L-ethoxyimino)butyl]-3-hydroxy-5-[2jl-tetrahydrothiopyran- 3-ylJ-2-cyclohexen-i-one and Sethoxydim (2-[l- '" ' ( ' eτhoxyi-__ino)butyl]-5-I2-ethylthio] propyl-3-hydroxy-2- cyclohexen-1-one) as selective post-emergent herbicides. Alloxydim and Sethoxydim have been disclosed in Australian Patent No. 464 655 and Australian Patent Application No. 35,314/78 respectively. Pyrones of the general Formula (I) have been claimed to show herbicidal activity (Japan Kokai 76 63175 (Chemical Abstracts , 86:72439y)). We have discovered that compounds similar to the general Formula (1) but which bear substituents at the 6-position other than hydrogen or geminal dimethyl exhibit particularly useful herbicidal activity, with special selectivity for weed grasses in crops, and plant growth regulating activity. Accordingly, the invention provides a compound of the general Formula (2 ) (2) wherein R is selected from the group consisting of: hydrogen; alkyl; alkenyl; alkynyl; cycloalkyl; cycloalkenyl substituted alkyl or substituted cycloalkyl wherein the alkyl or cycloalkyl group is substituted with a substituent selected from the group consisting of alkoxy, alkylthio, optionally substituted phenyl, optionally substituted heterocycle; optionally substituted phenyl; optionally substituted heterocycle; alkyl sulfonyl; optionally substituted benzene sulfonyl; an acyl group; and an inorganic or organic cation; FT is selected from the group consisting of: alkyl; alkenyl; cycloalkyl; cycloalkenyl; haloalkenyl; alkynyl; haloalkynyl; substituted alkyl or substituted cycloalkyl ' -> wherein the alkyl or cycloalkyl group is substituted with a substituent selected from the group consisting of halogen, alkoxy, alkylthio, optionally substituted phenyl, and optionally substituted heterocycle; optionally substituted phenyl; and optionally substituted heterocycle; 3 R is selected from the group consisting of: alkyl; haloalkyl; alkenyl; cycloalkyl; cycloalkenyl; alkynyl; and optionally substituted phenyl; R is selected from the group consisting of: alkynyl; haloalkyl; haloalkenyl; cycloalkyl; cycloalkenyl; substituted alkyl or substituted cycloalkyl wherein the alkyl or cycloalkyl group is substituted with a substituent selected froβ the group consisting of alkoxy, alkylthio, oxo, acyl, alkoxycarbonyl, (alkoxyiaino)alkyl, ketal, carboxyllc acid, optionally" , substituted phenyl, and optionally substituted heterocycle; 5 and optionally substituted heterocycle; R is selected from the group consisting of: alkyl; alkenyl; alkynyl; haloalkyl; haloalkenyl; cycloalkyl; cycloalkenyl; substituted alkyl or substituted cycloalkyl iu wherein the alkyl or cycloalkyl group is substituted with a substituent selected from the group consisting of alkoxy, alkylthio, oxo, acyl, alkoxycarbonyl, (alkoxyimino) lkyl, ketal, carboxyllc acid, optionally substituted phenyl, and optionally substituted heterocycle; and optionally substituted 5 hererocycle; OR 4 5 R and R together with the carbon to which they are attached form a substituted or unsubstituted saturated or partially saturated heterocyclic or carbocyclic ring 0 containing 3 or more ring atoms * The ring may be bridged or fused and the ring βubstltuents are selected from the group consisting of hydrogen; alkyl; alkenyl; alkynyl; substituted alkyl wherein the alkyl group is substituted with a substituent selected froø the group consisting of alkoxy, alkylthio, optionally substituted phenyl, *nd optionally -6- substituted heterocycle; optionally substituted phenyl; and optionally substituted heterocycle; oxo; acyl; alkoxy; alkylthio; alkoxycarbonyl; (alkoxyimino)alkyl; ketal; and carboxyllc acid. Compounds of Formula (2 ) within the general scope of the invention include: 6-cycloproρyl-3-[l-(ethoxyimino)butyl]-4-hydroxy-6 , -methyl- 5,6-dIhydro-2H-pyr n-2-on ; 3-[l-(ethoxyimino)butyl]-4-hydroxy-6-methyl-6-(2-thienyl)- 5,6-dihydro-2jI-pyran-2-one; 3-[l-(ethoxyimino)butyl]-4-hydroxy-7-π_ethyl-l- oxaspiro[5.5]undec-3-en-2-one; 3-[1-ethoxyimino)butyl]-4-hydroxy-8-methyl-l- oxaspiro[5.5]undec-3-en-2-one; 8,10-diπ.ethyl-3-[l-(ethoxyimino)butyl]-4-hydroxy-l- oxaspiro[5.5]-undec-3-en-2-one; 3-[l-(ethoxyimino)butyl)-9-ethyl-4-hydroxy-l- oxas piro [ 5.5 ] undec-3 -en-2 -one ; 9-tert-butyl-3-[ l-(ethoxyimino )butyl)-4-hydroxy-l- oxaspiro [5.5]undec-3-en-2 -one; 3-[ l-(ethoxyimIno)butyl)-4-hydroxy-l-oxaspiro[5.7] tridec-3- en-2 -one ; 3-[ l-(ethoxyimino)butyl)-4-hydroxy-l-oxaspiro[5.9]pentadec-3- en-2-one; 3-[ l-(ethoxyimino)butyl)-4-hydroxy-l-oxaspiro[5.11]heptadec- 3-en-2-one; 5 " -[ l-(allyloxyimino)butyl)-4' -hydroxyspiro[norbornane-2 O'jy-ό'ji-pyran-ό '' -one] ; 5 " -[ l-(ethoxyimino)butyl)-4' -hydroxyspiro[norbornane- 2-,2' (3'_H_)—6" i-pyran-6 '' -one] ; 5. 5 " -[ l-(ethoxyimino)propyl)-4' -hydroxyspiro[norbornane- 2 X (3' H)-6 ' H-pyran-6 " -one] ; 5-[ l-(ethoxyimino)butyl)-4-hydroxyspiro[6H_-pyran-6-one- 2 ,(3 H), T -(T X X -tetrahydronaphthalene)] ; 5 " -[ l-(allyloxyimino)butyl)-4' -hydroxyspiro [perhydronaphthalene-1 X (3'_H)-6 '' _H-pyran-6 '' -one] ; 5 * -[ l-(ethoxyimino)butyl)-4' -hydroxyspiro [perhydronaphthalene-1 X (3'_H)-6'_H-pyran-6' -one] ; and 5 " -[ l-(ethoxyimino)propyl]-4 ' -hydroxyspiro [perhydronaphthalene-1 X (3' H)-6' H-pyran-6'-one] . A preferred group of compounds of general Formula (2 ) consists of spirocyclic derivatives of the general Formulae (3), (4), (5) and (6). For these novel derivatives, R , R 2 3 and R are as specified above. For the spirocyclic derivatives (3), (4) and (5), the non-lactone ring may be 6 7 8 9 saturated or partially unsaturated and R , R , R and R are selected from the group consisting of: hydrogen; halo; alkyl; alkenyl; alkynyl; substituted alkyl wherein the alkyl * group is substituted with a εubstituent selected from the -8- group consisting of halo , alkoxy, alkylthio , optionally substituted phenyl, and optionally substituted heterocycle; optionally substituted phenyl; and optionally substituted heterocycle; oxo ; acyl; alkoxy; alkylthio; alkoxycarbonyl ; alkoxyimino) alkyl; ketal; and carboxyllc acid. (3) (4) For the novel derivatives (6), the polyatomic ring containing X and Y is a substituted or unsubstituted saturated or partially saturated heterocyclic ring containing 5,6 or 7 ring atoms. The heterocyclic ring may contain one or more heteroatoms selected from the group consisting of oxygen, nitrogen and sulfur, and the ring εubstituents are selected from the group consisting of: hydrogen; alkyl; alkenyl; oxo; acyl; alkoxy; alkylthio; ketal; alkoxycarbonyl;(alkoxyimino)alkyl; carboxyllc acid; substituted alkyl wherein the alkyl group is substituted with a substituent selected from the group consisting of alkoxy, alkythlo, 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 hete oatoms 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 pyridyl. 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 (2) of the invention may undergo tautomerism and exist in any one of five forms as shown below. (2c) (2d) All tautomeric forms are included in the scope of this invention. Particularly preferred choices for R Include hydrogen and the alkali metal cations. Preferred choices for Rr Include alkyl, alkenyl and haloalkenyl. Particularly preferred choices for Br include ethyl, allyl and 2- and 3-chlor allyl. 3 Particularly preferred choices for .include ethyl and n-propyl. Particularly preferred choices for R 6 , R 7 , R 8 , R 9 and εubstituents on the polyatomic chain XY include H and methyl. Where isomers may exist useful compositions may consist of the isomers separately or in mixtures in any possible ratio. Specific examples of compounds of the invention of Formula (2 ) include those compounds detailed in Tables 1-4 below. Table 1 details some examples of compounds of Formula (3) of the invention wherein the cyclopentyl ring is saturated and R =R°=R =R =H; Table 2 details some examples of compounds of Formula (4) of the invention wherein R =R =R =R =H; Table 3 details some examples of compounds of Formula (5) of the invention wherein R 1 =R 6 =R 7 =R 8 =R 9 =H; and Table 4 details some examples of compounds of Formula (6) of the invention wherein the heterocyclic ring is saturated and X and/or Y are sulfur and wherein R and the heterocyclic ring substituents -are hydrogen. -12 - Table 1 Compound 3.1 ethyl n-propyl a 3.2 CH^-C^CH^ n-propyl a 3.3 n-propyl a 3.4 ; n-propyl a 3.5 ethyl ethyl a 3.6 CH 2 -CH=CH 2 ethyl a 3.7 ethyl a 3.8 ethyl a 3.9 ethyl n-propyl methyl 3.10 CEJ-CH-CHJ n-propyl methyl 3.11 CE^-CCl^CE^ n-propyl methyl 3.12 CH 2 -CH=CHC1 n-propyl methyl 3.13 ethyl ethyl methyl 3.14 CE^-CR^CH-. ethyl methyl 3.15 CH 2 ~CC1'=CH 2 ethyl- methyl 3.16 Ci^-CR-CHCl ethyl methyl Table 2 Compound 4.1 ethyl n-propyl H cyclohexylidene 4.2 CH j -CH-CE, n-propyl a cyclohexylidene 4.3 n-propyl a 4 cyclohexylidene 4.4 Ci^-CH=CRC1 n-propyl a cyclohexylidene 4.5 ethyl ethyl a cyclohexylidene 4.6 CI^-CH-C^ ethyl a cyclohexylidene 4.7 O^-CCl β CH j ethyl a cyclohexylidene 4.8 - ethyl a cyclohexylidene 4.9 ethyl n-propyl ca 3 ' cyclohexylidene 4.10 n-propyl ca 3 cyclohexylidene 4.11 ca 2 -ccι=ca 2 n-propyl ca 3 cyclohexylidene 4.12 Ci^-CB=CHC1 n-propyl ca 3 cyclohexylidene 4.13 CI^-C≡CB n-propyl ca 3 cyclohexylidene 4.14 ca(ca 3 )co 2 CH 2 CH 3 n-propyl ca 3 cyclohexylidene 4.15 ethyl ethyl ca 3 cyclohexylidene 4.16 Ci^-CH-CI^ ethyl ca 3 cyclohexylidene 4.17 CI^-CCl-C^ ethyl ca 3 cyclohexylidene 4.18 Cl^-CH=CBC1 ethyl ca 3 cyclohexylidene 4.19 ethyl n-propyl a 2 -cyclohexen-1-ylidene 4.20 n-propyl a 2 -cyclohexen-1-ylidene 4.21 CH 2 -ccι-ca 2 - n-propyl a 2 -cyclohexen-1-ylidene 4.22 CH2-CH-CHC1 n-propyl a 1 - -cyclohexen-1-ylidene 4.23 ethyl n-propyl a 2 -cyclohexen-1-ylidene 4.24 CH j n-propyl a 2- -cyclohexen-1-ylidene 4.25 Cϊ^-CCl-C.^ n-propyl a 2- -cyclohexen-1-ylidene 4.26 CI^-CH=CEC1 n-propyl a 2- -cyclohexen-1-ylidene ■ 14- Table 3 Compound Ef 5. 1 ethyl n-propyl cycloheptylidene 5.2 ca 2 -CH=ca 2 n-propyl cycloheptylidene 5.3 C^-CCl^E^ n-propyl cycloheptylidene 5.4 CE^-CH-CHCI n-propyl cycloheptylidene 5.5 ca 2 -c≡ ca n-propyl cycloheptylidene 5.6 ethyl ethyl cycloheptylidene 5.7 ca^-CH-c^ ethyl cycloheptylidene 5.8 ethyl cycloheptylidene 5.9 CE^ -CH-CHCI ethyl cycloheptylidene 5. 10 ethyl n-propyl 2-cyclohe ten-1-ylidene 5. 11 CEJ -CH-CEJ n-propyl 2-cyclohepten-l-ylidene 5. 12 ca 2 -ccι=ca 2 n-propyl 2-cyclohepten-l-ylidene 5. 13 CE^-CH-CHCI n-propyl 2-cyclohepten-l-ylIdene 5. 14 ethyl ethyl 2-cyclohepten-l-ylIdene 5.15 ethyl 2-cyclohepten-l-ylidene 5. 16 CHj-CCl-CBj ethyl 2-cyclohepten-l-ylIdehe 5. 17 ethyl 2-cyclohepten-l-ylidene Table 4 Compound rt R J x y 6. 1 ethyl n-propyl tetrahydrothiophen-3-ylIdene 6.2 n-propyl tetrahydrothiophen-3-ylIdene 6.3 n-propyl tetrahydrothiophen-3-ylidene 6.4 CH2 -CH-CHCI • n-propyl tetrahydrothiophen-3-ylidene 6.5 ethyl * ethyl tetrahydrothiophen-3-ylidene 6.6 CB2 ethyl tetrahydrothiophen-3-ylidene 6.7 ca 2 -ccι=CH 2 ethyl tetrahydrothiophen-3-ylidene 6 .8 CB2 -ca=cacι ethyl tetrahydrothiophen-3-ylidene 6.9 ethyl n-propyl tetrahydrothiopyran-3-ylidene 6 . 10 n-propyl tetrahydrothiopyran-3-ylidene 6. 1 1 CH2 -CC1-CH2 n-propyl tetrahydrothiopyran-3-ylidene 6. 12 α^ -ca=cacι n-propyl tetrahydrothiopyran-3-ylidene 6. 1 3 ethyl ethyl tetrahydrothiopyran-3-ylidene 6. 14 CH* ethyl tetrahydrothiopyran-3-ylidene 6. 15 CH2 -CCl^l^ ethyl tetrahydrothiopyran-3-ylidene 6. 16 -ca=cacι ethyl tetrahydrothiopyran-3-ylidene 6. 17 ethyl n-propyl tetrahydrothiopyran-4-ylidene 6. 18 CB2 n-propyl tetrahydrothiopyran-4-ylidene 6. 19 CI^ -CCl-CH j n-propyl tetrahydrothiopyran-4-ylidene 6.20 CH^ -ca=cacι n-propyl tetrahydrothiopyran-4-ylidene 6.2 1 ethyl ethyl tetrahydrothiopyran-4-ylidene 6.22 CE^ -CH-CE j ethyl tetrahydrothiopyran-4-ylidene Table 4 Continued 6.23 CB2 -CCl-CI^ ethyl tetrahydrothiopyran-4-ylidene 6.24 c^ -ca=cacι ethyl tetrahydrothIopyran-4-ylidene 6.25 ethyl n-propyl 1,4-dithiacyclohept-6-ylidene 6.26 CH-, -CH=CH 2 n-propyl 1,4-dithiacyclohept-6-ylidene 6.27 n-propyl 1,4-dithiacyclohept-6-ylldene 6.28 CB 2 -ca=cacι n-propyl 1,4-dithiacyclohept-6-ylidene 6.29 ethyl ethyl 1,4-dithiacyclohept-6-ylidene 6.30 ca 2 -ca=ca 2 ethyl 1,4-dithiacyclohept-6-ylldene 6.3 1 CI^ -CCl-CI^ ethyl 1,4-dIthiacyclohept-6-ylIdene 6.32 ca 2 -ca=cacι ethyl 1,4-dithiacyclohept-6-ylidene The compounds of the Invention may be prepared from the dianion of an acetoacetate ester by condensation with an appropriate ketone (cf. auckin, S.N. , and Weiler, L. , Can. J. Chem. ,1974, 52, 2157) followed ' by cyclization with or without intermediate hydrolysis to novel tetrahydro-2JI-pyran-2 ,4-dIones (Formula 7) (Reaction Scheme 1 below). The pyrandiones or their tautomeric 4-hydroxy-5,6- dihydro-2_E-pyran-2-ones can also be obtained by customary methods described in the literature. The 6,6-disubstituted pyran-2 i4-diones thus obtained may be acylated on oxygen and the enol esters isomerized (Fries rearrangement) to give novel _C-substituted products (Formula 8). The ^-acylated derivatives may be reacted with - substituted hydroxyla ines to afford derivatives -of the general Formula (2 ) wherein R is hydrogen. (2 ;R L =a) ( 8) (7) Reaction Scheme 1 Compounds of the invention of Formula (2 ) wherein R is not hydrogen may be prepared by standard synthetic procedures. For example, compounds of the invention of Formula (2 ) wherein R is an inorganic or organic cation may be prepared from compounds of the invention of Formula (2 ) wherein R is hydrogen by reacting these latter compounds with an appropriate inorganic or organic base. Esterification of the vinylogous acid in compounds of Formula (2 ) wherein R is hydrogen provides further herbicidal and growth regulating derivatives. Compounds of Formula (7) and (8) where R , R and R are as hereinbefore defined are novel. The scope of the invention includes these compounds. Specific examples of compounds of the invention of Formula (7) include those compounds detailed in Table 5 below. . Table 5 ,6-Disubstituted-5,6-dihydro-2E-ρyran-2 ,4-diones Compound 6,6-Geminal substituents 7.2 cyclopropyl , methyl 7.4 methyl , 2-thienyl Compound Spirocyclic compounds 7.5 6-oxaspiro[4.5]deca-7 ,9-dione 7.6 2-π_e hyl-6-oxaspiro[4.5]deca-7 ,9-dione 7.7 l-oxaspiro[5.5] undeca-2 ,4-dione 7.8 7 methyl-l-oxaspiro[5.5]undeca-2 ,4-dione 7.9 8-methyl-l-oxas piro [5.5] undeca-2 ,4-dione 7.10 9-methyl-l-oxaspiro [5.5] undeca-2 ,4-dione 7. 11 8 , 10-dimethyl-l-oxaspiro [ 5.5] deca-7 , 9-dione 7.12 9-ethyl-l-oxaspiro[ 5.5]undeca- ,4-dione 7.13 9-tert-butyl- 1-oxaspiro [ 5.5] undeca-2 ,4-dione 7.14 l-oxaspiro[5.5]undec-7-en-2 ,4-dione 7.15 l-oxasρiro[5.6]dodeca-2 ,4-dione 7.16 1-oxaspiro [ 5.6] dodec-7-en-2 ,4-dione 7.17 1-oxaspiro [ 5.7 ] trideca-2 ,4-dione Table 5 continued 7.18 l-oxaspiro[5.9]pen adeca-2 ,4-dione 7.19 l-oxaspiro[5.11]heptadeca-2 ,4-dione 7.20 spiro[norbornane-2 X -tetrahydro-6'ji-pyran- 4' X -dione] 7.21 spiro[tetrahydro-6 jl-pyran-4 ,6-dione-2 (3_H) ,T - (T X X -tetrahydronaphthalene)] 7.22 spiro[ρerhydronaphthalene-l X tetrahydro-6'_R- pyran-4' , 6" -dione] 7.23 6-oxa-2-thiaspiro[4.5]deca-7 ,9-dione 7.24 l-oxa-8-thiaspiro[5.5]undeca-2 ,4-dione 7.25 l-oxa-9-thiaspiro[5.5]undeca-2 ,4-dione 7.26 l-oxa-8 , ll-dithiaspiro[5.6]dodeca-2 ,4-dione 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. (7a) (7b) (7c) All tautomeric and isomeric forms of compounds of Formula (7) are included In the scope of this invention. Specific examples of compounds of the invention of Formula (8) include those compounds detailed in Table 6. Table 6 3-Acyl-4-hydroxy-6,6-disubstituted-5,6-dihydro-2H-pyran-2-ones Compound 6,6-Geminal substituents 8.3 cyclopropyl, methyl n-propyl 8.4 cyclopropyl, methyl ethyl 8.7 methyl , 2-thienyl n-propyl 8.8 methyl , 2-thienyl ethyl Compound Spirocyclic 'compounds 8.9 9-hydroxy-8-propionyl-6-oxaspiro [4.5 ] dec-8-en-7-one 8.10 8-butyryl-9-hydroxy-6-oxaspiro [4.5] dec-8-en-7-σne 8. 11 9-hydroxy-2-methyl-8-propionyl-6-oxaspiro[4.5]dec- 8-en-7-one 8.12 . 8-butyryl-9-hydroxy-2 -methyl-6-oxasρiro [4.5] dec- 8-en-7-one 8.13 4-hydroxy-3-propionyl-l-oxasρiro [5.5 ] undec-3-en-2 -one 8. 14 3-butyryl-4-hydroxy- 1-oxasplro [5.5] undec-3-en-2 -one 8. 15 4-hydroxy-7-methyl-3-propionyl-l-o?as plro [ 5.5 ] undec- 3-en-2-one 8. 16 3-butyryl-4-hydroxy-7-_nethyl-l-oxaspiro [5.5 ] undec- 3-en-2-one Table 6 Continued 8. 17 4-hydroxy-8-methyl-3-propionyl-l-oxaspiro [ 5.5] undec- 3-en-2 -one 8. 18 3-butyryl-4-hydroxy-8-methyl-l-oxaspiro [ 5.5] undec- 3-en-2 -one 8. 19 4-hydroxy-9-methyl-3-propionyl-l-oxasplro [ 5.5] undec- 3-en-2 -one 8 .20 3-butyryl-4-hydroxy-9-methyl-l-oxaspiro [ 5.5 ] undec- 3-en-2 -one 8.2 1 8 , 10-dimethyl-4-hydroxy-3-propionyl-l- oxaspiro [ 5.5 ] undec-3-en-2 -one 8.22 8 , 10-dimethyl-3-butyryl-4-hydroxy-l- oxaspiro[5.5]undec-3-en-2-one 8.23 9-ethyl-4-hydroxy-3-propionyl-l-oxaspiro[5.5]undec- 3-en-2-one 8.24 3-butyryl-9-ethyl-4-hydroxy-l-oxaspiro[5.5]undec- 3-en-2-one 8.25 * ■ 9-teτt-butyryl-4-hydroxy-3-propionyl-l- oxaspiro[5.5]undec-3-en-2-one 8.26 9-tert-3-butyryl-4-hydroxy-1-oxaspiro[5.5]undec- 3-en-2-one 8.27 4-hydroxy-3-propionyl-l-oxasρiro[5.5]undeca-3 ,7- dien-2-one 8.28 3-butyryl-4-hydroxy-l-oxaspiro[5.5]undeca-3 ,7- dien-2-one 8.29 4-hydroxy-3-propionyl-l-oxaspiro[5.6]dodec- 3-en-2-one 8.30 3-butyryl-4-hydroxy-l-oxaspiro[5.6]dodec- 3-en-2-one 8.31 4-hydroxy-3-propionyl-l-oxaspiro[5.6]dodeca- 3 ,7-dien-2-one 8.32 3-butyryl-4-hydroxy-l-oxaspiro[5.6]dodeca- 3 ,7-dien-2-one 8.33 4-hydroxy-3-propionyl-l-oxaspiro[5.6]tridec- 3-en-2-one Table 6 Continued 8.34 3-butyryl-4-hydroxy-l-oxaspiro [5.6] tridec- 3 -en-2 -one 8.35 4-hydroxy-3-propionyl-I-oxaspiro [5.6] pentadec- 3 -en- 2 -one 8.36 3-butyryl-4-hydroxy-l-oxas piro [5.6] pentadec- 3-en-2-one 8.37 4-hydroxy-3-propionyl-l-oxaspiro [5.6] heptadec- 3 -en-2 -one 8.38 3-butyryl-4-hydroxy-l-oxaspiro [5.6 ] hep adec- 3-en-2 -one 8.39 i -hydroxy-5' -proplonyls lro [norborhane- 2 X (¥ _a)-6" E-pyran-6' one] 8.40 5 " -butyryI-4-hydroxyspiro [norbornane-2 ,2 (3'jl)- 6 ' jl-pyran-δ" one] 8. 1 4-hydroxy-5-ρropIonylspiro [6JI-pyran-6-one- .2(3_R) ,1" -(T X X X -tetrahydronaphthalene " )] 8.42 5-butyryl-4-hydroxyspiro[6jl-pyran-6-one- 2 3jl ,r- r X X -tetrahydronaphthalene)] 8.43 4' -Eydroxy-5 ' -proρionylspiro[perhydronaphthalene- 1 X B.)-6" a-pyran-6' -one] 8.44 5 " -butyryl-4' -hydroxyspiro[perhydronaphthalene- 1,2' (3 ' R)-6'E-pyran-6'-one] 8.45 9-hydroxy-8-propionyl-6-oxa-2-thiaspiro[4.5]dec- 8-en-7-one 8.46 8-butyryl-9-hydroxy-6-oxa-2-thiaspiro[4.5]dec- 8-en-7-one 8.47 4-hydroxy-3-propIonyl-l-oxa-8-thiaspiro[5.5]undec- 3-en-2-one 8.48 3-butyryl-4-hydroxy-l-oxa-8-thiaspiro[5.5]undec- 3-en-2-one 8.49 4-hydroxy-3-propionyl-l-oxa-9-thiaspiro[5.5]undec- 3-en-2-one 8.50 3-butyryl-4-hydroxy-l-oxa-9-thiasρlro[5.5]undec- 3-en-2-one Table 6 Continued 8.51 4-hydroxy-3-propionyl-l-oxa-8 ,11-dithiaspiro [5.6]dodec-3-en-2-one 8.52 3-butyryl-4-hydroxy-l-oxa-8 , 11-dithiaspiro [5.6]dodec-3-en-2-one 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 isomeric forms of compounds of Formula (8) are included in the scope of this invention. The compounds of Formula (2) may be applied directly to the plant (post-emergence application) or to the soil before the emergence of the plant (pre-emergence application). -23A- The compounds of the invention are substantially more effective against monocotyledenous plants or grass species than against dicotyledenous plants or broad—leaved species. In either pre-e ergent (soil treatment) or post emergent (foliar) application the compounds of the invention are superior to the prior art ompounds In their selectivity for weed grasses in broad-leafed crops. As demonstrated by the examples given at the end of this description, application of the quantity of- compound necessary to kill weed grasses such as Setaria afaceps or Echinochloa crus-galli does not harm broad-leaf crops such as soy bean, sugar beet, rape, tomato or squash. Certain of the compounds of Formula "(2) show selective herbicidal activity against wild grasses in monocotyledenous crop- species and hence may be used for selective control of wild grass in graminaceous crops. -23B- Certain of the compounds of this invention show postemergence and preemer.gence activity on weeds, including broadleaf weeds, and on grasses with safety to sugar beets. Such compounds are of formula (3) wherein: Rl is a, alkyl, alkenyl, or alkynyl, preferably H R2 is alkyl, alkenyl, alkynyl, halolkenyl, or haloalkynyl R3 is alkyl, alkenyl, alkynyl or haloalkynyl Preferred compounds are those wherein: Rl is H R2 is 2-chloroallyl, 3-chloroallyl, or propynyl R3 is methyl, ethyl, or propyl R6=R7=R8=R9=H and of formula (4) wherein: Rl is H, alkyl, alkenyl, or alkynyl, preferably H R2 is alkyl, alkenyl, alkynyl, halolkenyl, or haloalkynyl R3 is alkyl, alkenyl, alkynyl or haloalkynyl R8 is . alkyl R6=R7=R9=H Preferred compounds are those wherein: * Rl is H 2 is 2-chloroallyl, 3-chloroallyl, or propynyl R3 is methyl, ethyl, or propyl R8 is methyl, ethyl, or propyl and or formula (5) wherein: Rl is H, alkyl, alkenyl, or alkynyl, preferably H R2 is alkyl, alkenyl, alkynyl, halolkenyl, or haloalkynyl R3 is alkyl, alkenyl, alkynyl, or haloalkynyl R6=R7=R8=R9=H Preferred compounds are those wherein: Rl is H R2 is 2-chloroallyl, 3-chloroallyl, or propynyl R3 is methyl, ethyl, or propyl SUBSTITUTE SHEET -23C- ( 6a ) and of formula (6a) wherein: Rl is H, alkyl, alkenyl, or-alkynyl, preferably H R2 is alkyl, alkenyl, alkynyl, halolkenyl, or haloalkynyl R3 is alkyl, alkenyl, alkynyl or haloalkynyl Preferred compounds are those wherein: Rl is H R2 is 2-chloroallyl, 3-chloroallyl or propynyl R3 is methyl, ethyl, or propyl SUBSTITUTE SHEET -24- The compounds of Formula (2 ) 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 (2 ) as hereinbefore defined and an inert carrier therefor. 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 herein before 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 (2) as hereinbefore defined with at least one other herbicide. -25- Certain of the compounds of Formula (2) exhibit useful plant growth regulating activity. For example, while certain compounds of Formula (2 ) show 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 (2) 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 auxiliary 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 regulating 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 of the plant, an effective amount of a compound Formula (2), as-hereinbefore defined. To effect the plant growth regulating process of the present invention the compounds of Formula (2 ) may be applied directly to the plant (pos -emergence application) or to the seed or soil before the emergence of the plant (pre-emergence) application. -26- The compounds of Formula (2 ) may be used on their own to regulate 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 plant growth regulating compositions comprising a compound of Formula (2) 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 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 invention will vary depending on- the type of formulation and whether the 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 1 ppm 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 divided composition. Granules, grains and pellets may be prepared by bonding the active ingredient to a solid -27- carrier, for example, by coating or impregnating the 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, bentonite, kieselguhr, Fuller's earth, Attaclay, diatomaceous earth, talc, chalk, dolomite, limestone, lime, calcium carbonate, powdered magnesia, magnesium oxide, magnesium sulfate, gypsum, calcium sulfate, pyrophylllte, 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 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, anlonic and " non-ionic type. Cationic surface active agents include quaternary ammonium compounds, for example, the long chain alkylammonium salts such as cetyltrimethylammonium bromide. Anionlc surface active agents in'clude: soaps or the alkali metal, -28- alkaline earth metal and ammonium salts of fatty acids; the alkali metal, alkaline earth metal and ammonium salts of llgninsulfonic acid; the alkali metal, alkaline earth metal and ammonium salts of arylsulfonic acids including the salts of naphthalenesulfonic acids such as butylnaphthalenesulfonic acid , the di- and tri- isopropylnaphthalenesulfonlc acidβ, 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 alkylarylbenzenesulfonic acids such as dodecylbenzenesulfonic acid; the alkali metal, alkaline earth metal and ammonium salts of the long chain mono esters of sulfuric acid or alkylsulfates such as laurylsulfate 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/propylene oxide block copolymers; lauryl alcohol polyglycol ether acetal; and the lecithins. The liquid compositions may comprise a solution or dispersion of the active ingredient in a liquid carrier optionally containing one or more surface active agents which act as wetting, emulsifying -29- and/or dispersing agents. Examples of liquid carriers include: waterj 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, yclohexanone and isophorone; and strongly polar organic solvents such as, for example, _N,_N-"dimethylformamide, dimethyl sulfoxide, _N_- methylpyrrolidone and sulfolane. i 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 e ulsifiable concentrates of the salts are conveniently prepared by dissolving the active ingredient in an organic solvent containing one or more surface active agents used -30- 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 irrigation 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 identity 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. These examples of compounds of the invention were made by the same general procedure, starting from the dianion of acetoacetate and an appropriate ketone: the dianion of the acetoacetate was made by one of two ways. -31- General Procedure for Preparation of Examples of Compounds of the Invention (a) Synthesis of the Pyran-2 ,4-diones (7) To a stirred solution of the sodium salt of methyl acetoacetate [cav.55 mmol, either preformed (7.60 g) or made in situ from methyl acetcfaceCate. (5.93 ml, 55 mmol) and sodium hydride (55 mmol) a_c_ σrαing- to- the method of Buckin, S.N., and Weiler, L. , Can. J. Cheπr. , 1974, _52_, 2157] in dry tetrahydrofuran (50 ml) under nitrogen and cooled to 0°C, was added dropwise a solution of n- butyllithium (21.2 ml, 2.6M in hexane, 55 mmol). After 1 h the mixture was treated with an appropriate ketone (50 mmol) (solid ketones were dissolved in tetrahydrofuran prior to addition ) and left stirring at 0°C for 120 min before being ' quenched with methanol (2.4" ml, 60 mmol). After addition of further ethanol (20 ml) and water (10 ml) [and in certain instances acid; e.g. , in Example 10, acetic acid (3.2 ml, 56 mmol) was added] the mixture was boiled for ca. 30 min then diluted further with water (40ml> and concentrated (to ca. 40 ml) at reduced pressure. Upon cooling and addition of water (ca. 150 ml) the mixture was extracted with ether (2 x 100 ml). The ether extracts were washed with water (50 ml); and the combined aqueous phases were acidified to pB 1-2 with cone, hydrochloric acid and extracted with ether (100 ml). (At this stage of some reactions a first crop of the pyrandione crystallized from the ether solution and was recovered by filtration.) The ether solution was then evaporated and the residual water removed from the product mixture by azeotropic distillation with ethanol/benzene and then with henzene. The -32- residue was either chromatographed (SiCU , dichloromethane) or, in some instances, crystallization of the pyrandione was achieved by diluting a concentrated benzene solution (ca. 20 ml) of the residue cautiously with cyclohexane to a faint turbidity, and then stirring vigorously. When crystallization ensued, the mixture was cautiously diluted with more cyclohexane (ca. 20 ml) and stirred for a further 4 h, after which the precipitate was collected and washed with cyclohexane/benzene (4:1) to afford the pyrandione (7). Method B A solution of n-butyllithium (45 ml, 2.45M in hexane, 110 mmol) was added to a stirred solution of diisopropylamine (15.6 ml, 111 mmol) in tetrahydrofuran (50 ml) maintained at 0°C under argon. The stirring was continued for 15 min at room temperature; the mixture was then chilled in ice. Methyl acetoacetate (5.67 ml, 52.5 mmol) was then added and the resultant mixture stirred at 0°C for 30 min; whereupon an appropriate ketone (50 mmol dissolved in the minimum quantity of tetrahydrofuran to form a homogeneous solution) was added and stirring continued for an additional 90 min (or until the reaction mixture paled to light orange or yellow) before quenching with methanol (4.8 ml, 120 π_mol). The reaction mixture was then worked up as in Method A to give the pyrandione (7). (b) Acylation of Pyrandiones To a stirred solution of the pyrandione (7) (6.10 mmol) and DBU [l,8-diazabicyclo(5.4.0.)-7-undecene](0.99 g Λ 6.5 mmol) in toluene -33- (20ml) at 0°C was added an appropriate acyl chloride (6.6 mmol) and the mixture stirred at 0°C for 2 h, then at room temperature for 24 h. Dilution with water (50 ml) and toluene (30 ml) and shaking the mixture gave an organic phase which was quickly washed with 5% hydrochloric acid, dried (sodium sulfate) and evaporated in vacuo. The residue and 4-dimethylaminopyridIne (40 g, 0.3 mmol) were heated under reflux In toluene (10 ml) for 3 h (or until thin layer chromatography showed that the reaction was complete) and then the toluene was removed in vacuo and the residue chromatographed [SiC, , dichlorome hane:light petroleum (b.p. 40- 60 C C): ethyl acetate (4:4:1)] to give the C-acylated compound (8). (c~) Oximation of Acylated Compounds. A mixture of the C_-acylated compound (8) (3.75 mmol), the appropriate _p-substitued hydroxylamine hydrochloride (4.00 mmol), triethylamine (0.41 g, 4.0 mmol) and methanol (5 ml) was stirred at room temperature for 48 h, then poured into water (50 ml). Acidification of the mixture to pB 4 with 5M hydrochloric acid, extraction with diethyl ether or ethyl acetate (2 x 50 ml), evaporation of the organic phase and chromatography [SiCL , dichloromethane or dichloromethane:light petroleum (b.p. 40- 60°C):ethyl acetate (4:4:4)] of the residue then afforded examples of compounds "of the invention (2). The compounds made using Method A include those in the following examples (1 - 8). -34- Example 1 Preparation of 3-[ l-(Ethoxyimino)butyl]-4-hydroxy-9-methyl-l- oxaspiro[5.5]undec-3-en-2-one (4.9) (a) 9-Methyl-l-oxaspiro[5.5]undeca-2 ,4-dione (7.10) 4-Methylcyclohexanone (6.2 ml, 51 mmol) was reacted with the dianion of methyl acetoacetate (ca. 55 mmol) as described in Method A above. The pyrandione (7.10)(6.51 g, 65%) crystallized from benzene/cyclohexane as a white powder m.p. 161-163 C C. Mass spectrum m/ 197 (M+l). 13 C n.m.r. δ (CDCI3) 200.5, C4; 167.4, C2 ; 81.50, C6; 46.06, C5; 44.53, C3 ; 36.08; .30.61 ; 20.85, CB3. L B * n.m.r. <5(CDC1 3 ) 3.42, s. 203; 2.77, s, 2B5; 1.95 -1.4, complex, 7B; 1.2 - 0.98, m, 2B; 0.93, d, _ 6 Bz,CB 3 . (b) 3-Butyryl-4-hydroxy-9-methyl-1-oxaspiro[5.5]undec-3-en-2-one (8.20) The pyrandione (7.10)(1.20 g, 6.11 mmol) was acylated with butyryl chloride (0.70 g, 6.57 mmol) in the presence of DBU, and the _0-butyryl intermediate rearranged by heating with 4- dimethylaminopyridine, as described in Part (b) of the general procedure above, to afford the C-acylated compound (8.20)( 1.06 g, 65%) as pale yellow granules m.p. 60 - 63°C. Mass spectrum m/z 267 (M+l). l E n.m.r δ (CDC1 3 ) 17.85, broad s, OB; 3.02, t, J_ 7 Bz, C^Ca^Ca^ " 2.85 - 2.7, , 2B5; 2.0 - 1.3, complex, 11B; 0.98, t, J_ 7.5 az, (nujol) 1723 s, 1690 , 1644 m, 1567 s, 1462 s, 1068 m cm -1 . -35- (c ) 3-[ l-(Ethoxyimino )butyl ] -4-hydroxy-9-methyl-l-oxaspiro [5.5] undec-3 -en-2 -one (4.9) The acylated compound (8.20)(1.00 g, 3.75 πmol) was oximated with ethoxyamine hydrochloride (0.39 g, 4.0 mmol) in the presence of triethylamine as described in Part (c) of the general procedure above, to afford the title compound (4.9)(1.00 g, 86%) as a mobile pale yellow oil. (Found: M, 309.196. C j yH^tK^ requires 309.194.) L B n.m.r. δ (CDC1 3 ) 14.80, very broad s, IB; 4.08, q, J_ 7 Bz, OCB2Ca 3 ; 3.00, t, __ 7.5 Bz, Ca2CB2Ca 3 ; 2.68, s, 2B5; 2.2-1.2 complex, 11B; 1.30, t, _7.5 z, OCHgCB 3 ; 1.15 - 0.7, , CB,CH^CB 3 Example 2 : 3-[l-[(2-chloro-2-propenyl)oxyimino]butyl]-4-hydroxy-9- methyl-l-oxaspiro[5.5]undec—3-en-2-one (4.11) [from 4- methylcyclohexanone, butyryl chloride and (2-chloro-2- propenyl)oxyamine hydrochloride] as a viscous light yellow oil which solidified to a white waxy solid m.p. 64 - 68°C. Mass spectrum m/z 356 (M+l). B n.m.r. δ (CDC1 3 ) 5.57, unresolved d, ; 2.73, s, 2B5; 2.4 - 0.7 , 17B. Example 3: 3-[l-(Ethoxyimino)butyl]-4-hydroxy-l-oxaspiro [5.5]undeca-3 ,7-dien-2-one (4.19) (from 2-cyclohexen-l-one, butyryl chloride and ethoxyamine hydrochloride) as a viscous light yellow oil. (Found:M+B, 294.170. C^B^NO^B requires 294.171.) L B n.m.r. (CDCI3) 14.96, very broad s, IB; 6.10 - 5.77, m, 2x=CB; 4.11, q, _ 7 Bz, OCB;CB3; 3.03, t, 7.5 Bz, CB2CH2CB3; 2.68, s, 2B5; 2.45 - 1.4, m, 8B: 1.37, t, J_ 7.5 Bz, OCH2CB3 1.02, t, _ 7.5 -36- Bz; Ca 2 C 2 CB 3 . > maχ (film) 1706 s, 1623 s, 1407 s, 1048 s cm -1 . Example 4: 8-[ l-(Ethoxyimino)butyl] -9-hydroxy-6-oxaspiro [4.5] dec-8-en-7-one (3.1) (from cyclopentanone, butyryl chloride and ethoxyamine hydrochloride) as a pale yellow oil. (Found:M, 281.164. C^H^N^ requires 281.163.) X B n.m.r. δ. (CDC1 3 ) 14.74, very broad s, IB; 4.10, q, J_ 6 Bz , 0CB 2 CB 3 ; 2.99 , f.,. ..7.5 Bz, _CH 2 CH 2 CH 3 ; 2.67, broad s, 2B10; 2.3 - 1.15, m, 10B; 1.35, t , ■ J_ 7 Bz OCB-, CB 3 ; 0.98, t , J_ 7 Bz , CH^ CH^ CB 3 . v maχ (film) 1707 s. 1623 s, 1410 s, 1050 s cm "1 . Example 5: 8-[ l-(Ethoxyimino)butyl] -9-hydroxy-2-methyl-6- oxas iro [4.5] dec-8-en-7-one (3.9) (from 3-methylcylopentanone, butyryl chloride, and ethoxyamine hydrochloride) as a mobile pale yellow oil. (Found:M+B, 296.185. C^E^NO^+H requires 296.186.) L B n.m.r. δ (CDCI3) 14.9, very broad s, IB; 4.06, q, J 7 Hz, OCB^ CB3 ; 2.97, t, _J 7.5 Bz , CΑ^CR^CE^; 2.65, broad s, 2B10; 2.4 - 0.7, m, 15B; 1.32, t, £ 7 Bz , OCBg CB-, . v maχ (film) 1710 s, 1623, 1411 s, 1052 s cm -1 . Example 6: A 1.0:1.8 Mixture of (Z):(E) 8-[ l-[(3-Chloro-2- propenyl )oxyimino )butyl ] -9-hydroxy-2 -methyl-6-oxasρiro [4.5] dec-8-en-7-one (3.12) (from 3-methylcyclopentanone , butyryl chloride and a mixture of (Z)-and (E)-3-chloro-2-propenyloxyamine hydrochloride) as a viscous amber oil. (Found:M+H, 342.146. C 17 H 24 C1N0 4 +H rec I uires 342.147.) l E n.m.r. (CDCI3) 14.20, broad s, IB; 6.5 - 5.85, m, 2x-CB; 4.74, d, J_ 6.5 Bz, N0CH2 of (Z)_ isomer; 4.48, d, J_ 6 Hz, NOCI^ of (Z)_ -37- isomer; 2.95, t, _J 7.5 Bz , CB 2 CB 2 CB 3 2.70, unresolved d, 2B5; 2.4 - 0.7, m, 15B. maχ (film) 1712 s, 1623 s, 1410 s cm -1 . Example 7: A 1.0:2.0 Mixture of (Z):(E) 3-[ l-[(3-Chloro-2- propenyl )oxyimlno )butyl ] -4-hydroxy- 1-oxasplro [5.6] dodec-3 -en-2 -one (5.4) [from cycloheptanone, butyryl chloride and a mixture of (Z)- aπd: (E)-3-chloro-2 -propenyloxya ine Hydrochloride) as a pale yellow oil which solidified on cooling (5 - I0°C) to a white waxy solid m.p. <20° - 50°C. (Found:M, 355.156. C 18 H 26 C1N0 4 re< l uiιes 355.155.) l E n.m.r. (CDC1 3 ) 14.12, very broad s, IB; 6.5 - 5.75, m, 2x=CB; 4.74, d, J_ 6 Bz , tΛX^ of (Z) Isomer; 4.52, d, J_ 6 Bz , NOCB-. of (E) isomer; 2.94, broad t, 7.5 Bz, α^CB ^ CB^ 2.61, broad s, 2B5; 2.2 - 0.9, m, 14B; .0.97 ,"t, _J 7 Bz, CB 3 . v maχ (nujol) 1714 s, 1622 s, 1406 s, 1378 s, 1025 s cm -1 . Example 8: 3-[ l-(Ethoxyimlno)butyl]-4-hydroxy-l-oxa-9- thiaspiro[5.5]undec-3-en-2-one (6.17) (from tetrahydrothiopyran-4- ocne;, butyryl chloride and ethoxyamine hydrochloride) as a viscous pale yellow oil. (Found :M, 313.134. C j ^B^NO^ requires 313.135.) l E n.m.r. δ (CDC1 3 ) 15.0, very broad s, IB; 4.08, q, _ 7 Bz, 3.27 -2.79, & 2.07 - 1.4, , 12B; 2.57, s, 2B5; 1.35, t, J_ 7.5 Bz, OCBQ CB 3 ; 1.00, t, _ 7.5 Bz, CB^^^. v m ax (film) 1707 s, 1623 s, 1412 s, 1049 s cm "1 . The compounds made using Method B (for the synthesis of the pyrandiones) include those of the following examples (9 - 11). -38- Example 9 Preparation of 3-[ l-(Ethoxyimino)butyl]-4-hydroxy-l-oxa- 8 > U-dithiaspiro[5.6]dodec-3-en-2-one (6.25) (a) l-0xa-8,11-dithiasρiro[5.6]dodeca-2 ,4-dione (7.26) 1 ,4-Dithiacycloheptan-6-one (4.93 g, 33.3 mmol in 5 ml of tetrahydrofuran) was reacted with the dianion of methyl acetoacetate (ca. 33 mmol) as described in Method B in the general procedure above. (The ice-cold mixture was quenched with methanol 30 min after addition of the ketone.) A first crop crystallized immediately upon acidification of the final aqueous solution, and was filCered and washe d with ether to give the pyrandione (7.26) (3.33 g.* 43%) as off-white "microgranules m.p. 174 - 178°C. Mass spectrum m/z 233 (M+l). (b) 3-Butyryl-4-hydroxy-l-oxa-8 ,11-dithiasρiro[5.6]dodec-3- en-2-one (8.52 ) The pyrandione (7.26) (2.32 g, 10.0 mmol) was acylated with butyryl chloride (1.38 g, 13.0 mmol) in the presence of DBU, and the _0-butyryl intermediate rearranged by heating with 4-dimethylaminopyridine, as described in Part (b) of the general procedure above, to afford the C-acylated compound (8.52) (1.70 g, 56%) as a pale brown oil which solidified to a beige solid m.p. 88 - 93°C. Mass speςtru m/z 303 (M+l). l E n.m.r. (CDC1 3 ) 13.8, very broad s, OB; 4.1 - 1.35, complex, 14H; 1.35 - 0.80, m, CH 3 . -39- (c) 3-[l-(Ethoxylmino)butyl]-4-hydroxy-l-oxa-8,11- dlthiasplro[5.6]dodec-3-en-2-one (6.25) The acylated compound (8.52) (0.453 g, 1.50 mmol) was oxlmated with ethoxyamine hydrochloride (0.195 g, 2.00 mmol) In methanol (10 ml) as described in Part (c) of the general procedure above to afford a product which was recrystalllzed from ether to give the title compound (6.25) (0.170 g, 33%) as white microcrystals m.p. 108 - 110°C. Mass spectrum m/z 346 (M+l). l R n.m.r. δ (CDC1 3 ) 4.11, q, 7 Bz, 0Ca 2 Ca 3 ; 3.95 - 1.1, complex, 14B; 1.33, t, £ 7 Bz, 1.00, t, _ 7 az CH 2 ca 2 ca 3 . Example 10: 8-[l-(Ethoxyimino)butyl]-9-hydroxy-6-oxa-2- thiaspiro[4.5]dec-8-en-7-one (6.1) (from tetrahydrothlophen- 3-one, butyryl chloride and ethoxyamine hydrochloride using acetic acid to aid lactonization in Step (a) of the general synthetic procedure) as a viscous pale yellow oil. Mass spectrum m/z 300 (M+l). B n.m.r. δ (CDCI3) 4.10, q, £ 7 Bz, QCa,CB 3 ; 4.0 - 0.6, complex, 12B; 1.35, t, 7 Bz, OCB^CBg,- l.oo, t, J_ 7 az, ca, ca, ca 3 . Example 11 : 3-[ l-(Ethoxylmino)butyl]-4-hydroxy-l-oxaspiro [5.6 ] dodeca-3 ,7-dien-2 -one (5. 10) ( from 2-cyclohepten-l-one , butyryl chloride and ethoxyamine hydrochloride) as a viscous light yellow oil . Mass spectrum m/z 308 (M+l ) . l E n.m. r. ≤ (CDCI3 ) 6.2 - 5.4 , m, 2x-CH; 4.06 , q , 7 Bz , OCE^ CBg ; 3.3 - 2 .55 , m, 2B5 & 2 H & _CB 2 CH 2 CB 3 ; 2 .55 - 1.0 , m , 8B ; 1.33 , t , £ 7 Bz , OCb^ CB^ ; 0.98 , , £ 7 Bz , C ^-^ CB^ EXAMPLE 12 The pre-emergent herbicidal activities of the compounds of the invention were assessed by the following procedure: Seeds of each of the test species were sown 5 mm deep in 5 presterilized soil in square plastic pots approximately 6cm x 7cm with an appropriate number of seeds per pot to avoid overcrowding and allow satisfactory plant development. The pots were then placed at randomised positions in trays 30cm x 34 cm so that each tray contained one of each test .species. 10 The required quantity of the test compound was dissolved in acetone and the acetone solution dispersed in water to give a spray liquid volume equivalent to 1000 1/ha. Two trays were sprayed with the test compound for each application rate using a flat fan even swathe nozzle. One 5 tray for each ten chemical treatments was sprayed with acetone/water only and was included in the remainder of the test procedure to act as control. All the trays were placed in a glasshouse, lightly watered with an overhead spray to initiate germination and then spray irrigated as required for 0 optimum plant growth. After three weeks the trays were -41- removed from the greenhouse and the effect of the treatment was assessed. The assessments were on a 1-10 scale, where 0 = no effect and 10 = plants dead. The test species and results are shown for the compounds of Examples 1 - 8 In Tables 7 - 14 respectively. EXAMPLE 13 The post-emergent herbicidal activities of the compounds 5 of the invention were assessed by the following procedure: Seeds of each of the test species were sown 5 mm deep In presterilized soil in square plastic pots approximately 6cm x 7cm with an appropriate number of seeds per pot to avoid overcrowding and allow satisfactory plant development. The 10 pots were then placed at randomised positions in trays 30cm x 34 cm so that each tray contained one of each test species. All the trays were placed in a glasshouse, lightly watered with an overhead spray to initiate germination and then spray Irrigated as required for optimum plant growth. 15 After the plants had grown to a height of 10 to 12.5 cm the required quantity of the t§st compound was dissolved In acetone and the acetone solution dispersed in water to give a spray liquid volume equivalent to 1000 1/ha. Two trays were sprayed with the test compound for each 20 application rate using a flat fan even swathe nozzle. One tray for each ten chemical treatments was sprayed with acetone/water solution only and was included in the remainder of the test procedure to act as control. The treated trays were then returned to the greenhouse. After three weeks post-treatment the effect of the treatment was visually assessed. The assessments were on a 0-10 scale, where 0 = no effect and 10 = plants dead. The test species and results are shown for the compounds of Examples 1-8 in Tables 7-14 respectively. The results demonstrate the herbicidal activity of the compounds of Formula (2) in either pre-emergent (soil treatment) or post emergent (foliar) application; they also demonstrate that the comounds of the invention are superior to the prior art compounds in their selctivity for weed grasses in broad- 4 . . . leafed crops. The following Example provides a further illustration of the selectivity of the compounds of Formula (2) wherein crop and weed species are planted and treated in the same container. EXAMPLE 14 18 cm diameter plastic flower pots containing sandy loam were planted with sugarbeets and key grass weeds. Three pots were used, each containing 3-4 species at about 5 plants/species, with each species confined to a distinct' area. The required quantity of test comound was dissolved in a non-phytotoxic solvent and sprayed onto the soil surface at an application rate of 1 kg/ha. After spraying, the planted pots were imediately placed In a greenhouse. -42A- After 30 days the pots were removed from the greenhouse and the effect of the treatment was assessed. The assessments were on a 1-10 scale, where 0 = no injury and 10 = plants dead. All treated plants were compared with untreated controls. Compound 4.13 (Table 2) was compared with the compound Nortron (ethofumesate) sold for pre-emergence control of grasses with the following results: COMPOUND RATING Sugar Wheat Wild Barley Rye Black- Green beet oats grass grass foxtail 4.13 10 10 10 10 10 10 Nortron ' 10 10 10 10 10 The compound of this invention killed all grasses without harming sugar beet while Nortron damaged sugar beet and gave only partial control of rye grass. -43- TABLE 7 HERBICIDAL ACTIVITY OF CGHPOϋND (4.9 ) PIAHT MEAN BERB ICIDAL RATING PRE-EMERGENT POST-EMERGENT FAMILY - Species APPLICATION RATE kg/ha APPLICATION RATE •kg/ha 0 0. 1 0.5 0 0. 1 0.5 MONOCOTYLEDONS GRAMINEAE - Echinochloa crus-galli 0 0. 5 10 0 4 9. 5 - Panicum sp. 0 0 10 0. , 5 9.5 10 - Lolium rigidum 0 1 9.5 0. 5 4.5 10 - maize [Zea mays] 0 2 8 0 1 .5 10 - rice [Oryza sativa] 0 0 10 0 4.5 8. 5 - wheat [Triticum sp.] 0 2 .5 8.5 0 2 10 CYPERACEAE - cyperus rotundus 0 0 0 0 0 0 ALLIACEAE - onion [Allium cepa] 0 0 0 _ _. — DICOTYLEDONS CBEN0P0DIACEAE - Chenopodium album AMARANTBACEAE - Amaranthus sp. (weed) - red beet [Amaranthus retroflexus] 0 0 0 0 0 0 CRUCIFERAE - rape [Brassica napus] 0 0 0 0 0 0 LEGUMINOSAE - soybean [Glycine max] 0 0 0 0 0 0 - lucerne [Medicago sativa] 0 0 0 - - - MALVACEAE - cotton [Gossypium sp.] 0.5 0.5 0.5 SOLANACEAE - tomato [Lycopersicum esculentum] 0.5 0 0 0 0 0 CURCURBITACEAE - squash [Curcurblta pepo] 0 0 0 0 0 0 COMPOSITAE - sunflower [Belianthus annuus] 0 0 4 0 0 0 - safflower [Carthamus tinctorius] 0 0 0 0 0 0 -44- TABLE 8 HERBICIDAL ACTIVITY OF CGKPOϋHD (4. 11 ) PI_ANT MEAN HERBICIDAL RATING PRE-EMERGENT POST-EMERGENT FAMILY - Species APPLICATION RATE kg/ha APPLICATION RATE kg/ha 0 0. 1 0.5 0 0. 1 0.5 MONOCOTYLEDONS GRAKINEAE: - Setaria- anceps 1 8.5 8.5 0 6.5 9.5 --Echinochloa crus-galli 1.5 5 10 0 7 10 —Panicum sp. 0.5 10 10 - - - - Lolium rigidum 0 10 10 ' 0 8 9.5 - maize [Zea mays] 0 0.5 3 0 3 10 - rice [Oryza sativa] 0 0 2 .5 0 9 10 - wheat [Triticum sp.] 0 4 10 0 9 10 CYPERACEAE —cyperus rotundus 0 0 0 0 0 0 ALLIACEAE --onion [Allium cepa] 0 0 2 _ _ _ DICOTYLEDONS CHENOPODIACEAE - Chenopodium album 0 2 .5 7.5 0 5 8.5 AMARANTBACEAE - Amaranthus sp. (weed) 0 2 .5 5 0 1.5 1.5 - red beet [Amaranthus retroflexus] 0 0 0 0 5 7.5 CRUCIFERAE -rape [Brassica napus] 0 0 0 0 1.5 4.5 LEGUMINOSAE - soybean [Glycine max] 0 0 0 0 4 2 - lucerne [Medicago sativa] 1 0 1 - - - MALVACEAE - cotton [Gossypiu sp.] 3.5 SOLANACEAE - tomato [Lycoperslcum esculenturn] 0 0 0 0 1 6.5 CUCURBITACEAE - squash [Cucurbita pepo] 0.5 0 0 0 1 1 COMPOSITAE - sunflower [Belianthus annuus] 1.5 0 2 .5 0.5 1.5 0.5 - safflower [Carthantus tinctorius] 0 8 8.5 0 2 3.5 -45- TABLE 9 HERBICIDAL ACTIVITY OF COMPOUND (4. 19 ) PLAHT MEAN HERB ICIDAL RATING PRE-EMERGENT POST-EMERGENT FAMILY - Species APPLICATION RATE kg/ha APPLICATION RATE kg/ ha 0 0. 1 0. 5 0 0. 1 0. 5 MONOCOTYLEDONS GRAM I EAE - Setaria anceps 0 0 9.5 0 8. 5 9 - Echinochloa crus-galli 0 5 8.5 0 10 10 - Panic um sp . 0 1 8 - - - - Lolium rigidum „ 0 1 7.5 0 8.5 9 - maize [Zea mays] 0 0 8 0 6. 5 10 - rice [Oryza sativa] 0.5 0 8 0 3 .5 9 - wheat [Triticum sp.] 0 0 4. 5 0 1 7 CYPERACEAE - cyperus rotundus 0 0 0 0 0 0 ALLIACEAE * - onion [Allium cepa] • 0 0 • 0 _ _. _ DICOTYLEDONS CHEN0P0DIACEAE - Chenopodium album 0.5 0 3 0 0 0 AMARA TBACEAE - Amaranthus sp. (weed) 0 0 0 0 0 0 - red beet [Amaranthus retroflexus] 0 0 0 0 0 0 CRUCIFERAE - rape [Brassica napus] 0 0 0 0 0 0 LEGUMIN0SAE - soybean [Glycine max] 0 , 0 0 0 0 0 - lucerne [Medicago sativa] 0 0 0 - - - MALVACEAE - cotton [Gossypium sp.] SOLANACEAE - tomato [Lycopersicum esculentum] 0 0 0 0 0 0 CUCURBITACEAE - squash [Cucurbita pepo] 0 0 0 0 0 0 COMPOSITAE - sunflower [Helianthus . annuus] o- 0 0 0 0 0 - safflower [Carthamus tinctorius] 0 0 0 0 0 0 -46- TABLE 10 HERBICIDAL ACTIVITY OF COMPOUND (3. 1 ) PIANT MEAN BERBICIDAL RATING RE-EMERGENT POST-EMERGENT FAMILY - Species APPLICATION RATE kg/ha APPLICATION RATE kg/ha 0 0. 1 0.5 0 0. 1 • 0.5 MONOCOTYLEDONS GRA INEAE - Setaria anceps 0 4 8.5 0 8.5 10 - Echinochloa crus-galli 0.5 7 10 0 8 9 - Panicurn sp. 0 5.5 10 0 7.5 9 - Lolium rigidum 0 5 10 * 0 8.5 9 - maize [Zea mays] 0 9.5 9.5 0.5 0 8.5 - rice [Oryza sativa] 0 0 0 0 1 6.5 - wheat [Triticum sp.] 0 1 4 0 0.5 7.5 CYPERACEAE - cyperus rotundus 0 0 0 0 0 0 ALLIACEAE - onion [Allium cepa] 0 0 0 0 0 0 ' DICOTYLEDONS CBENOPODIACEAE - Chenopodium album 0 0 0 0 0 0 AMARANTBACEAE - Amaranthus sp. (weed) 0 0 0 0 0 0 - red beet [Amaranthus retroflexus] 0.5 0 0 0 0 0 CRUCIFERAE - rape [Brassica napus] 0 0 0 0 0 0 LEGUMINOSAE - soybean [Glycine max] — — — 0 0 0 - lucerne [Medicago sativa] 0 0 0 0 0 0 MALVACEAE - cotton [Gossypium sp.] 0 , 2 .5 2 0 0 0 SOLA ACEAE - tomato [Lycopersicum esculentum] 0.5 0 0 0 0 0 CUCURBITACEAE - squash [Cucurbita pepo] 0.5 0 0 0 0 0 COMPOSITAE - sunflower [Belianthus annuus] 0 0 0 0.5 0 0 - safflower [Carthamus tinctorius] 0 0 0 0 0 0 -47- TABLE 1 1 HERBICIDAL ACTIVITY OF COMPOUND (3.9 ) PLAHT MEAN BERB ICIDAL RATING PRE-EMERGENT POST-EMERGENT FAMILY - Species APPLICATION RATE kg/ha APPLICATION RATE kg/ha 0 0.1 0.5 0 0.1 0.5 MONOCOTYLEDONS GRAMINEAE - Setaria anceps 0 0 10 0 8 9 - Echinochloa crus-galli 0 1.5 3 0 9 10 - Panicum sp. 0 1 8.5 - - - - Lolium rigidum 0 0 6.5 0 4.5 9 - maize [Zea mays] 0 0 3 0 1 10 - rice [Oryza sativa] 0.5 0 6 0 0 7 - wheat [Triticu sp.] 0 0 4 0 0 2 CYPERACEAE - cyperus rotundus 0 0 0 0 0 0 ALLIACEAE - onion [Allium cepa] ' .0 0 0 - - - DICOTYLEDONS CHENOPODIACEAE - Chenopodium album 0.5 0 4 0 0 0 AMARANTHACEAE - Amaranthus sp. (weed) 0 0 0 0 0 0 - red beet [Amaranthus retroflexus] 0 0 0 0 0 0 CRUCIFERAE - rape [Brassica napus] 0 0 0 0 0 0 LEGUMINOSAE - soybean [Glycine max] 0 0 0 0 0 0 - lucerne [Medicago sativa] 0 0 0 - - - MALVACEAE - cotton [Gossypium sp.] 0 0 1 0 0 0 SOLA ACEAE - tomato [Lycopersicum esculentum] 0 0 0.5 0 0 0 CUCURBITACEAE - squash [Cucurbita pepo] 0 0 0 0 0 0 COMPOSITAE - sunflower [Belianthus annuus] 0 0 0 0 0 0 - safflower [Carthamus tinctorius] 0 0 3.5 0 0 0 -48- TABLE 1 2 HERBICIDAL ACTIVITY OF A 1.0:1.8 MIXTURE OF (Z):(E) COMPOUND (3.12) PLANT MEAN HERBICIDAL RATING PRE-EMERGENT POST-EMERGENT FAMILY - Species APPLICATION RATE kg/ha APPLICATION RATE kq/ha 0 0.1 0.5 0 0.1 0.5 MONOCOTYLEDONS GRAMINEAE - Secaria anceps 0 3 9 . 5 0 7.5 1 0 - Echinochloa crus-galli 0 1 .5 3 .5 0 7.5 1 0 - Panicum sp. 0 2 6 « — - - - Lolium rigidum 0 0 1 0 0 4 9. 5 - maize [Zea mays] 0 2.5 4. 5 0 1 2 - rice [Oryza sativa] 0.5 1 .5 4 0 2 6. 5 - wheat [Triticum sp.] 0 1 4 0 1 1 . 5 CYPERACEAE - cyperus rotundas 0 0 0 0 0 0 ALLIACEAE - onion [Alllu cepa] 0 0 1 .5. «. _ _. DICOTYLEDONS CHENOPODIACEAE - Chenopodium album 0.5 4 6.5 0 0 0 AMARANTHACE E - Amaranthus sp. (weed) 0 0 0 0 0 - red beet [Amaranthus retroflexus] 0 0 0 0 0 CRUCIFERAE - rape [Brassica napus] 0 0 0 0 0 LEGUMINOSAE - soybean [Glycine max] 0 0 0 0 0 0 - lucerne [Medicago sativa] 0 0 0 MALVACEAE - cotton [Gossypium sp.] SOLANACEAE - tomato [Lycopersicum escule tum] 0 0 0 0 0 CUCURBITACEAE - squash [Cucurbita pepo] 0 0 0 0 0 COMPOSITAE - sunflower [Helianthus annuus] 0 - safflower [Carthamus tinctorius] 0 -49- TABLE 13 HERBICIDAL ACTIVITY OF A 1.0:2.0 MIXTURE OF (Z):(E) COMPOUND (5.4) PLANT MEAN BERBICIDAL RATING PRE-EMERGENT POST-EMERGENT FAMILY - Species APPLICATION RATE kg/ha APPLICATION RATE kg/ha 0 0.1 0.5 0 0.1 0.5 MONOCOTYLEDONS GRAMINEAE - Setaria anceps 0.5 5.5 10 0 0. 5 9 - Echinochloa crus-galli 0.5 2 .5 10 0 2 9 —Panicum sp. 0.5 5.5 10 0 1 . 5 8. 5 - -Lollum rlgidum 0 8 10 0 1 .5 7 - maize [Zea mays] 0.5 0 0 0 0 1 - rice [Oryza sativa] 1 0 0 0 0 0 - wheat [Triticum sp.] 0 0 0 0 0 0. 5 CYPERACEAE - cyperus rotundus 0 0 0 0 0 0 ALLIACE^E - onion [Allium cepa] 0 0 • 0 _ _ _ DICOTYLEDONS CBENOPODIACEAE - Chenopodium album 0 0 2 .5 0 0 0 AMARANTBACEAE - Amaranthus sp. (weed) 0 0 0 0 0 0 - red beet [Amaranthus retroflexus] 0 0 0 0 0 0 CRUCIFERAE - rape [Brassica napus] 0 0 0 0 0 0 LEGUMIN0SAE - soybean [Glycine max] 0 0 0 0 0 0 - lucerne [Medicago sativa] 0 0 0 0 0 0 MALVACEAE - cotton [Gossypium sp.] SOLA ACEAE - tomato [Lycopersicum esculentum] 0 0 0 0 0 0 CUCURBITACEAE - squash [Cucurbita pepo] 0 0 1 0 0 0 COMPOSITAE - sunflower [Belianthus annuus] 0 0 0 0 0 0. - safflower [Carthamus tinctorius] 0.5 0 0 — — _ -50- TABLE 14 HERBICIDAL ACTIVITY OF COMPOUND (6. 17 ) PLAMΓΓ MEAN BERBICIDAL RATING PRE-EMERGENT POST-EMERGENT FAMILY - Species APPLICATION RATE kg/ha APPLICATION RATE kg/ha 0 0.1 0.5 0 0.1 0.5 MONOCOTYLEDONS GRAMINEAE - Setaria anceps 0.5 0 10 0 10 10 - Echinochloa crus-galli 1 1.5 10 0 9.5 10 —Panicum sp. 0.5 0.5 10 - - - - Lolium rlgidum 0 10 10 0 8 10 - maize [Zea mays] 0 4.5 10 ' 0 6 9 - rice [Oryza sativa] 2.5 9 9.5 0 9.5 10 - wheat [Triticum sp.] 0 9 10 0 9.5 9.5 CYPERACEAE - cyperus rotundus ALLIACEAE - onion [Allium cepa] DICOTYLEDONS CBENOP0DIACEAE - Chenopodium album 1 " 0 0 0 0 1 AMARANTBACEAE - Amaranthus sp. (weed) 0 0 0 0 0 0 - red beet [Amaranthus retroflexusI 0 0 0 0 0 0 CRUCIFERAE - rape [Brassica napus] 0 0 0 0 0 0 LEGUMINOSAE - soybean [Glycine max] 0 0 0 0 1.5 0 - lucerne [Medicago sativa] 0 0 0 - — - MALVACEAE - cotton [Gossypium sp.] SOLANACEAE - tomato [Lycopersicum esculentum] 0 0 0 0 0 0 CUCURBITACEAE - squash [Cucurbita pepo] 0 0 0 0 0 0 COMPOSITAE - sunflower [Belianthus annuus] 0 0 0 0.5 0 0 - safflower '[Carthamus tinctorius] 0 0 0 _- _ .__.

Claims: -51- CLAIMS 1. A compound of the general formula (2) and isomeric and/or tautomeric forms thereof 1 . . characterized in that R is selected from the group consisting of: hydrogen; alkyl; alkenyl; alkynyl; cycloalkyl; cycloalkenyl; substituted alkyl or substituted cycloalkyl wherein the alkyl or cycloalkyl group is substituted with a substituent selected from the group consisting of alkoxy, alkylthio, optionally substituted phenyl, optionally substituted heterocycle; optionally substituted phenyl; optionally substituted heterocycle, alkyl sulfonyl; optionally substituted benzene sulfonyl; an acyl group; and an inorganic or organic cation; 2 R is selected from the group consisting of: alkyl; alkenyl; cycloalkyl; cycloalkenyl; haloalkenyl; alkynyl; haloalkynyl; substituted alkyl or substituted cycloalkyl wherein the alkyl or cycloalkyl group is substituted with a substituent selected from the group consisting of halogen, alkoxy, alkylthio, optionally substituted phenyl, and optionally substituted heterocycle; optionally substituted phenyl; and optionally substituted heterocycle; -52- R is selected from the group consisting of: alkyl; haloalkyl; alkenyl; cycloalkyl; cycloalkenyl; alkynyl; and optionally substituted phenyl; 4 R is selected from the group consisting of: alkynyl; haloalkyl; haloalkenyl; cycloalkyl; cycloalkenyl; substituted alkyl or substituted cycloalkyl wherein the alkyl or cycloalkyl group is substituted with a substituent selected from the group consisting of alkoxy, alkylthio, oxo, acyl, alkoxycarbonyl, (alkoxyimino) alkyl, ketal, carboxylic acid optionally substituted phenyl, and optionally substituted heterocycle; and optionally substituted heterocycle; 5 R is selected from the group consisting of: alkyl; alkenyl; alkynyl; haloalkyl; haloalkenyl; cycloalkyl; cycloalkenyl; substituted alkyl or substituted cycloalkyl wherein the alkyl or cycloalkyl group is substituted with a substituent selected from the group consisting of alkoxy, alkylthio, oxo, acyl, alkoxycarbonyl, (alkoxyimino) alkyl, betal, carboxylic acid optionally substituted phenyl, and optionally substituted heterocycle; and optionally substituted heterocycle; _ OR 4 5 R and R together with the carbon to which they are attached form a substituted or unsubstituted saturated or partially saturated heterocyclic or carbocyclic ring containing 3 or more ring atoms, which ring may be bridged or fused and may contain substituents selected from the group consisting of hydrogen; 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; oxo; acyl; alkoxy; alkylthio-; alkoxycarbonyl; (alkoxyimino) alkyl; ketal; and carboxylic acid. -53- 2. A compound as claimed in Claim 1, having the general formula (3), (4) or (5) characterized in that R , R and R are as specified in Claim 251, the non-lactone ring is saturated or partially unsaturated and 6 7 8 9 . . R , R , R and R are selected from the group consisting of: hydrogen; halo; alkyl; alkenyl; alkynyl; substituted alkyl wherein the alkyl group is substituted with a substituent selected from the group consisting of halo, alkoxy, alkylthio, optionally 30 substituted phenyl, and optionally substituted heterocycle; optionally substituted phenyl; and optionally substituted hererocycle; oxo; acyl; alkoxy; alkylthio; alkoxycarbonyl; -54- (alkoxyimino)alkyl; ketal; and carboxylic acid. 3. A compound as claimed in Claim 1, having the general formula (6) (6) 1 2 3 characterized in that R , R and R are as specified in Claim 1, the polyatomic ring containing X and Y is a substituted or unsubstituted, saturated or partially saturated, heterocyclic ring containing 5, 6 or 7 ring atoms which may include one or more heteroatoms selected from the group consisting of oxygen, nitrogen, and sulfur, and the ring substituents are selected from the group consisting of: hydrogen; alkyl; alkenyl; oxo; acyl; alkoxy; alkylthio; ketal; alkoxycarbonyl; (alkoxyimino)alkyl; carboxylic acid; substituted alkyl wherein the alkyl group is substituted with a substituent selected from the group consisting of alkoxy, alkythio, optionally substituted phenyl, and optionally substituted heterocycle; optionally substituted phenyl and optionally substituted heterocycle. - - 4. A compound as claimed in Claim 1, which is selected from the group consisting of: 8-[l-(Ethoxyimino)butyl]-9-hydroxy-6-oxaspiro[4.5]dec-8-en-7-one; 8-[l-(Allyloxyimino)butyl]-9-hydroxy-6-oxaspiro[4.5]dec-8-en-7-one; 8-[l-[(2-Chloro-2-propenyl)oxyimino]butyl]-9-hydroxy-6-oxaspiro[4.5]dec-8-en-7- 5 one; 8-[l-[(3-Chloro-2-propenyl)oxyimino]butyl]-9-hydroxy-6-oxaspiro[4.5]dec-8-en-7- one; 8- [ 1 -(Ethoxyimino)propyl] -9-hydroxy-6-oxaspiro[4.5]dec-8-en-7-one; 8-[l-(AUyloxy__mino)propyl]-9-hydroxy-6-oxaspiro[4.5]dec-8-en-7-one; 8-[l-[(2-Chloro-2-propenyl)oxyimino]propyl]-9-hydroxy-6-oxaspiro[4.5]dec-8-en-7- one; 8-[l-[(3-Chloro-2-propenyl)oxyimino]propyl]-9-hydroxy-6-oxaspiro[4.5]dec-8-en-7- 15 one; 8-[l-(Ethoxyimino)butyl]-9-hydroxy-2-methyl-6-oxaspiro[4.5]dec-8-en-7-one; 8-[l-(Allyloxyimino)butyl]-9-hydroxy-2-methyl-6-oxaspiro[4.5]dec-8-en-7-one; ? 0 8- [ 1 - [ (2-Chloro-2-propeny l)oxy imino] butyl] - 9-hydroxy-2-methy 1-6- oxaspiro[4.5]dec-8-en-7-one; 8-[l-[(3-Chloro-2-propenyl)oxyimino]butyl]-9-hydroxy-2-methyl-6- oxaspiro[4.5]dec-8-en-7-one; 258-[l-(Ethoxyimino)propyl]-9-hydroxy-2-methyl-6-oxaspiro[4.5]dec-8-en-7-one; 8-[l-(Allyloxyimino)propyl]-9-hydroxy-2-methyl-6-oxaspiro[4.5]dec-8-en-7-one; 8-[l-[(2-Chloro-2-propenyl)oxyimino]propyl]-9-hydroxy-2-methyl-6- oxaspiro[4.5]dec-8-en-7-one; 30 8-[l-[(3-Chloro-2-propenyl)oxyimino]propyl]-9-hydroxy-2-methyl-6- oxaspiro[4.5]dec-8-en-7- one; 3- [ 1 -(Ethoxyimino)buty 1] -4-hydroxy- 1 -oxaspiro [5.5] undec-3-en-2-one; 3-[l-(AUyloxyin ino)butyl]-4-hydroxy-l-oxaspiro[5.5]undec-3-en-2-one; 35 3-[l-[(2-Chloro-2-propenyl)oxyimino]butyl]-4-hydroxy-l-oxaspiro[5.5]undec-3-en- 2-one; -56- 3-[l-[(3-Chloro-2-propenyl)oxyi ino]butyl]-4-l ydroxy-l-oxaspiro[5.5]undec-3-en- 2-one; 3-[l-(Ethoxyimino)propyl]-4-hydroxy-l-oxaspiro[5.5]undec-3-en-2-one; 3- [ 1 -( Allyloxy imino)propyl]-4-hy droxy- 1-oxaspiro [5.5] undec-3-en-2-one; 3-[l-[(2-Chloro-2-propenyl)oxyimino]propyl]-4-hydroxy-l-oxaspiro[5.5]undec-3- en-2-one; 3-[l-[(3-Chloro-2-propenyl)oxyimino]propyl]-4-hydroxy-l-oxaspiro[5.5]undec-3- en-2-one; 3-[l-(Εthoxyi_mino)butyl]-4-hydroxy-9-methyl-l-oxaspiro[5.5]undec-3-en-2-one; 3-[l-(Aπyloxyi_mino)butyl]-4-hydroxy-9-methyl-l-oxaspiro[5.5]undec-3-en-2-one; 3-[l-[(2-CMoro-2-propenyl)oxyimino]butyl]-4-hydroxy-9-methyl-l- oxaspiro[5.5]undec-3-en-2-one; 3-[l-[(3-Chloro-2-propenyl)oxy__mino]but l]-4-hydroxy-9-metlιyl-l- oxaspiro[5.5]undec-3-en-2-one; 3-[l-(2-Propynyloxyimino)bu^l]-4- ydroxy-9-r etlιyl-l-oxasp_ιo[5.5]undec i 3-en-2- ° ne; 3-[l-[Ethyl 2-propionate)oxy__mino]butyl]-4-hydroxy-9-methyl-l-oxaspiro[5.5]undec- 3-en-2-one; 3-[l-CEthoxy___nino)propyI]-4- ydroxy-9-methyl-l-oxaspiro[5.5]undec-3-en-2-one 3-[l-(Allyloxy__mino)propyl]-4- ydroxy-9-methyl-l-oxaspiro[5.5]undec-3-en-2-one; 3- [1 -[(2-Chloro-2-propenyl)oxy imino]propyl] -4-hydroxy-9-methyl- 1- oxaspiro[5.5]undec-3-en-2-one; 3-[l-[(3 i C oro-2-propenyl)oxyimino]propyll-4-hydroxy-9-methyl-l- oxaspiro [5.5] undec-3-en-2-one; 3-[l-^tiιoxy_-mino)butyl]-4-hydroxy-l-oxaspiro[5.5]undeca-3,7-dien-2-one; 3-[l-(Allyloxyimiao)butyl]-4-hydroxy-l-oxaspiro[5.5]undeca-3,7-dien-2-one; 3-[l-[(2-Chloro-2-propenyl)oxyiinino]butyl]-4-hydroxy-l-oxaspiro[5.5]undeca-3 ) 7- dien-2-one; 3-[l-[(3-Chloro-2-propenyl)oxyimino]butyl]-4-hydroxy-l-oxaspiro[5.5]undeca-3,7- dien-2-one; 3-[l-(Ethoxyimino)propyl]-4-hydroxy-l-oxaspiro[5.5]undeca-3,7-dien-2-one; 3-[l-(Allyloxyi_ι_j-no)propyl]-4-hydroxy-l-oxaspiro[5.5]undeca-3,7-dien-2-one; 3-[l-[(2-Chloro-2-propenyl)oxyimino]propyl]-4-hydroxy-l-oxaspiro[5.5]undeca- 3,7-dien-2-one; 3-[l-[(3-Chloro-2-propenyl)oxyimino]propyl]-4-hydroxy-l-oxaspiro[5.5]undeca- 3,7-dien-2-one; 3-[l-(Ethoxyimino)butyl]-4-hydroxy-l-oxaspiro[5.6]dodec-3-en-2-one; 3-[l-(Allyloxyimino)butyl]-4-hydroxy-l-oxaspiro[5.6]dodec-3-en-2-one; 3-[l-[(2-Chloro-2-propenyl)oxyimino]butyl]-4-hydroxy-l-oxaspiro[5.6]dodec-3-en- 2-one; 3-[ 1 - [(3-Chloro-2-propenyl)oxyimino]buty 1] -4-hydroxy- 1 -oxaspiro[5.6] dodec-3-en- 2-one; 3-[l-(2-Propynyloxyimino)butyl]-4-hydroxy-l-oxaspiro[5.6 dodec-3-en-2-one; 3-[l-(Ethoxy_ιmno)propyl]-4-hydroxy-l-oxaspiro[5.6]dodec-3-en-2-one; 3-[l-(AUyloxyimino)propyl]-4-hydroxy-l-oxaspiro[5.6]dodec-3-en-2-one; 3-[l-[(2-Chloro-2-propenyl)oxyimino]propyl]-4-hydroxy-l-oxaspiro[5.6]dodec-3- en-2-one; 3-[l-[(3-Chloro-2-propenyl)oxyimino]propyl]-4-hydroxy-l-oxaspiro[5.6]dodec-3- en-2-one; 3-[l-(Ethoxyimino)butyl]-4-hydroxy-l-oxaspiro[5.6]dodeca-3,7-dien-2-one; 3-[l-(Allyloxyimino)butyl]-4-hydroxy-l-oxaspiro[5.6]dodeca-3,7-dien-2-one; 3-[l-[(2-Chloro-2-propenyl)oxyimino]butyl]-4-hydroxy-l-oxaspiro[5.6]dodeca-3,7- dien-2-one; 3-[l-[(3-Chloro-2-propenyl)oxyimino]butyl]-4-hydroxy-l-oxaspiro[5.6]dodeca-3,7- dien-2-one; 3-[l-(Ethoxyimino)propyl]-4-hydroxy-l-oxaspiro[5.6]dodeca-3,7-dien-2-one; 3-[l-(Allyloxyimino)propyl]-4-hydroxy-l-oxasp_ro[5.6]dodeca-3,7-dien-2-one; 3-[l-[(2-Chloro-2-propenyl)oxyimino]propyl]-4-hydroxy-l-oxaspiro[5.6]dodeca- 3,7-dien-2-one; 3-[l-[(3-Chloro-2-propenyl)oxyimino]propyl]-4-hydroxy-l-oxaspiro[5.6]dodeca- 3,7-dien-2-one; 8-[l-(Ethoxyimino)butyl]-9-hydroxy-6-oxa-2-thiaspiro[4.5]dec-8-en-7-one; 8-[l-(AUyloxyimino)butyI]-9-hydroxy-6-oxa-2-thiaspiro[4.5]dec-8-en-7-one; 8-[l-[(2-Chloro-2-propenyl)oxyimino]butyl]-9-hydroxy-6-oxa-2-thiaspiro[4.5]dec-8- en-7-one; 8-[l-[(3-Chloro-2-propenyl)oxyimino]butyl]-9-hydroxy-6-oxa-2-thiaspiro[4.5]dec-8- en-7-one; 8-[l-(Εl_hoxyimino)propyl]-9-l ydroxy-6-oxa-2-thiaspiro[4.5]dec-8-en-7-one; 8-[l-(AUyloxyiπ_ino)propyll-9-hydroxy-6-oxa-2-thiaspiro[4.5]dec-8-en-7-one; 8-[l-[(2-CMoro-2-propenyl)oxyi τώιo]propyl]-9-hydroxy-6-oxa-2-thiaspiro[4.5]dec- 8-en-7-one; 8-[l-[(3-CMoro-2-propenyl)oxyimino]propyl]-9-lιydroxy-6-oxa-2-thiaspiro[4.51dec- 8-en-7-one; 3-[l-(Et_boxyimino)butyl]-4-hydroxy-l-oxa-8-t_hiaspiro[5.5]undec-3-en-2-one; 3-[l-(AUyloxyi_mino)butyl]-4-hydroxy-l-oxa-8-thiaspiro[5.5]undec-3-en-2-one; 3-[l-[(2-Chloro-2-propenyl)oxyimino]butyl]-4-hydroxy-l-oxa-8-thiaspiro[5.5]undec- 3-en-2-one; 3-[l-[(3-Chloro-2-prorιenyl)oxyiminolbutyl]-4-hydroxy-l-oxa-8-thiaspiro[5.5]undec- 3-en-2-one; 3-[l-(Ethoxyimino)propyl]-4-hydroxy-l-oxa-8-thiaspiro[5.5]undec-3-en-2-one; 3-[l-(Allyloxyimino)propyl]-4-hydroxy-l-oxa-8-thiaspiro[5.5]undec-3-en-2-one; 3-[l-[(2-Chloro-2-propenyl)oxyimino]propyl]-4-hydroxy-l-oxa-8- thiaspiro[5.5]undec-3-en-2-one; 3- [ 1- [(3-Chloro-2-propeny l)oxy iminojpropyl] -4-hy droxy- 1 -oxa-8- tbiaspiro[5.5]undec-3-en-2-one; 3-[l-(Ethoxyi_mino)butyl]-4-hydroxy-l-oxa-9-thiaspiro[5.5]undec-3-en-2-one; 3-[l-(Allyloxyimino)butyl]-4-hydroxy-l-oxa-9-thiaspiro[5.5]undec-3-en-2-one; 3- [ 1 - [(2-Chloro-2-propeny l)oxyimino] butyl]-4-hydroxy- 1 -oxa- ' 9-thiaspiro[5.5] undec- ' 3-en-2-one; 3- [ 1 -[(3-Chloro-2-propenyl)oxy imino] buty 1] -4-hydroxy- 1 -oxa-9-thiaspiro[5.5] undec- 3-en-2-one; 3-[l-(Ethoxyimino)propyl]-4-hydroxy-l-oxa-9-thiaspiro[5.5]undec-3-en-2-one; 3-[l-(Allyloxyimino)propyl]-4-hydroxy-l-oxa-9-thiaspiro[5.5]undec-3-en-2-one; 3- [ 1 -[(2-Chloro-2-propeny l)oxyimino]propyl]-4-hydroxy- 1 -oxa-9- thiaspiro[5.5]undec-3-en-2-one; 3-[l-[(3-Chloro-2-propenyl)oxyimino]propyl]-4-hydroxy-l-oxa-9- thiaspiro[5.5]undec-3-en-2-one; 3-[l-(Ethoxyimino)butyl]-4-hydroxy-l-oxa-8,ll-dithiaspiro[5.6]dodec-3-en-2-one; 3-[l-(AUyloxyimino)butyl]-4-hydroxy-l-oxa-8,l l-dithiaspiro[5.6]dodec-3-en-2-one; 3-[l-[(2-Chloro-2-propenyl)oxyimino]butyl]-4-hydroxy-l-oxa-8,l l- dithiaspiro[5.6]dodec-3-en-2-one; 3-[l-[(3-Chloro-2-propenyl)ox ' yimino]butyl]-4-hydroxy-l-oxa-8,l l- dithiaspiro[5.6]dodec-3-en-2-one; 3- [ 1 -(Ethoxyimino)propyl]-4-hydroxy- 1 -oxa-8, 1 l-dithiaspiro[5.6]dodec-3-en-2-one; 3-[l-(AUyloxyimino)propyl]-4-hydroxy- l-oxa-8, 1 l-dithiaspiro[5.6]dodec-3-en-2- one; 3-[ 1 -[(2-Chloro-2-propeny l)oxy imino] propy 1] -4-hydroxy- 1 -oxa- 8,11- dithiaspiro [5.6] dodec-3 -en-2-one; 3-[l-[(3-Chloro-2-ρropenyl)oxyimino]propyl]-4-hydroxy-l-oxa-8,l l- dithiaspiro [5.6] dodec-3 -en-2-one; -60- 5. A compound as claimed in Claim 1, which is selected from the group consisting of : 6-cycloprop l-3- ( 1 -( ethoxyiπino ) butyl] -4-hydroxy-6-methyl- 5 , 6-dihydro-2H-ρyran-2-one; 3-[ 1 -(ethoxyimino) butyl] -4-hydroxy-6-methyl.-6-( 2-thienyl)- S, 6-dihydro-2H-pyran-2-one; 3-[ 1 -< ethoxyimino ) butyl] -4-hydroxy-7-methyl-1 - " 0 oxaspiro[S.5]undec-3-en-2-one; 3-[1-ethoxyimino)butyl]-4-hydroxy-8-methyl-1- oxaspiro[5.5]undec-3-en-2-one; 5 8,10-dimethyl-3-[1-(ethoxyimino)butyl]-4-hydroxy-1- oxaspiro[5.-5]undec-3-en-2-one; 3-[1-(ethoxyimino)butyl)-9-eth l-4-hydroxy-1- oxaspiro[5.5]undec-3-en-2-one; 0 9-tert-butyI-3-[1-(ethoxyimino)butyl)-4-hydroxy-1- oxaspiro[5.5]undec-3-en-2-one; 3-T1-(ethoxyimino)butyl)-4-hydroxy-1-oxaspiro [S .7]tridec-3- en-2-one; 5 3- [ 1 -( ethoxyimino )but l ) - -hydroxy-1 -oxaspiro ( 5.9 ] pentadec-3 - en-2-one; 3- [ 1 -{ ethoxyimino )butyl) -4 -hydroxy-1 -oxaspiro [5.1 1 ]heptadec- 0 3-en-2-one; S' -f1 -( allyloxyimino)butyl)-4' -hydroxyspiro [norbornane-2, 2 ( 3 ) -6 " ; H-pyran-6' -one] ; S -( 1-(ethoxyimino)butyl)-4" -hydroxyspiro [norbornane- 3 5 * ÷ 2, 2 ( 3 R ) - ji-pyran-6' -one ] ; S' - [ 1 - ( e th oxyimino )pro p yl )-4' -hydroxyspirotnorbornane- 2, 2' ( 3'jO-6"^-p ran-6' -one] ; 5-[1-(ethoxyimino)butyl)-4-hydroxyspiro[6H_-pyran-6-one- 2 (3 R ) , 1 ' -( ' ,2' , 3" , A -tetrahydronaphthalene)]; » 5" -f1-(allyloxyimino)butyl)-4'-hydroxyspiro [perhydronaphthalene-1 X ( -one]; s" -[1-(ethoxyimino)butyl)-4 -hydroxyspiro [perhydronaphthalene-1 , 2" (3"j -6'jT-pyran-6'-one]; and 5"-[1- (ethoxyimino)ρropyl]-4' -hydroxyspiro [perhydronaphthalene-1 , l' ( 'H)-6"H-pyran-6'-one]. -62- 6. A compound as claimed in any one of Claims 1 to -3, characterized in that R is hydrogen or an alkali metal cation. 7. A compound as claimed in any one of Claims 1 to 3 and 6, 2 cchhaarraacctteerriizzeedd in that R is ethyl, allyl, 2-chloroallyl or 5 3-chloroallyl. 8. A compound as claimed in any one of Claims 1 to 3, 6 and 7, characterized in that R is ethyl or n-propyl. 10 9. A compound as claimed in Claim 2 or Claim 3 characterized in that R , R , R and R in formulae (3),(4) and (5) or the substituents on the polyatomic chain Xϊ in formula (6) are hydrogen or methyl. * 15 10. A process for preparing a compound of the general formula (2) as stated and defined in Claim 1, characterized in that a compound of the general formula (8), 3 4 5 wherein R , R and R are as defined in Claim 1, is reacted 2 with an 0-substituted hydroxylamine of the formula R ONH , 2 2 30 wherein R is as defined in Claim 1, to yield a compound of formula (2), wherein R = H and thereafter, if desired converting the compound thus obtained by a known method to a compound in which R is other than H. 35 -63- 11. A process as claimed in Claim 10, characterized in that the compound of formula (8) is prepared by acylating and isomerizing a 4 4 . „5b ccoommppoouunndd ooff ffoorrmmuullaa ((77)),, wwhheerreeiinn IR and R are as defined in Claim 1, by a Fries rearrangement. 12. A process as claimed in Claim 11, characterized in that the 5 compound of formula (7) is prepared by reacting the di-anion (a) of an acetoacetate ester wherein M is Li or Na with a ketone 4 5 (b), wherein R and R are as defined in Claim 1, ( ~ CH C0C ~ H 2 C00R)Li + M + R 4 -C0-R 5 0 (a) (b) and cyclizing the resulting product, with or without intermediate hydrolysis. 13. A plant growth inhibiting, plant damaging, or plant killing 5 composition comprising a compound of formula (2), as defined in Claim 1, and an inert carrier therefor. 14. 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 0 growth medium of the plant, an effective amount of a compound of formula (2), as defined in Claim 1. -64- 15. A method for selectively inhibiting, damaging or killing weed grasses in a broad-leaf crop which comprises applying to the crop or its locus an effective amount of a compound of formula (2), as defined in Claim 1. 16. A herbicidal composition comprising a compound of formula (2), as defined in Claim 1, and at least one other herbicide. 17. A plant growth regulating composition comprising a compound of formula (2), as defined in Claim 1, and an inert carrier therefor. 18. The use of a compound of formula (2) as a herbicide or plant growth regulator. . 19. A compound of formula (7) as stated and defined in Claim 11. 20. A compound of formula (8) as stated and defined in Claim 10.

Inventors: ANDERSON-MCKAY JANET ELIZABETH, LIEPA ANDRIS JURIS, ANDERSON-MCKAY, JANET, ELIZABETH, LIEPA, ANDRIS, JURIS
Applicants: DUNLENA PTY LTD, DUNLENA PTY. LIMITED
Application year: 1987
Main classification: C07D309
IPC codes: A01N43, C07D309, C07D311, C07D409, C07D495