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European Patent Office 00 Publication Number: 0 302 599 Office Europeen Des Brevets A2 Europaisches Patentamt $ European Patent Office 00 Publication number: 0 302 599 Office europeen des brevets A2 EUROPEAN PATENT APPLICATION @ Application number: 88306197.0 int. ci.4: C07D 493/08 , C07D 493/20 C07D 497/08 , C07D 493/18 (§) Date of filing: 07.07.88 A01N 43/90 , //(C07D493/08, 317:00,31 1 :00),(C07D493/08, 31 9:00,31 1 :00),(C07D493/20, 317:00,311:00,311:00), (C07D493/1 8,31 7:00,31 1 :00, 303:00),(C07D497/08,327:00, 311:00) The title of the invention has been amended © Applicant: HER MAJESTY THE QUEEN IN (Guidelines for Examination in the EPO, A-lll, RIGHT OF NEW ZEALAND DEPARTMENT OF 7.3). SCIENTIFIC AND INDUSTRIAL RESEARCH CHEMISTRY DIVISON Gracefield Road Priority: 08.07.87 NZ 221006 Lower Hutt(NZ) 08.07.87 NZ 221007 08.07.87 NZ 221008 © Inventor: Furneaux, Richard Hubert 08.07.87 NZ 221009 35 Huntingdon Street Wilton Weilington(NZ) Date of publication of application: Inventor: Mason, Jennifer Mary 08.02.89 Bulletin 89/06 11 Rakeiora Grove Petone(NZ) Designated Contracting States: Inventor: Tyler, Peter Charles AT BE CH DE ES FR GB GR IT LI LU NL SE 143CreswickTce Northland Wellington(NZ) Inventor: Blattner, Regine 281 B Muritai Drive Eastbourne(NZ) Inventor: Lawson, Kevin Robert High Style Piddington Lane Piddington High Wycombe, Bucks HI11 2BB(GB) Inventor: Chrystal, Ewan James Turner CM 7 Coombe Pine Crown Wood < Bracknell Berkshire RG12 3TG(GB) Inventor: Mitchell, Glynn CO 159 High Street If) Iver, Bucks SL0 9OB(GB) Inventor: Pilkington, Brian Leslie o 9 Highway Road CO Maidenhead Berkshire SL6 5AE(GB) © Representative: Holmes, Michael John et al 0. UJ Frank B. Dehn & Co. Imperial House 15-19 Kingsway London WC2B 6UZ(GB) Xerox Copy Centre EP 0 302 599 A2 © Bicyclo-octane and bicyclo-nonane derivatives, processes for their preparation and their use as herbicides. @ Bicyclo-octane and bicyclo-nonane derivatives are described having herbicidal and plant growth regulating properties. The derivatives are based on the general formula (I) •Rl R4 X EP 0 302 599 A2 Chemical Compounds and Compositions The present invention relates to bicyclo-octane and -nonane derivatives and their analogues, processes for their production and their use as herbicides and plant growth regulants. The compounds of the invention have the formula (I) (I) 10 •ai 75 in which R1 represents a hydrogen or halogen atom, an O-, N-, P- or S-linked organic or optionally substituted 20 hydrocarbyl group or R\ together with X, E or Z, may form an optionally substituted fused alicyclic or heterocyclic member; R2 represents a hydrogen or fluorine atom, a hydroxy group or an optionally substituted hydrocarbyl or O-linked hydrocarbyl group or R2, together with X, may form a ketonic oxygen atom -0- or a group of the formula -CH2O-; 25 R3 represents a hydrogen or halogen atom, a hydroxy group or an optionally substituted hydrocarbyl or O-linked hydrocarbyl group or R3, together with R*, may form an optionally substituted hydrocarbyl group; R* represents a hydrogen or halogen atom, a hydroxy group or an optionally substituted hydrocarbyl or O-linked hydrocarbyl group 30 or R*, together with X, may form an oxygen atom; R5 represents an optionally substituted aralkyl, alicyclicalkyl, heterocyclicalkyl, aryl, alicyclic, heterocyclic, alkyl, alkenyl or alkynyl group R6 represents a hydrogen atom or an optionally substituted hydrocarbyl group; R7 represents a hydrogen or halogen atom, an O-, N-, P- or S-linked organic or optionally substituted 35 hydrocarbyl group or together with M or E, R7 may form an optionally substituted fused alicyclic or heterocyclic member; X represents an O-, N- or S-linked organic group, an optionally substituted hydrocarbyl group, a halogen atom, a hydroxy, amino, alkoxyamino, nitro, cyano, azido, sulpho or phospho group, M, E and Z 40 independently of each other represent an 0 or S atom, a sulphinyl, sulphonyl, amino, phosphinico or re- linked organic group, a single bond, or the group CR8R3, wherein Ra represents a hydrogen or halogen atom, an O-, N-, P- or S-linked organic or optionally substituted hydrocarbyl group, a hydroxy, amino, alkoxyamino, nitro, cyano, azido, sulpho or phospho group or R8, together with R9, may form an optionally substituted spiroalicyclic or spiroheterocyclic member, an 45 optionally substituted hydrocarbyl group or a double bonded oxygen atom; and wherein R9 represents a hydrogen or halogen atom, an O-, N-, P- or S-linked organic or optionally substituted hydrocarbyl group, a hydroxy, amino, alkoxyamino, nitro, cyano, azido, sulpho or phospho group or; and wherein, adjacent M, E or Z groups may be joined by a double bond; and 50 wherein, two or more of M, E and Z may form an optionally substituted fused alicyclic or heterocyclic ring; with the proviso that only one of the group M, E or Z may represent a single bond; J represents an O or S atom, a sulphinyl, sulphonyl, amino, phosphinico or N-linked organic group or an optionally substituted hydrocarbyl group; and the enantiomers, salts and mixtures thereof; with the following provisos: EP 0 302 599 A2 (i) when one of M, E and Z is a single bond and J is an oxygen atom then at least one of the remainder of M, E and Z represents an 0 or S atom, a sulphinyl, suiphonyl, amino, phosphinico or N-linked organic group or the group CR8R3, in which at least one of R8 or R9 is not a hydrogen atom or O-linked organic or optionally substituted hydrocarbyl group; (ii) when -M-E-Z- is -OCH2-, J is an 0 atom, X and R5O are the same aralkoxy group, and R1 is hydrogen, then the enantiomer thereof is not included; (iii) when -M-E-Z- together form the group -CH2O-, J is an oxygen atom, R7 is a hydrogen atom, and R5 is an optionally substituted araikyi group, then (a) R1 represents an O-, N-, P- or S-linked organic group; or 10 (b) R\ together with X, forms an optionally substituted fused alicyclic or heterocyclic member; or (c) R2 represents a fluorine atom; or (d) R3 or R+ represents a halogen atom; or (e) R3, together with R*. forms an optionally substituted hydrocarbyl group; or (f) R*, together with X, forms an oxygen atom; 75 (iv) when -M-E-Z- is -OCH2-, J is an oxygen atom, R1 is a hydrogen atom and X is an optionally substituted aralkoxy group, then (a) R2 represents a fluorine atom; or (b) R3 or R* represents a halogen atom; or (c) R3, together with R+, forms an optionally substituted hydrocarbyl group; or 20 (d) R\ together with X, forms an oxygen atom; (v) when J is 0, -M-E-Z- is -CH2O- and R1 and R7 both represent a hydrogen atom then: (a) OR5, X and R3 are not the same substituted alkyloxy group; (b) when R3 is a hydroxy or O-linked organic group, X is a fluorine atom, or a hydroxy, O-linked organic, amino, azido, methyl, acetamido or benzylamino group, R5 is not an unsubstituted C1-C+ alkyl or 25 C2-C* alkenyl or a tetrahydrofuran-1 -methyl group in which each of the 2, 3 and 4 positions is substituted with an O-linked organic or hydroxy group; or a substituted alkyl group where the substituent is O-linked or contains oxygen as the only heteroatom; and (vi) when -M-E-Z- is -CR8R3O-, R8 is an exo-ethyl or exo-fluoro group and R\ R7 and R9 are hydrogen, then OR5, X and R3 are not all benzyloxy; 30 (vii) when -M-E-Z- is -CH2O-, J is an oxygen atom, and R1, R2, R3, Rs and R7 are hydrogen atoms, then RSO, R* and X are not all methoxy groups; (viii) when -M-E-Z- is -C(phenyl)20-, J is an oxygen atom, and R1, R2, R*. R6 and R7 represent hydrogen atoms then R5O, R3 and X are not all methoxy; (ix) when -M-E-Z- is -CH2O-, R5 is methyl, J is an oxygen atom, R1, R3, R\ Rs and R7 are hydrogen 35 atoms then X and R2 are not jointly an oxygen atom, or not both hydroxy or methoxy groups or X is not hydroxy when R2 is a hydrogen atom. Whilst the invention excludes in provisos (v) to (ix) compounds known in the art, the prior art does not suggest any herbicidal or plant growth regulating activity for those compounds. Throughout this specification and claims the six-membered ring bearing the R5O and X substituents in 40 the structural formulae is given according to the Hawarth projection wherein the ring substituents are indicated as being above or below the plane of the ring. Hydrogen atoms are not indicated. The typical stable conformation of this six membered ring in these compounds is the chair form shown in formula (A) 45 (A) 50 55 In some circumstances the chair form may be distorted with substituents X, R3 and R5O becoming wholly or partially equatorial. Preferred compounds of formula (I) for the present invention include those compounds wherein EP 0 302 599 A2 R1 represents a hydrogen atom or an optionally substituted hydrocarbyl group of Ci -6 carbon atoms; R2 represents a hydrogen atom; R3 represents a hydrogen atom; R* represents a hydrogen atom; 5 R5 represents a benzyl, methylbenzyl, benzothienyl, 2-thiophenemethyl, 3-thiophenemethyl, indan-2-yl, tetrahydropyran-2-ylmethyl, (Cs-s-cycloalkyl)methyl, 2-alkyl-alkyl or cycloalkenemethyl group optionally substituted with up to two substituents independently chosen from chlorine, bromine or fluorine atoms, a methoxy group or a Ci -3 alkyl group optionally substituted with up to three fluorine atoms; R6 represents a hydrogen atom; 70 R7 represents a hydrogen atom or an optionally substituted hydrocarbyl group of d-s carbon atoms; M, E or Z independently represent an 0 or S atom, an amino, sulphinyl, sulphonyl or Ci -6 alkylamino group, a single bond, a Ci-s alkylene group or the group -CR8R9- wherein R8 represents a hydrogen, fluorine, chlorine or bromine atom, an optionally substituted hydrocarbyl group of 75 Ci.6 carbon atoms or an alkylthio group; R9 represents a hydrogen, fluorine, chlorine or bromine atom, an optionally substituted hydrocarbyl group of Ci -s carbon atoms, or an alkylthio group; X represents a Ci -s alkoxy group, an optionally substituted hydrocarbyl group of Ci -6 carbon atoms, a fluorine, chlorine or bromine atom or an azido group; 20 J represents an 0 or S atom, an amino or a Ci -s alkyiamino group or a Ct -s alkylene group.
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