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WO2005123667A1 - Bicyclooctenes substitues et leur utilisation en tant qu'herbicides - Google Patents

Bicyclooctenes substitues et leur utilisation en tant qu'herbicides Download PDF

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WO2005123667A1
WO2005123667A1 PCT/EP2005/006707 EP2005006707W WO2005123667A1 WO 2005123667 A1 WO2005123667 A1 WO 2005123667A1 EP 2005006707 W EP2005006707 W EP 2005006707W WO 2005123667 A1 WO2005123667 A1 WO 2005123667A1
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alkyl
alkoxy
alkylthio
alkoxycarbonyl
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Renaud Beaudegnies
Christoph Lüthy
Andrew Edmunds
Jürgen Schaetzer
Sebastian Wendeborn
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Syngenta Participations Ag
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    • C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
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    • C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
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    • C07C45/512—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups the singly bound functional group being a free hydroxyl group
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    • C07C45/56—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds
    • C07C45/57—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with oxygen as the only heteroatom
    • C07C45/59—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with oxygen as the only heteroatom in five-membered rings
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    • C07C49/385—Saturated compounds containing a keto group being part of a ring
    • C07C49/417—Saturated compounds containing a keto group being part of a ring polycyclic
    • C07C49/423—Saturated compounds containing a keto group being part of a ring polycyclic a keto group being part of a condensed ring system
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    • C07C49/617—Unsaturated compounds containing a keto groups being part of a ring polycyclic a keto group being part of a condensed ring system
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    • C07C49/703—Unsaturated compounds containing a keto groups being part of a ring containing hydroxy groups
    • C07C49/723—Unsaturated compounds containing a keto groups being part of a ring containing hydroxy groups polycyclic
    • C07C49/727—Unsaturated compounds containing a keto groups being part of a ring containing hydroxy groups polycyclic a keto group being part of a condensed ring system
    • C07C49/733—Unsaturated compounds containing a keto groups being part of a ring containing hydroxy groups polycyclic a keto group being part of a condensed ring system having two rings
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    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/76—Ketones containing a keto group bound to a six-membered aromatic ring
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    • C07D261/02—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings
    • C07D261/04—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
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    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
    • C07D307/10—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
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    • C07C2602/00—Systems containing two condensed rings
    • C07C2602/36—Systems containing two condensed rings the rings having more than two atoms in common
    • C07C2602/44—Systems containing two condensed rings the rings having more than two atoms in common the bicyclo ring system containing eight carbon atoms

Definitions

  • the present invention relates to novel, herbicidally active benzoyl derivatives, to processes for their preparation, to compositions comprising those compounds, and to their use in controlling weeds, especially in crops of useful plants, or in inhibiting plant growth.
  • Benzoyl derivatives of bicyclo[3.2.1]oct-3-en-2-ones having herbicidal action are known and are described, for example, in US 5,801 ,120, WO 00/37437, WO 04/024687 and WO 03/074475.
  • Novel benzoyl derivatives having herbicidal and growth-inhibiting properties the structures of which are distinguished by a double bond at the 6,7-position of the bicyclo[3.2.1]oct-3-en-2- ones and of the related bicyclo[3.2.2]nona-3-en-2-one, 8-oxa-bicyclo[3.2.1]octa-3-en-2-one, 8-aza-bicyclo[3.2.1]octa-3-en-2-one, 8-thia-bicyclo[3.2.1]octa-3-en-2-one and bicyclo[3.2.1]- octa-3-en-2,8-dione systems have now been found.
  • the present invention accordingly relates to compounds of formula I
  • R 4a and R 5a are each independently of the other hydrogen, CrC 6 alkyl, d-Cehaloalkyl, cyano, formyl, CrC 6 alkylcarbonyl, C ⁇ -C 6 alkoxycarbonyl, carbamoyl, C- ⁇ -C 6 alkylaminocarbonyl, di(C C 6 alkylamino)carbonyl, di(C 1 -C 6 alkylamino)sulfonyl, C 3 -C 6 cycloalkylcarbonyl, C C 6 - alkylsulfonyl, phenylcarbonyl, phenylaminocarbonyl or phenylsulfonyl, wherein the phenyl groups may in turn be substituted one, two, three, four or five times by C ⁇ -C 6 alkyl, CrC 6 - haloalkyl, C C 6 alkoxy, CrC 6 haloalkoxy, halogen, cyano, hydroxy and
  • R 6a is hydrogen, CrC 6 alkyl, CrC 6 alkylcarbonyl or CrC ⁇ alkylcarbonyloxy;
  • R 6b is hydrogen or C- ⁇ -C 6 alkyl; or R 6a together with R 6b is a C 2 -C 5 alkylene chain;
  • a T is nitrogen or CR 7 ;
  • a 2 is nitrogen or CR 8 ;
  • R-i, R 2 , R 6 , R 7 and R 8 are each independently of the others hydrogen, C ⁇ -C 6 alkyl, C 2 -C 6 - alkenyl, C 2 -C 6 alkynyl, halogen, hydroxy, mercapto, nitro, cyano, CrC 6 alkoxycarbonyl, CrC 6 - alkylcarbonyl, formyl, hydroxyiminomethylene, C ⁇ -C 6 alkoxyiminomethylene, CrC 6 alkoxy, CrC 6 haloalkoxy, C 3 -C 6 alkenyloxy, C 3 -C 6 alkynyloxy, CrC alkoxy-C ⁇ -C 2 alkoxy, CrC 6 alkoxy- carbonyloxy, CrC 6 alkylcarbonyloxy, C ⁇ -C 6 alkylthio, C ⁇ -C 6 alkylsulfonyl, C- ⁇ -C 6 alkylsulfinyl, N(R 9 R ⁇ o), tri(
  • R 1 ; R 2 , Re, R 7 and R 8 are each independently of the others a methyl, vinyl or ethynyl group which is substituted once, twice or three times or, as applicable, once by halogen, hydroxy, mercapto, nitro, cyano, formyl, C C 6 alkoxy, C 3 -C 6 alkenyloxy, C 3 -C 6 alkynyloxy, C C 6 halo- alkoxy, C ⁇ -C 4 alkoxy-CrC 2 alkoxy, CrC 4 alkoxycarbonyloxy, C C 4 alkylcarbonyloxy, C C 4 - alkoxycarbonyl, C C alkylcarbonyl, CrC 6 alkylthio, C C 6 alkylsulfinyl, CrC 6 alkylsulfonyl, N(R ⁇ 2 R ⁇ 3 ), C 3 -C 6 cycloalkyl, tri(C C 6 alkyl)silyl, phenyl
  • R L R 2 , Re, R 7 and R 8 are each independently of the others a C 2 -C 6 alkyl, C 3 -C 6 alkenyl or C 3 -C 6 alkynyl group which is interrupted once or twice by oxygen, sulfur, sulfinyl, sulfonyl, -N(R 15 )- and/or by -C(O)-, with the proviso that two oxygen atoms, two sulfur atoms and/or an oxygen atom and a sulfur atom cannot be adjacent to one another, and/or is substituted one or more times by hydroxy, mercapto, nitro, cyano, halogen, formyl, d-C ⁇ alkoxy, C 3 -C 6 - alkenyloxy, C 3 -C 6 alkynyloxy, C ⁇ -C 6 haloalkoxy, d-C ⁇ lkoxy-d-Caalkoxy, C ⁇ -C 4 alkoxy- carbonyloxy, C ⁇
  • R 6 or two substituents R 6 at different carbon atoms together form an oxygen bridge or a C ⁇ -C 4 alkylene chain which may in turn be substituted one or more times by R 6d ;
  • Rg, i 3 , R 15 and R 17 are each independently of the others hydrogen, d-C 6 alkyl, d-C 6 halo- alkyl, d-C 6 alkylcarbonyl, d-C 6 alkoxycarbonyl, d-C 6 alkylsulfonyl or U 9 ;
  • 6 are each independently of the others hydrogen or d-C 6 alkyi;
  • Re c , Re and R 6e are each independently of the others C C 6 alkyl or d-C 6 haloalkyl;
  • R 3 is hydroxy, O " M + , halogen, d-C 8 alkoxy, mercapto, d-C 8 alkylthio, d-C 8 alkylsulfinyl, d-C 8 alkylsulfonyl, C ⁇ -C 8 haloalkylthio, C C 8 haloalkylsulfinyl, d-C 8 haloalkylsulfonyl, d-C 4 - alkoxy-d-C 4 alkylthio, d-C alkoxy-d-C alkylsulfinyl, C- ⁇ -C 4 alkoxy-C C 4 alkylsulfonyl, C 3 -C 8 - alkenylthio, C 3 -C 8 alkynylthio, d-C 4 alkylthio-C C 4 alkylthio, C 3 -C 4 alkenylthio-d-C 4 alkylthi
  • Q is a phenyl group having one, two, three or four identical or different R 02 substituent(s);
  • each R 02 independently of any other(s) is halogen, C ⁇ -C 6 alkyl, C ⁇ -C 6 haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C 2 -C 6 alkynyl, C 2 -C 6 haloalkynyl, C Cealkoxy, d-C 6 haloalkoxy, C 3 -C 6 - alkenyloxy, C 3 -C 6 haloalkenyloxy, C 3 -C 6 alkynyloxy, C 3 -C 6 haloalkynyloxy, d-C 6 alkoxy- C ⁇ -C 6 alkoxy, cyano-CrC 6 alkoxy, cyano-d-C 6 alkenyloxy, d-Cealkoxycarbonyl-d-Cealkoxy, aminocarbonyl-C ⁇ -C 6 alkoxy, Ci-Cealkylaminocarbonyl
  • cyano, hydroxy, nitro, phenyl, phenoxy or by benzyloxy wherein the phenyl, phenoxy or benzyloxy group may in turn be substituted one, two, three, four or five times on the phenyl group by C C 3 alkyl, d-C 3 haloalkyl, d-C 3 alkoxy, d-C 3 haloalkoxy, halogen, cyano or by nitro, and wherein the substituents on the nitrogen atom in such a three- to ten-membered monocyclic or bicyclic ring system are other than halogen;
  • R 016 , R 017 , R 033 and R 034 are each independently of the others hydrogen or d-C 6 alkyl; n 0 ⁇ is 0, 1 or 2; R 015 is C C 6 alkyl;
  • R 039 is hydrogen, C C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, d-C 6 haloalkyI or d-C 4 alkoxy- d-C 6 alkyl;
  • Ro ⁇ 8 and R 024 are each independently of the other hydrogen, d-C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, d-C 6 haloalkyl, C C alkoxy-d-C 6 alkyl, phenyl or benzyl, wherein the phenyl- containing groups may in turn be substituted one, two, three, four or five times on the phenyl group by halogen, C ⁇ -C alkyl, d-C 2 haloalkyl, d-C 2 alkoxy, d-C 2 haloalkoxy or by nitro;
  • R 04 o is d-C 6 alkoxy, C 3 -C 6 alkenyloxy, C 3 -C 6 alkynyloxy, CrC 6 haloalkoxy, benzyloxy, C ⁇ -C 6 - alkylamino, di(C 1 -C 6 alkyl)amino, phenylamino, N-(CrC 6 alkyl)phenylamino or U 7 , wherein the phenyl-containing groups may in turn be substituted one, two, three, four or five times on the phenyl group by halogen, d-C 4 alkyl, d-C 2 haloalkyl, d-C 2 alkoxy, d-C 2 haloalkoxy or by nitro;
  • R052 is hydroxy, d-C 6 alkoxy, C 3 -C 6 alkenyloxy, C 3 -C 6 alkynyloxy, benzyloxy, cyano or nitro; Ro 4 6, Ro 4 7> R 04 8. o5o, R0511 o 4 6a. Ro 7a. Ro 4 8a, Ro5oa. Roeia, Ro53 and R 0 53a are each independ ⁇ ently of the others hydrogen or d-C 6 alkyl;
  • R 0 9 and R 049a are each independently of the other C ⁇ -C 6 alkyl, C- ⁇ -C 6 haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C 2 -C 6 alkynyl, C 2 -C 6 haloalkynyl, C 3 -C 6 cycloalkyl, C 3 -C 6 cycloalkyl-d-C 3 alkyl, d-C ⁇ lkoxy-d-Csalkyl, C ⁇ -C 4 alkylthio-C C 3 alkyl, d-C 4 alkylsulfinyl-CrC 3 alkyl, C C 4 alkyl- sulfonyl-CrC 3 alkyl, cyano-C C 3 alkyl, hydroxy-d-C 3 alkyl, d-C 6 alkylcarbonyloxy-d-C 3 alkyl, d-C 4 alk
  • Ro 4 ⁇ , Ro 2 , Ro 3 and R 0 are each independently of the others hydrogen, d-C 6 alkyl, C 2 -C 6 - alkenyl, C 2 -C 6 alkynyl, CrC 6 haloalkyl, Crdalkoxy-d-dalkyl, phenyl or benzyl, wherein the phenyl-containing groups may in turn be substituted one, two, three, four or five times on the phenyl group by halogen, d-C alkyl, C C 2 haloalkyl, C C 2 alkoxy, C C 2 haloalkoxy or by nitro;
  • R 028 is d-C 6 alkoxy, d-C 3 alkoxy-CrC 3 alkoxy, C ⁇ -C 6 haloalkoxy, C ⁇ -C 4 alkoxycarbonyl, d-C ⁇ - alkylthio, C C 6 alkylsulfinyl, d-C 6 alkylsulfonyl, phenyl, phenoxy or benzyloxy, wherein the phenyl-containing groups may in turn be substituted one, two, three, four or five times on the phenyl group by d-C 3 alkyl, d-C 3 haloalkyl, d-C 3 alkoxy, C C 3 haloalkoxy, halogen, cyano or by nitro;
  • R 029 and R 03 o are each independently of the other hydrogen or d-C 6 alkyl; or R 029 together with R 030 , together with the nitrogen atom to which they are bonded, form a three- to seven-membered ring system in which a carbon atom of the ring system may have been replaced by oxygen, sulfur, sulfinyl, sulfonyl or by -N(R 07 b)-;
  • R 07b being hydrogen, d-Cealkyl, d-C ⁇ haloalkyl, d-C 4 alkoxycarbonyl, d-C 4 alkylcarbonyl or di(C C 4 alkyl)aminocarbonyl or phenyl, wherein the phenyl group may in turn be substituted one, two, three, four or five times by d-C 4 alkyl, d-C 4 haloalkyl, d-C 4 alkoxy, C C 4 halo- alkoxy, d-C 4 alkylcarbonyl, d-C 4 alkoxycarbonyl, C C alkylamino, di-C C alkylamino, d-C 4 alkylthio, d-C 4 alkylsulfinyl, C ⁇ -C 4 alkylsulfonyl, C C 4 alkylsulfonyloxy, C ⁇ -C 4 haloalkyl- thio, d-C
  • R 020 is d-C 6 alkoxy, CrC 3 alkoxy-d-C 3 alkoxy, C-
  • X 02 is oxygen, sulfur or NR0 1 2; R 012 is hydroxy or d-C 4 alkoxy;
  • each Ron independently of any other(s) is halogen, C-
  • R 3b and R 0 ⁇ 4b are each independently of the other hydrogen or C C 6 alkyl
  • R 02 o b is d-Cealkoxy, d-Csalkoxy-d-dalkoxy, d-C 6 haloalkoxy, d-C 4 alkoxycarbonyl,
  • X 03 is oxygen, sulfur or NR 045a ;
  • Ro 4 5 a is hydrogen or d-C 6 alkyl
  • R 25 is hydrogen, hydroxy, d-C 6 alkyl, d-C 6 haloalkyl, d-C 6 alkoxy, d-C 6 alkylcarbonyl, C ⁇ -C 6 alkoxycarbonyl or d-C 6 alkylsulfonyl;
  • alkyl groups appearing in the substituent definitions may be straight-chain or branched and are, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl and all branched isomers thereof.
  • Alkoxy, alkylthio, alkenyl and alkynyl radicals are derived from the mentioned alkyl radicals.
  • Alkenyl and alkynyl groups may additionally be mono- or poly-unsaturated, with allenyl or mixed alkene-alkynyl groups also being included.
  • alkoxy groups are accordingly methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy.
  • Alkylthio groups and the oxidised forms thereof preferably have a chain length of one, two or three carbon atoms and are, for example, methylthio, ethylthio, n-propylthio and isopropylthio; especially methylthio and ethylthio.
  • Alkylsulfinyl is, for example, methylsulfinyl, ethylsulfinyl, n-propylsulfinyl or isopropylsulfinyl
  • alkylsulfonyl is preferably methylsulfonyl, ethylsulfonyl, propylsulfonyl or isopropylsulfonyl; especially methylsulfonyl or ethylsulfonyl.
  • Alkylamino is, for example, methylamino, ethylamino, n- propylamino, isopropylamino or a butylamine isomer.
  • Dialkylamino is, for example, dimethyl- amino, methylethylamino, diethylamino, n-propylmethylamino, dibutylamino or diisopropyl- amino.
  • alkylamino and dialkylamino groups including as part of (N- alkyl)-alkylsulfonylamino and N,N-(dialkyl)-aminosulfonyl groups, such as (N-methyl)-methyl- sulfonylamino and N,N-(dimethyl)-aminosulfonyl - each having a chain length of one, two, three or four carbon atoms.
  • Halogen is generally fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine.
  • Halogen as a substituent in alkyl groups that is to say in haloalkyl groups, preferably have a chain length of from 1 to 6 carbon atoms.
  • d-C 4 Ha!oalkyl is, for example, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2,2,2-trifluoroethyl, 2-fluoroethyl, 2-chloroethyl, pentafluoroethyl, 1 ,1-difluoro-2,2,2- trichloroethyl, 2,2,2-thchloroethyl, 1 ,1 ,2,2-tetrafluoroethyl, 2,2,3,3-tetrafluoropropyl, 2,2,3,3,3- pentafluoropropyl, 2,2,3,4,4,4-hexafluorobutyl; preferably fiuoromethyl, difluoromethyl, difluorochloromethyl, dichlorofluoromethyl, trifluoromethyl, 2-chloroethyl, 2,2,2-trifluoroethyl, 2,2,3,3
  • Haloalkenyl groups may contain one or more halogen substituents, such as, for example, in 2,2-difluoro-1-methylvinyl, 3-fluoropropenyl, 3-chloropropenyl, 3-bromopropenyl, 2,3,3- trifluoropropenyl, 2,3,3-trichloropropenyl and 4,4,4-thfluoro-but-2-en-1-yl.
  • halogen is especially fluorine and chlorine.
  • haloalkynyl groups there likewise come into consideration alkynyl groups substituted one or more times by halogen, halogen being both bromine and iodine as well as fluorine and chlorine, for example 3-fluoropropynyl, 3-chloropropynyl, 3- bromopropynyl, 3,3,3-trifluoropropynyl and 4,4,4-trifluoro-but-2-yn-1 -yl.
  • halogen in conjunction with other haloalkyl-containing definitions, such as haloalkoxy, haloalkylthio, haloalkylsulfinyl, haloalkylsulfonyl and halophenyl, for example fluoromethoxy, difluoromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy, 1 ,1 ,2,2-tetrafluoroethoxy, 2-fluoro- ethoxy, 2-chloroethoxy, 2,2-difluoroethoxy, 2,2,2-trichloroethoxy, difluoromethylthio, trifluoro- methylthio, trifluoroethylthio, difluoromethylsulfinyl, chloromethylsulfonyl, 4-chlorophenyl, 2- fluorophenyl and pentafluorophenyl.
  • fluoromethoxy difluoromethoxy, trifluo
  • R 02 having the above meaning of a monocyclic or bicyclic ring system bonded by way of a N atom is to be understood as being, for example, morpholin-4-yl, cis- and/or trans-2,6-di- methyl-morpholin-4-yl, thiomorpholin-4-yl, N-methyl-piperidin-1-yl, 1 H-pyrrol-1-yl, 1 H-pyrazol- 1 -yl, 3-methyl-1 H-pyrazol-1 -yl, 3,5-dimethyl-1 H-pyrazol-1 -yl, 3-trifluoromethyl-1 H-pyrazol-1 - yl, 3-methyl-1 H-1 ,2,4-thazol-1 -yl, 5-methyl-1 H-1 ,2,4-triazol-1 -yl or 4H-1 ,2,4-thazol-4-yl.
  • R 02 having the above meaning of a five- or six-membered, monocyclic aromatic ring system is to be understood as being especially an aromatic 5- or 6-membered heteroaryl group bonded via a carbon atom, which may contain an oxygen, a sulfur and/or one, two or three nitrogen atoms, for example 1 -methyl-1 H-pyrazol-3-yl, 1-ethyl-1 H-pyrazol-3-yl, 1 -propyl-1 H- pyrazol-3-yl, 1 H-pyrazol-3-yl, 1 ,5-dimethyl-1 H-pyrazol-3-yl, 4-chloro-1 -methyl-1 H-pyrazol-3-yl, 3-isoxazolyl, 5-methy!-3-isoxazolyl, 3-methyl-5-isoxazolyl, 5-isoxazolyl, 1 H-pyrrol-2-yl, 1- methyl-1 H-pyrrol-2-yl, 1 -methyl-1 H-pyrrol-3-yl, 2-
  • R 02 having the above meaning of a four-, five- or six-membered monocyclic ring system that is partially or fully saturated and contains one, two, three or four hetero atoms selected from nitrogen, oxygen and sulfur and in which one or two carbon atoms of the ring system have been replaced by a carbonyl or thiocarbonyl group is to be understood as being, for example, a heterocyclic group, such as, for example,
  • R 31 and R 34 are C C 3 alkyl, especially methyl
  • R 28 is hydrogen or d-C 3 alkyl
  • R 29 , R 30 and R 33 are amino, d-C 3 alkyl, C C 3 haloalkyl, cyclopropyl, methoxymethyl or C C 3 alkoxy
  • R 32 is preferably hydrogen, chlorine, bromine, d-C 3 a!kyl, C ⁇ -C 3 haloalkyl, cyclopropyl, d-C 3 alkoxy, d-C 3 alkylthio
  • r 0, 1 , 2 or up to 8.
  • R 0113 Ron is d-C 3 alkyl
  • R 0112 is C C 3 alkyl or C ⁇ -C 3 alkoxy-CrC 2 alkyl
  • R 0122 is hydrogen, d-C 4 alkyI, C 3 -C 4 alkenyl, C 3 - C 4 alkynyl, d-C 4 haloalkyl, C 1 -C 3 alkoxy-C ⁇ -C 2 alkyl, d-C 3 haloalkoxy-C 1 -C 2 alkyl or benzyl
  • R 0201 preferably independently from each other each Rom, R 0113 , Ron is d-C 3 alkyl
  • R 0112 is C C 3 alkyl or C ⁇ -C 3 alkoxy-CrC 2 alkyl
  • R 0122 is hydrogen, d-C 4 alkyI, C 3 -C 4 alkenyl, C 3 - C 4 alkynyl, d-C 4 haloalkyl, C 1 -C
  • R 02 o 4 are halogen, d-C 3 haloalkyl, CrC 3 alkylthio, d-C 3 alkylsulfinyl, d-C 3 alkylsulfonyl, C C 3 haloalkoxy or cyano;
  • R 0202 is halogen, C ⁇ -C 3 alkyl, d-C 3 haloalkyl, d-C 3 alkoxy, d- C 2 alkoxy-CrC 2 alkoxy, d-C 3 alkylthio, C C 3 alkylsulfinyl or d-C 3 alkylsulfonyl;
  • alkylene chains which may in addition be interrupted by oxygen, sulfur, sulfinyl or by sulfonyl for example d-C 4 alkylene chains which may in addition be interrupted by oxygen, sulfur, sulfinyl or by sulfonyl, such as -CH 2 -, -CH 2 CH 2 -, -CH 2 CH 2 CH 2 -, -CH 2 CH 2 CH 2 CH 2 -, -OCH 2 -, -CH 2 O-, -OCH2CH 2 -, -CH 2 CH 2 O-, -CH 2 OCH 2 -, -CH 2 OCH 2 CH2-, -CH 2 OCH 2 OCH 2 -, -CH 2 OCH 2 CH 2 OCH 2 -, -SCH 2 CH 2 -, -CH 2 SCH 2 -, -CH 2 S(O)CH 2 - or -CH 2 SO 2 CH 2 -, such as, for example, in R 02 o-C ⁇
  • alkylene chains in cycloalkyl groups may be substituted one or more times by d-C 3 alkyl groups, especially by methyl groups, for example 4-methyl- [1 ,3]dioxolan-2-yl, cis- and trans-4,5-d
  • substituted one or more times which appears in the above definitions of substituents, such as, for example, in the definition of the substituents Y, R ⁇ R 2 , R 6 , R 7 and R 8 , typically denotes substitution from one to eight times, preferably from one to five times, more especially once, twice or three times.
  • phenyl groups as substituents are substituted one, two, three, four or five times by substituents, such as, for example, d-C 6 alkyl, halogen or cyano; such phenyl groups are preferably substituted once, twice or three times.
  • substituents such as, for example, d-C 6 alkyl, halogen or cyano
  • specific groups according to the invention for example the phenyl group Q, have a substitution pattern different from that above, which is described at the relevant places in the text.
  • the compounds of formula I may generally occur in various tautomeric forms, as shown below by way of example for compounds of formula I wherein R 3 is hydroxy by formulae I', I", I'", , I V , I VI and " , the forms I', I", l v and l ⁇ being preferred as isolated forms, and formula I" also representing a rotameric form of l v ⁇ , and formula I' being a preferred rotameric form of l v " and formula l v being a preferred rotameric form of l " .
  • the compounds of formula I may, when asymmetry exists, be in the ⁇ ' or in the 'Z' form. If at least one asymmetric centre is present, for example an asymmetric sulfinyl group or an asymmetric carbon atom in the group Y, A 1 , A 2 or in the substituents R ⁇ R 2 , R 02 , Ron, then chiral 'R' and 'S' forms forms may also occur.
  • Ri and R 2 as well as R 7 and R 8 may, as a result of the spatial arrangement of Ai and A 2 , independently of one another have the same or different meanings, compounds of formula I may also be obtained in a variety of constitutional isomeric forms.
  • the substituent R 3 may be located on the bridging member, as already indicated above in formulae l" and l v ⁇ wherein R 3 is hydroxy.
  • the invention therefore relates also to all those constitutional isomeric forms in respect of the spatial arrangement of A T and A 2 and the substituents R ⁇ and R 2 with respect to the substituent R 3 , as shown generally by formulae l", l v and l v ⁇ .
  • the present invention therefore relates also to all stereoisomeric, rotameric, tautomeric and constitutional isomeric forms of compounds of formula I. Those arrangements of A 1 ? A 2 , Q, Y and the substituents R 1 ( R 2 and R 3 accordingly also relate to all possible tautomeric and stereoisomeric forms of all compounds used hereinbelow as intermediates in the preparation of compounds of formula I.
  • the invention relates likewise to the salts which the compounds of formula I are able to form especially with amines, alkali metal and alkaline earth metal cations or quaternary ammonium bases.
  • Suitable salt formers are described, for example, in WO 98/41089.
  • alkali metal and alkaline earth metal hydroxides as salt formers special mention should be made of the hydroxides of lithium, sodium, potassium, magnesium and calcium, but especially the hydroxides of sodium and potassium.
  • amines suitable for ammonium salt formation include ammonia as well as primary, secondary and tertiary C C 18 alkylamines, d-C hydroxyalkylamines and C 2 -C 4 alkoxyalkylamines, for example methylamine, ethyl- amine, n-propylamine, isopropylamine, the four butylamine isomers, n-amylamine, isoamyl- amine, n-hexylamine, heptylamine, octylamine, nonylamine, decylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, methylethylamine, methylisopropyl- amine, methylhexylamine, methylnonylamine, methylpentadecylamine, methyloctadecyl- amine
  • pyridine quinoline, isoquinoline, morpholine, piperidine, pyrrolidine, indoline, quinuclidine and azepine
  • primary arylamines such as, for example, anilines, methoxy- anilines, ethoxyanilines, o-, m- and p-toluidines, phenylenediamines, benzidines, naphthyl- amines and o-, m- and p-chloroanilines; but especially triethylamine, isopropylamine and diisopropylamine.
  • Preferred quaternary ammonium bases suitable for salt formation correspond e.g.
  • R 6a is hydrogen, d-C 6 alkyl or d-C 6 alkylcarbonyl; and each R 02 independently of any other(s) is halogen, d-C 6 alkyl, d-C 6 haloalkyl, C 2 -C 6 - alkenyl, C 2 -C 6 haloalkenyl, C 2 -C 6 alkynyl, C 2 -C 6 haloalkynyl, CrC 6 alkoxy, CrC 6 haloalkoxy, C 3 -C 8 alkenyloxy, C 3 -C 6 haloalkenyloxy, C 3 -C 6 alkynyloxy, C 3 -C 6 haloalkynyloxy, CrC 6 alkoxy- C ⁇ -C 6 alkoxy, cyano-d-C 6 alkoxy, cyano-CrC 6 alkenyloxy, d-Cealkoxycarbonyl-d-d-
  • Preferred compounds of formula I are also those wherein Q is a phenyl group having two or three identical or, preferably, different R 02 substituents, which phenyl group is preferably substituted once in the ortho-position to the carbonyl group.
  • R0 2 0 2 is halogen, d-C 4 alkyl, C 1 -C 4 haloalkyl, C 2 -C 4 alkenyl, C 2 -C 4 haloalkenyl, C 2 -C 4 alkynyl, C 2 -C 4 haloalkynyl, d-C alkoxy, d-C 4 haloalkoxy, C 3 -C 4 alkenyloxy, C 3 -C 4 haloalkenyloxy, C 3 -C 4 alkynyloxy, d-C 3 alkoxy-C C 3 alkoxy, cyano-d-C 3 alkoxy, CrC 3 alky[thio-d-C- 3 alkoxy, C ⁇ -C 4 alkylthio, d-C alkylsulfinyl, d-C alkylsulfonyl, C C 4 haloalkyl
  • Especially preferred compounds of formula I are also those wherein Q is a phenyl group of formula Q 0 wherein R 0203 is C ⁇ -C 4 alkylthio, C C 4 alkylsulfinyl, C C 4 alkylsulfonyl, C C 4 alkoxy- d-C 4 alkylthio, d-C 4 alkoxy-d-C 4 alkylsulfinyl, C ⁇ -C 4 alkoxy-d-C alkylsulfonyl or cyano, especially CrC 4 alkylthio or C ⁇ -C 4 alkoxy-C ⁇ -C 3 alkylthio or cyano.
  • Q is a phenyl group of formula Qo wherein R 0204 is d-C 3 haloalkyl, nitro or cyano, especially trifluoromethyl, difluoromethyl or cyano.
  • Q is a phenyl group of formula Qo wherein R 0202 is chlorine, bromine, C ⁇ -C 3 alkyl, C C 3 haloalkyl, d-Csalkoxy-d-Csalkyl, d-C 2 alkoxy-CrC 2 alkoxy-d-C 2 alkyl, C C 3 alkoxy, d-C 3 alkoxy-d-C 2 alkoxy, d-C 3 alkylthio, d-C 3 alkylsulfinyl, C C 3 alkylsulfonyl, cyano or nitro; R 0203 is hydrogen, halogen, C ⁇ -C alkyl, d-dhaloalkyl, C 2 -C 4 alkenyl, C 2 -C 4 haloalkenyi, C 2 -C alkynyl, C 2 -C 4 haloalkynyl, CrC 6 alkoxy, C ⁇ -C
  • Q is a phenyl group of formula Q 0 wherein R 02 o 2 is chlorine, bromine, d-C 3 alkyl, d-C 3 alkylsulfonyl or nitro; R0 203 is hydrogen, d-C 8 alkoxy, d-C ⁇ haloalkoxy, C 3 -C 6 alkenyloxy, C 3 -C 6 alkynyloxy, C ⁇ -C 4 alkoxy- d-C 3 alkoxy, C ⁇ -C 4 alkylcarbonylamino-d-C 3 alkoxy, CrC 4 alkoxycarbonylamino-d-C 3 alkoxy, d-C 4 alkylthio, d-C 4 alkoxy-d-C 3 alkyl ⁇ hio, d-C 4 alkoxycarbonyl, cyano, d-C 4 alkoxy-d-C 3 - alkyl or d-C 4 haloal
  • Q is a phenyl group of formula Q 0 wherein R 02 0 2 is chlorine, bromine, C ⁇ -C 3 alkyl, C ⁇ -C 3 alkylsulfonyl or nitro; R0 203 is hydrogen, d-C 6 alkoxy, d-dhaloalkoxy, C 3 -C 6 alkenyloxy, C 3 -C 6 alkynyloxy, C ⁇ -C 4 alkoxy- d-C 3 alkoxy, d-C 4 alkylcarbonylamino-CrC 3 alkoxy, CrC 4 alkoxycarbonylamino-d-C 3 alkoxy, d-C 4 alkylthio, d-C 4 alkoxy-C ⁇ -C 3 alkylthio, d-C 4 alkoxycarbonyl, cyano, C ⁇ -C 4 alkoxy-d-C 3 - alkyl or d-C 4 haloalkoxy
  • Q is a phenyl group of formula Q 0 wherein R 0202 is chlorine, bromine, C ⁇ -C 3 alkyl, d-C 3 alkylsulforiyl or nitro; R 0203 is hydrogen, CrC 6 alkoxy, C 1 -C 6 haloalkoxy, C 3 -C 6 alkenyloxy, C 3 -C 6 alkynyloxy, d-C 4 alkoxy- d-C 3 alkoxy, C C 4 alkylcarbonylamino-C ⁇ -C 3 alkoxy, d-C 4 alkoxycarbonylamino-d-C 3 alkoxy, C ⁇ -C 4 alkylthio, d-C 4 alkoxy-C ⁇ -C 3 alkylthio, d-C 4 alkoxycarbonyl or cyano; R 0204 is halogen, d-C 3 haloalkyl, d-C 3 alkylsulf
  • R 0 ns is d-C 3 alkyl
  • R 0205 is halogen, d-C 3 alkyl, C C 3 haloalkyl, C ⁇ -C 3 alkoxy, C C 2 - alkoxy-C C 2 alkoxy, C ⁇ -C 3 alkylthio, d-C 3 alkylsulfinyl or d-C 3 alkylsulfonyl
  • R 0206 is hydrogen, fluorine, chlorine or methyl
  • a T is CR 7 ;
  • a 2 is CR 8 ;
  • R 6a is hydrogen, d-C 6 alkyl or C C 6 alkyl- carbonyloxy;
  • R 6b is hydrogen or d-C 6 alkyl;
  • R- t , R , Re, R 7 and R 8 are each independently of the others hydrogen, halogen, d-C 6 alkyl, CrC 6 alkoxy or C C 6 alkoxycarbonyl; or two substituents R 6 at the same carbon atom together form a C 2 -C 5 alkylene chain; and
  • R 3 is hydroxy.
  • the compounds of formula I can be prepared by methods known perse, such as those described, for example, in WO 00/39094, as illustrated below using the example of the preparation of compounds of formula la,
  • A-i, A 2 , R , R 2 , R 02 and Y are as defined for formula I and p is 1 , 2, 3 or 4.
  • R 02 and p are as defined above, and E n is a leaving group, for example halogen or cyano, is first reacted in an inert, organic solvent, in the presence of a base, with a compound of formula III
  • R 02 and p are as defined above, is reacted with a compound of formula III, as indicated above, in an inert, organic solvent in the presence of a base and a coupling reagent, to form a compound of formula Ila and/or lib as indicated above, which is/are then isomerised as described for route a) by addition of a cyanide ion catalyst in the presence of a base, for example triethylamine, in a preferably polar aprotic solvent, e.g. acetonitrile.
  • a base for example triethylamine
  • a preferably polar aprotic solvent e.g. acetonitrile
  • the starting materials used are carboxylic acid derivatives of formula Qa wherein Ei is a leaving group, for example fluorine, chlorine, bromine, especially chlorine, or N-oxyphthalimide, N,O-dimethylhydroxylamino or part of an activated ester, for example (formed from dicyclohexylcarbodiimide (DCC) and the O' corresponding carboxylic acid) or ⁇ _ (formed from N-ethyl-N'-(3-dimethyl- GJ-UN] M (CH 2 ) 3 N(CH 3 ) 2 aminopropyl)-carbodiimide (EDC) and the corresponding carboxylic acid ).
  • Ei is a leaving group, for example fluorine, chlorine, bromine, especially chlorine, or N-oxyphthalimide, N,O-dimethylhydroxylamino or part of an activated ester, for example (formed from dicyclohexylcarbodiimide (DCC) and the O' corresponding carboxylic acid) or ⁇ _ (
  • the isomerisation of the enol ester derivatives of formulae Ila and lib or mixtures thereof to form the compounds of formula la is known and can be carried out, for example, analogously to EP-A-0 353 187, EP-A-0 316 491 or WO 97/46530 in the presence of a base, such as an alkylamine, for example triethylamine, a carbonate, for example potassium carbonate, and a catalytic amount of DMAP or a catalytic amount of a source of cyanide ions, for example acetone cyanohydrin, potassium cyanide or trimethylsilyl cyanide.
  • a base such as an alkylamine, for example triethylamine, a carbonate, for example potassium carbonate, and a catalytic amount of DMAP or a catalytic amount of a source of cyanide ions, for example acetone cyanohydrin, potassium cyanide or trimethylsilyl cyanide.
  • the two reaction steps can be carried out in situ, without isolation of the intermediates of formula Ila and/or lib, especially when a cyanoketone compound of formula Qa wherein Ei is cyano is used or in the presence of a catalytic amount of acetone cyanohydrin or potassium cyanide.
  • the desired compounds of formula la can be obtained, for example, analogously to E. Haslem, Tetrahedron, 2409-2433, 36, 1980, by first preparing enol esters of formula Ila and/or lib by esterification of the carboxylic acids of formula Qb with diones of formula III in an inert solvent, such as a halogenated hydrocarbon, for example dichloromethane, a nitrile, for example acetonitrile, or an aromatic hydrocarbon, for example toluene, in the presence of a base, such as an alkylamine, for example triethylamine, and a coupling reagent, such as dicyclohexylcarbodiimide (DCC) or 2-chloro-1 - methyl-pyridinium iodide, and then converting those esters ⁇ ' n situ or in a second step into the compounds of formula la.
  • an inert solvent such as a halogenated hydrocarbon, for example dichlorome
  • That reaction takes place, depending upon the solvent used, at temperatures of from 0°C to 110°C, preferably at temperatures of from 10°C to 40°C, and first yields, as described under Reaction Scheme 1 (route a), the isomeric enol ester(s) of formula Ila and/or lib, which are then isomerised to form the desired compounds of formula la either in a second step or in situ, likewise as described under Reaction Scheme 1 (route a), for example in the presence of a base, such as triethylamine, and a catalytic amount of DMAP or a source of cyanide ions, for example acetone cyanohydrin.
  • a base such as triethylamine
  • the activated carboxylic acid derivatives of formula Qa in Reaction Scheme 1 (route a) wherein E ⁇ is a leaving group, such as fluorine, bromine or, especially, chlorine, can be prepared in accordance with known standard methods, for example in the case of acid chlorides with oxalyl chloride or with phosgene. Such reactions are generally known and are well described in the literature with different variations in respect of the leaving group Ei.
  • mercaptans, thiophenols or heterocyclic thiols are used in the presence of a base, for example 5-ethyl-2-methylpyridine, diisopropylethylamine, triethylamine, sodium hydrogen carbonate, sodium acetate or potassium carbonate.
  • a base for example 5-ethyl-2-methylpyridine, diisopropylethylamine, triethylamine, sodium hydrogen carbonate, sodium acetate or potassium carbonate.
  • Compounds of formula I wherein the substituent R 3 is a mercapto group can be oxidised in analogy to known standard methods, for example using peracids, e.g. meta-chloroper- benzoic acid (m-CPBA) or peracetic acid, to form the corresponding sulfoxides and/or sulfones of formula I.
  • peracids e.g. meta-chloroper- benzoic acid (m-CPBA) or peracetic acid
  • m-CPBA meta-chloroper- benzoic acid
  • peracetic acid peracetic acid
  • Ai, A 2 , Ri, R 2 and Y are as defined for formula I, and Xa is chlorine or bromine and Ya is hydroxy or d-C 8 alkoxy, using a suitable reducing agent, for example tributyltin hydride, or iron or zinc in acetic acid, and subjecting the resulting compound of formula Ilia
  • A-i, A 2 , Ri, R 2 , R 3 and Y are as defined above, to aftertreatment, optionally, when Ya is C ⁇ -C 8 alkoxy, in the presence a hydrolysing agent, for example dilute hydrochloric acid, or aqueous p-toluenesulfonic or acetic acid, in order thus to obtain a compound of formula Ilia wherein Ai, A 2 , Ri, R 2 and Y are as defined above, and Ya is hydroxy, in the tautomeric form lllb of the compound of formula III.
  • a hydrolysing agent for example dilute hydrochloric acid, or aqueous p-toluenesulfonic or acetic acid
  • the compounds of formula III used as starting materials can accordingly be prepared very generally in accordance with those known methods, for example by reacting a dienophilic compound of formula VI
  • Ai, A 2 , Ri, R 2 and Y are as defined above, in an inert solvent, such as dichloromethane, 1 ,2-dichloroethane, toluene or chlorobenzene, and optionally at elevated temperature and/or under elevated pressure, in a reaction similar to a Diels-Alder reaction with a cyclopropene of formula XII
  • Xa is hydrogen, chlorine, bromine or iodine
  • Xb and Xc are halogen and Za is halogen, C C 6 alkoxy, phenoxy, C C 6 alkylthio, d-C 6 alkylsulfinyl, C ⁇ -C 8 alkylsulfonyl, phenylthio, phenylsuifinyl or phenylsulfonyl, or preferably Xa, Xb, Xc and Za are all simultaneously chlorine or bromine (formula Xlla), and then hydrolysing the resulting bicyclic compound of formula V
  • Xa, Xb, Xc, Za and Y are as defined above, optionally in the presence of a suitable catalyst, for example silver nitrate or silver tetrafluoroborate, or in the presence of a strong acid, such as 90-98% sulfuric acid, 90% trifluoroacetic acid or p-toluenesulfonic acid, or, in a special, milder variant, by first partially hydrolysing that compound to form a compound of formula IVc
  • Ai, A 2) Ri, R , Xa, Xc, Za and Y are as defined above, and then reacting with an alcoholate, for example sodium methanolate, potassium ethanolate or lithium isopropanolate, in order thus to obtain a compound of formula IV
  • Ai, A 2 , R 1 ( R 2 and Y are as defined above and, depending upon the reaction conditions, Ya is hydroxy (formula IVa), C ⁇ -C 8 alkoxy (formula IVc), chlorine or bromine (formula IVd), which is/are then reduced to form the compounds of formula Ilia
  • Ai, A 2 , R , R 2 and Y are as defined above, and Ya is hydroxy or C ⁇ -C 8 alkoxy, and/or hydrolysed directly to a compound of formula III
  • compounds of formula V and/or V 1 can thus be hydrolysed further, in the presence of 90-98% sulfuric acid at elevated temperature of about 80-100°C, to form the compounds of formula IVa, that is to say the compounds of formula IV and/or IV* wherein Ya is hydroxy and Xa is chlorine or bromine, as described in detail in J. Amer. Chem. Soc. 1968, 90, 2376.
  • Compounds of formula IVd can then be converted with good yields, at ambient temperatures, into compounds of formula IVc wherein Ya is d-C 8 alkoxy and Xa is chlorine or bromine in the presence of alcoholates of formula R 3a O " M + , wherein R 3a is d-C 8 alkyl and M a + is an alkali metal cation, in a solvent, such as an alcohol R 3a OH, toluene or ether, for example tetra- hydrofuran or dimethoxyethane.
  • a solvent such as an alcohol R 3a OH, toluene or ether, for example tetra- hydrofuran or dimethoxyethane.
  • compounds of formula IVc wherein Xa is chlorine or bromine and Ya is hydroxy or d-C 8 a!koxy can be reduced in the presence of reducing agents, for example tributyltin hydride, in an organic solvent, such as toluene or tetrahydrofuran, to form compounds of formula Ilia, as known in accordance with general methods from the literature for the reduction of halogens in a position adjacent to a carbonyl group (see, for example, Comprehensive Org. Fund Group. Transformations, Vol. 1. ed. S.M. Roberts, Pergamon Press Oxford, 1995, page 1 -1 1 ).
  • reducing agents for example tributyltin hydride
  • organic solvent such as toluene or tetrahydrofuran
  • compounds of formula Ilia wherein Ya is C C 8 alkoxy, chlorine or bromine can be hydrolysed in the presence of acids, for example dilute hydrochloric acid, dilute sulfuric acid, p-toluenesulfonic acid in water or acetic acid, or in the presence of aqueous hydroxide solutions, for example lithium, sodium or potassium hydroxide solutions, directly to compounds of formula III or their tautomeric form lllb, there advantageously being formed in the latter case a lithium, sodium or potassium salt of formula Ilia wherein Ya is O " M + and M + is the relevant alkali metal ion, that salt being formed directly for the coupling in accordance with route a).
  • acids for example dilute hydrochloric acid, dilute sulfuric acid, p-toluenesulfonic acid in water or acetic acid
  • aqueous hydroxide solutions for example lithium, sodium or potassium hydroxide solutions
  • the tetrachlorocyclopropene can be prepared from the pentachlorocyclopropane Xllla
  • the pentachlorocyclopropane (formula Xllla wherein Xa is chlorine) can be obtained, for example, in accordance with Synthesis, 1986, 260 by dichlorocarbene addition to trichloroethylene, by reacting the latter with the sodium salt of trichloroacetic acid by heating in dimethoxyethane.
  • the compound of formula XIII wherein Xa, Xb, Xc, Xd are chlorine and Za is phenoxy can be prepared, for example, in accordance with Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya 1985, 1 , 222.
  • Hvdrolvsis Hvdrolvsis: e.g. 6% CF g COOH e.g. 95% H 2 SO 4 in AcOH/dioxane/H 2 O v or 30% NaOH
  • Ai, A 2 , Ri, R 2 , R 3a and Y are as defined above, and by means of subsequent hydrolysis, for example with aqueous acetic acid, dilute hydrochloric acid or a catalytic amount of p-toluenesulfonic acid in water, to form the compounds of formula III
  • a compound of formula III can also be prepared by converting either a compound of formula IX wherein Ai, A 2 , R-,, R 2 and Y are as defined above, and Rb is in each case d-C 6 alkyl or two Rb together are -CH 2 CH 2 -, by hydrolysis, for example by treatment with an aqueous acid (route c); or a compound of formula X
  • a , A 2 , R-i, R 2 and Y are as defined above, by means of an oxidising agent, for example selenium dioxide (route d), firstly into a 1 ,2-diketo compound of formula XI
  • Ai, A 2 , Ri, R 2 and Y are as defined above, and then, by a carbene insertion, for example by means of diazomethane or by means of trimethylsilyl-diazomethane, into the 1 ,3- dione compound of formula III
  • a 1 ; A 2 , Ri, R 2 and Y are as defined above.
  • Such processes are also known perse io the person skilled in the art; the compounds can be prepared, according to the functionality of groups Ai, A 2 , R 1 ( R 2 and Y, in accordance with general reaction routes shown in the following scheme:
  • the transformations according to route d) are likewise known, for example from Tetr. 1986, 42, 3491.
  • Oxidation is preferably carried out with selenium dioxide in a solvent, such as acetic acid, at temperatures of from 20°C to 120°C.
  • the carbene insertion by means of diazomethane is preferably effected at from -40°C to 50°C in a solvent, such as dichloromethane or diethyl ether.
  • the carbene insertion can also be carried out using trimethylsilyl- diazomethane, it being advantageous to work in the presence of a Lewis acid catalyst, such as boron trifluoride etherate, and at temperatures of from -15°C to 25°C.
  • the compounds of formulae III, Ilia, IV, IV 1 , IVa, IVc, IVc 1 , IVd, V, V 1 , VI, VII, VIII, IX, X and XI used as starting materials and as intermediates can be prepared, in dependence upon the substituent pattern Ai, A 2 , R-i, R and Y and also in dependence upon the availability of the starting materials, according to any desired methods and reaction routes, there being no limitation in respect of the process variants indicated above.
  • the reactions to form compounds of formula I are advantageously carried out in aprotic, inert organic solvents.
  • solvents are hydrocarbons, such as benzene, toluene, xylene or cyclohexane, chlorinated hydrocarbons, such as dichloromethane, trichloromethane, tetra- chloromethane or chlorobenzene, ethers, such as diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran or dioxane, nitriles, such as acetonitrile or propionitrile, amides, such as N,N-dimethylformamide, diethylformamide or N- methylpyrrolidinone.
  • the reaction temperatures are preferably from -20°C to +120°C.
  • the reactions generally proceed slightly exothermically and can generally be carried out at room temperature. In order to shorten the reaction time or to initiate the reaction, brief heating, up to the boiling point of the reaction mixture, can be carried out.
  • the reaction times can likewise be shortened by the addition of a few drops of base as reaction catalyst.
  • Suitable bases are especially tertiary amines, such as trimethylamine, triethylamine, quinuclidine, 1 ,4- diazabicyclo[2.2.2]octane, 1 ,5-diazabicyclo[4.3.0]non-5-ene or 1 ,5-diazabicyclo[5.4.0]undec- 7-ene.
  • bases inorganic bases, such as hydrides, e.g. sodium or calcium hydride, hydroxides, e.g. sodium or potassium hydroxide, carbonates, e.g. sodium or potassium carbonate, or hydrogen carbonates, e.g. potassium or sodium hydrogen carbonate.
  • the bases can be used as such or alternatively with catalytic amounts of a phase transfer catalyst, e.g. crown ethers, especially 18-crown-6, or tetraalkylammonium salts.
  • the end products of formula I can be isolated in conventional manner by concentration or evaporation of the solvent and purified by recrystallisation or trituration of the solid residue in solvents in which they are not readily soluble, such as ethers, aromatic hydrocarbons or chlorinated hydrocarbons, by distillation or by means of column chromatography or by means of the HPLC technique using a suitable eluant.
  • the present invention relates also to a novel process for the preparation of substituted 8- oxa-bicyclo[3.2.1]octane-, bicyclo[3.2.1]octane- and bicyclo[3.2.2]nonane-1 ,3-diones having a double bond in the 6,7-position.
  • Xa is hydrogen, chlorine, bromine or iodine
  • Ai, A 2 , Y, Ri and R 2 are as defined for formula I, Xa preferably being hydrogen, chlorine or bromine, comprises a) converting a compound of formula XIII
  • Xa is hydrogen, chlorine, bromine or iodine
  • Xb, Xc and Xd are halogen and Za is halogen, C C 6 alkoxy, phenoxy, C C 8 alkylthio, d-C 6 alkylsulfinyl, C -C 8 alkylsulfonyl, phenyl- thio, phenylsulfinyl or phenylsulfonyl
  • Xa preferably being hydrogen, chlorine or bromine
  • Xb, Xc, Xd preferably being chlorine or bromine
  • Za preferably being chlorine, bromine, C -C 6 alkoxy, d-C 6 alkylsulfinyl or phenylsulfinyl; in the presence of an inert solvent under anhydrous conditions, with an alkali metal hydroxide into a compound of formula XII
  • Ai, A 2 , Y, Ri and R 2 are as defined for formula I, and Xa, Xb, Xc and Za are as defined for formula XIII, and c) hydrolysing that compound in the presence of an aqueous base.
  • the alkali metal hydroxide is used in an amount of from 1 to about 3 equivalents, preferably in an amount of from 1 .2 to 1 .3 equivalents.
  • the temperatures can be selected in a range of from about 0°C to the boiling temperature of the solvent used. Temperatures of from 20°C to 90°C, especially from 70°C to 85°C, are advantageous.
  • the reaction times range from a few minutes to a few hours, depending upon the progress of the reaction and upon the reaction temperatures selected.
  • Inert solvents suitable for the reaction are especially dichloromethane, 1 ,2-dichloroethane, toluene, chlorobenzene, dimethoxyethane, tetrahydrofuran and, preferably, dioxane.
  • the reaction of the compound of formula XII with the compound of formula VI to form the compound of formula V 1 is preferably carried out at a temperature of from ambient temperature to 110°C. A temperature range of from 80°C to 90°C is preferred, however.
  • the compound of formula VI is used in an amount of from 1 to 6 equivalents, preferably in an amount of from 1 to 5 equivalents, especially in an amount of from 3 to 4 equivalents, more especially in an amount of 4 equivalents.
  • aqueous base in step c) it is preferable to use an alkali metal hydroxide, especially potassium hydroxide or sodium hydroxide.
  • the alkaline solution is used in an amount of from 5 to 50 equivalents, preferably in an amount of 10 equivalents, and in a temperature range from ambient temperature to 100°C, preferably in a temperature range of from 80 to 90°C.
  • the basic hydrolysis of the compound of formula V 1 to form the compound of formula IVa is a particular advantage of the process according to the invention. That process step can advantageously be carried out also when the compound of formula V 1 has been prepared by a different method or by procedures known in the literature.
  • the present invention therefore relates especially to the process step wherein the compound of formula V 1 is subjected to basic hydrolysis to form the compound of formula IVa.
  • An especially preferred embodiment of the process according to the invention can be carried out without isolation of intermediates, it being especially advantageous that the intermediate of formula XII or, in a preferred variant, of formula Xlla obtained from Process step a), which has low stability, can be reacted directly with the dienophile of formula VI or, in a preferred variant, of formula Via according to Process step b) without further isolation and purification.
  • Xa is preferably hydrogen, chlorine or bromine;
  • Ai is preferably CR 7 ;
  • a 2 is preferably CR 8 ;
  • Y is preferably oxygen or a d-C 2 alkylene chain which may be substituted one or more times by R 6 ;
  • Ri, R 2 , R7 and R 8 are each independently of the others preferably hydrogen, d-C 6 alkyl, trialkylsilyloxy or d-C 6 alkoxy; and
  • R 6 is preferably hydrogen, C ⁇ -C 6 alkyl, C ⁇ -C 6 alkoxy, tri(C C 6 alkyl)silyl or phenyl-di(C C 6 alkyl)silyl.
  • the process according to the invention is especially suitable for the preparation of those compounds of formula IVa wherein Y is oxygen, methylene or ethylene, especially methylene.
  • the process according to the invention is also preferably used for the preparation of those compounds wherein R 1 ? R 2 , R & , R 7 and R 8 are each independently of the others hydrogen, C ⁇ -C 3 alkyl or d-C 3 alkoxy, especially hydrogen, methyl, ethyl or methoxy.
  • the process is more especially used for the preparation of compounds of formula IVa wherein Y is methylene and Ri, R 2 , Re, R 7 and R 8 are each hydrogen.
  • the starting materials used are preferably compounds of formula Via wherein A 1 is preferably CR 7 ; A 2 is preferably CR 8 ; Y is preferably oxygen or a d-C 2 alkylene chain which may be substituted one or more times by R 6 ; Ri, R 2 , R7 and R 8 are each independently of the others preferably hydrogen, d-C 6 alkyl, trialkylsilyloxy or d-C 6 alkoxy; and R 6 is preferably hydrogen, d-C 6 alkyl, d-Cealkoxy, tri(C ⁇ -C 6 alkyl)silyl or phenyl-di(CrC 6 alkyl)silyl; and in accordance with the preferred meanings of formula IVa there are used the preferred starting materials of formula Va 1 wherein Ai is preferably CR 7 ; A 2 is preferably CR 8 ; Y is preferably oxygen or a d-C 2 alkylene chain which may be substitute
  • Xa, Xb, Xc, Xd and Za in compounds of formula XIII are preferably chlorine or bromine, especially chlorine.
  • the compounds in question are described under formula Xllla above.
  • reaction mixture is then concentrated by evaporation under reduced pressure to about 1/3 of its original volume and then filtered through Celite.
  • the filtrate is concentrated by evaporation in vacuo until a mixture of an oil and a white solid is obtained.
  • the oil is then separated off and crystallised in petroleum ether.
  • a total of 164.1 g of 2,3,4,4-tetrachloro-bicyclo[3.2.1]octa-2,6-diene is then obtained from the two combined solid phases.
  • a solution of 5.45 g (237 mmol) of sodium hydroxide in 14 ml of water is added at ambient temperature to 3.3 g (13.6 mmol) of 2,3,4,4-tetrachloro-bicyclo[3.2.1]octa-2,6-diene in 64 ml of dioxane.
  • the reaction mixture is then heated at a temperature of 90°C, with stirring, for 2 hours.
  • the reaction mixture is then reduced to about half its original volume under reduced pressure and then extracted with ethyl acetate.
  • the aqueous phase is adjusted to pH 1 by addition of concentrated (6N) hydrochloric acid and then extracted three times with ethyl acetate.
  • Example P A 4 Preparation of 3-chloro-4-hvdroxy-bicvclof3.2.1locta-3,6-dien-2-one (one-pot process):
  • aqueous phase is then separated off, acidified to pH 1 with 2N hydrochloric acid and then extracted three times against ethyl acetate to yield 3-chloro-4-hydroxy-bicyclo[3.2.1]octa-3,6-dien-2-one.
  • the compounds of formula IVa can be converted in a simple manner into further, valuable intermediates for the preparation of herbicidally active, bridged cyclohexanedione derivatives, as described, for example, in US 5,802,102, WO 00/37437, WO 00/15615, WO 01/94339 or in WO 04/58712.
  • a suitable catalyst e.g. 5% palladium/carbon
  • k ⁇ is preferably CR 7
  • a 2 is preferably CR 8
  • Y is preferably oxygen or an unsubstituted or R 6 -substituted C ⁇ -C 2 alkylene chain
  • Ri, R 2 , R 7 and R 8 are each independently of the others preferably hydrogen, CrC 6 alkyl, halogen, trialkylsilyloxy or d-C 6 alkoxy
  • R 6 is preferably hydrogen, d-C 6 alkyl, halogen, d-C 6 alkoxy, tri(d-C 6 alkyl)silyl or phenyl- di(d-C 6 alkyl)silyl, as also used, for example, in WO 04/58712.
  • a solution of 0.29 g (4.37 mmol, 4 eq.) of freshly prepared cyclopentadiene in 2.5 ml of dioxane is then added and the reaction mixture is stirred for 3 hours at a temperature of 85°C.
  • 3.5 ml of water are added together with 5.5 ml (10.9 mmol, 10 eq.) of 2N sodium hydroxide solution and stirring is continued for a further 2 hours at a temperature of 85°C.
  • the reaction mixture is acidified to pH 4 to 5 with concentrated acetic acid.
  • the reaction mixture is then degassed with argon, and a catalytic amount of 5 % palladium on active carbon is added.
  • reaction mixture is then degassed with hydrogen and maintained at a temperature of 55°C, with stirring, for 6 hours under a hydrogen atmosphere (1000 hPa).
  • the reaction mixture is then filtered (Celite) and the filtration residue is washed with ethyl acetate and water.
  • the aqueous phase is then separated off, acidified to pH 1 with 6N hydrochloric acid and extracted three times with ethyl acetate.
  • the combined organic phases are dried over sodium sulfate. After filtration, and concentration under reduced pressure, toluene is added twice, evacuation being carried out after each addition.
  • bicyclo[3.2.1]octane-2,4-dione 0.10 g is obtained in the form of a brown oil which is purified by filtration through silica gel (eluant: CH 2 CI 2 /MeOH 1/0; 9/1 ) to yield 0.070 g of pure bicyclo[3.2.1]octane-2,4-dione in the form of a white solid.
  • a ⁇ A 2 , Y, Ri and R 2 are as defined for formulae I and IVa, and Xa, Xb, Xc and Za are as defined for formula XIII.
  • the process according to the invention therefore also includes processes in which the tautomeric forms V and Va are used as intermediates or in mixture with compouns of the formula V 1 and Va 1 for the manufacture of compounds of the formula IVa.
  • Compounds of formula IVa can be obtained in the process according to the invention also in the form of their salts, for example the potassium or sodium salts. Such salts are obtained in the alkaline aqueous phase and can be converted into the neutral compounds of formula IVa by acidification.
  • a further advantage of the process according to the invention is that, prior to acidification, impurities can readily be removed as neutral components in order further to improve the purity of the end product.
  • tautomeric salt forms such as the tautomeric salt forms IVa', IVa" and IVa'", which are illustrated below ( ⁇ + is especially an alkali metal ion, for example the lithium, sodium or potassium ion):
  • the invention therefore relates also to a herbicidal and plant-growth-inhibiting composition
  • a herbicidal and plant-growth-inhibiting composition comprising a herbicidally effective amount of a compound of formula I according to claim 1 on an inert carrier.
  • the compounds of formula I according to the invention can be used as herbicides in unmodified form, as obtained in the synthesis, but they are generally formulated into herbicidal compositions in various ways using formulation adjuvants, such as carriers, solvents and surface-active substances.
  • formulation adjuvants such as carriers, solvents and surface-active substances.
  • the formulations can be in various physical forms, e.g.
  • the formulations can be prepared e.g. by mixing the active ingredient with the formulation adjuvants in order to obtain compositions in the form of finely divided solids, granules, solutions, dispersions or emulsions.
  • the active ingredients can also be formulated with other adjuvants, such as finely divided solids, mineral oils, oils of vegetable or animal origin, mod- ified oils of vegetable or animal origin, organic solvents, water, surface-active substances or combinations thereof.
  • the active ingredients can also be contained in very fine micro- capsules consisting of a polymer. Microcapsules contain the active ingredients in a porous carrier. This enables the active ingredients to be released into the environment in controlled amounts (e.g. slow-release).
  • Microcapsules usually have a diameter of from 0.1 to 500 microns. They contain active ingredients in an amount of about from 25 to 95 % by weight of the capsule weight.
  • the active ingredients can be in the form of a monolithic solid, in the form of fine particles in solid or liquid dispersion or in the form of a suitable solution.
  • the encapsulating membranes comprise, for example, natural or synthetic rubbers, cellulose, styrene/butadiene copolymers, polyacrylonitrile, polyacrylate, polyesters, polyamides, polyureas, polyurethane or chemically modified polymers and starch xanthates or other polymers that are known to the person skilled in the art in this connection.
  • very fine microcapsules can be formed in which the active ingredient is contained in the form of finely divided particles in a solid matrix of base substance, but the microcapsules are not themselves encapsulated.
  • liquid carriers there may be used: water, toluene, xylene, petroleum ether, vegetable oils, acetone, methyl ethyl ketone, cyclohexanone, acid anhydrides, acetonitrile, acetophenone, amyl acetate, 2-butanone, butylene carbonate, chlorobenzene, cyclohexane, cyclohexanol, alkyl esters of acetic acid, diacetone alcohol, 1 ,2-dichloropropane, diethanolamine, p-diethylbenzene, diethylene glycol, diethylene glycol abietate, diethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ether, N,N-dimethylformamide, dimethyl sulfoxide, 1 ,4-dioxane, diprop
  • Water is generally the carrier of choice for diluting the concentrates.
  • suitable solid carriers are, for example, talc, titanium dioxide, pyrophyllite clay, silica, attapulgite clay, kieselguhr, limestone, calcium carbonate, bentonite, calcium montmorillonite, cottonseed husks, wheat flour, soybean flour, pumice, wood flour, ground walnut shells, lignin and similar substances, as described, for example, in CFR 180.1001. (c) & (d).
  • a large number of surface-active substances can advantageously be used in both solid and liquid formulations, especially in those formulations which can be diluted with a carrier prior to use.
  • Surface-active substances may be anionic, cationic, non-ionic or polymeric and they can be used as emulsifiers, wetting agents or suspending agents or for other purposes.
  • Typical surface-active substances include, for example, salts of alkyl sulfates, such as diethanolammonium lauryl sulfate; salts of alkylarylsulfonates, such as calcium dodecyl- benzenesulfonate; alkylphenol/alkylene oxide addition products, such as nonylphenol ethoxylate; alcohol/alkylene oxide addition products, such as tridecylalcohol ethoxylate; soaps, such as sodium stearate; salts of alkylnaphthalenesulfonates, such as sodium dibutylnaphthalenesulfonate; dialkyl esters of sulfosuccinate salts, such as sodium di(2- ethylhexyl)sulfosuccinate; sorbitol esters, such as sorbitol oleate; quaternary amines, such as lauryltrimethylammonium chloride, polyethylene glycol esters
  • Further adjuvants that can usually be used in pesticidal formulations include crystallisation inhibitors, viscosity modifiers, suspending agents, dyes, anti-oxidants, foaming agents, light absorbers, mixing auxiliaries, antifoams, complexing agents, neutralising or pH-modifying substances and buffers, corrosion inhibitors, fragrances, wetting agents, take-up enhancers, micronutrients, plasticisers, glidants, lubricants, dispersants, thickeners, antifreezes, microbicides, and also liquid and solid fertilisers.
  • the formulations may also comprise additional active substances, for example further herbicides, herbicide safeners, plant growth regulators, fungicides or insecticides.
  • compositions according to the invention can additionally include an additive comprising an oil of vegetable or animal origin, a mineral oil, alkyl esters of such oils or mixtures of such oils and oil derivatives.
  • the amount of oil additive in the composition according to the invention is generally from 0.01 to 10 %, based on the spray mixture.
  • the oil additive can be added to the spray tank in the desired concentration after the spray mixture has been prepared.
  • Preferred oil additives comprise mineral oils or an oil of vegetable origin, for example rapeseed oil, olive oil or sunflower oil, emulsified vegetable oil, such as AMIGO® (Rh ⁇ ne-Poulenc Canada Inc.), alkyl esters of oils of vegetable origin, for example the methyl derivatives, or an oil of animal origin, such as fish oil or beef tallow.
  • a preferred additive contains, for example, as active components essentially 80 % by weight alkyl esters of fish oils and 15 % by weight methylated rapeseed oil, and also 5 % by weight customary emulsifiers and pH modifiers.
  • Especially preferred oil additives comprise alkyl esters of C 8 -C 2 fatty acids, thre being important especially the methyl derivatives of C ⁇ 2 -C ⁇ 8 fatty acids, for example the methyl esters of lauric acid, palmitic acid and oleic acid.
  • Those esters are known as methyl laurate (CAS-111-82-0), methyl palmitate (CAS-112-39-0) and methyl oleate (CAS-112-62-9).
  • a preferred fatty acid methyl ester derivative is Emery® 2230 and 2231 (Cognis GmbH).
  • Those and other oil derivatives are also known from the Compendium of Herbicide Adjuvants, 5th Edition, Southern Illinois University, 2000.
  • the application and action of the oil additives can be further improved by combination with surface-active substances, such as non-ionic, anionic or cationic surfactants.
  • surface-active substances such as non-ionic, anionic or cationic surfactants.
  • suitable anionic, non-ionic and cationic surfactants are listed on pages 7 and 8 of WO 97/34485.
  • Preferred surface-active substances are anionic surfactants of the dodecyl- benzylsulfonate type, especially the calcium salts thereof, and also non-ionic surfactants of the fatty alcohol ethoxylate type. Special preference is given to ethoxylated C ⁇ 2 -C 2 fatty alcohols having a degree of ethoxylation of from 5 to 40.
  • Examples of commercially available surfactants are the Genapol types (Clariant AG).
  • silicone surfactants especially polyalkyl-oxide-modified heptamethyltriloxanes which are commercially available e.g. as Silwet L-77®, and also perfluorinated surfactants.
  • concentration of the surface- active substances in relation to the total additive is generally from 1 to 30 % by weight.
  • oil additives consisting of mixtures of oils or mineral oils or derivatives thereof with surfactants are Edenor ME SU®, Turbocharge® (Syngenta AG, CH) and ActipronC (BP Oil UK Limited, GB).
  • an organic solvent may contribute to an additional enhancement of action.
  • Suitable solvents are, for example, Solvesso® (ESSO) or Aromatic Solvent® (Exxon Corporation). The concentration of such solvents can be from 10 to 80 % by weight of the total weight.
  • Oil additives that are present in admixture with solvents are described, for example, in US-A-4,834,908.
  • a commercially available oil additive disclosed therein is known by the name MERGE® (BASF Corporation).
  • a further oil additive that is preferred according to the invention is SCORE® (Syngenta Crop Protection Canada).
  • alkyl- pyrrolidones e.g. Agrimax®
  • formulations of alkyl- pyrrolidones e.g. Agrimax®
  • synthetic latices e.g. polyacrylamide, polyvinyl compounds or poly-1 -p-menthene (e.g. Bond®, Courier® or Emerald®)
  • propionic acid for example Eurogkem Pen-e-trate®
  • compositions according to the invention may additionally comprise growth regulators, for example trinexapac (744), chlormequat chloride (129), clofencet (148), cyclanilide (170), etheph (281 ), flurprimidol (355), gibberellic acid (379), inabenfide (421), maleic hydrazide (449), mefluidide (463), mepiquat chloride (465), paclobutrazol (548), prohexadione-calcium (595), uniconazole (746) or thidiazuron (703).
  • growth regulators for example trinexapac (744), chlormequat chloride (129), clofencet (148), cyclanilide (170), etheph (281 ), flurprimidol (355), gibberellic acid (379), inabenfide (421), maleic hydrazide (449), mefluidide (463), mepiquat chloride (465), paclo
  • composition according to the invention may comprise fungicides, for example azoxystrobin (43), epoxiconazole (48), benomyl (( bromuconazole (89), bitertanol (77), carbendazim (107), cyproconazole (189), cyprodinil (190), diclomezine (220), difenoconazole (228), diniconazole (247), epoxiconazole (48), ethirimol (284 etridiazole (294), fenarimol (300), fenbuconazole (302), fenpiclonil (311), fenpropidin (313), fenpropimorph (314), ferimzone (321), fludioxonil (334), fluquinconazole (349), flutolanil (360), flutriafol (361 ), imazalil (410), ipconazole (426), iprod
  • fungicides
  • the herbicidal compositions generally comprise from 0.1 to 99 % by weight, especially from 0.1 to 95 % by weight, compounds of formula I and from 1 to 99.9 % by weight of a formulation adjuvant which preferably includes from 0 to 25 % by weight of a surface-active substance.
  • a formulation adjuvant which preferably includes from 0 to 25 % by weight of a surface-active substance.
  • commercial products will usually preferably be formulated as concentrates, the end user will normally employ dilute formulations.
  • the rates of application of compounds of formula I may vary within wide limits and depend on the nature of the soil, the method of application (pre- or post-emergence; seed dressing; application to the seed furrow; no tillage application etc.), the crop plant, the grass or weed to be controlled, the prevailing climatic conditions, and other factors governed by the method of application, the time of application and the target crop.
  • the compounds of formula I according to the invention are generally applied at a rate of from 1 to 2000 g/ha.
  • Emulsifiable concentrates active ingredient: 1 to 95 %, preferably 60 to 90 % surface-active agent: 1 to 30 %, preferably 5 to 20 % liquid carrier: 1 to 80 %, preferably 1 to 35 %
  • Dusts active ingredient: 0.1 to 10 %, preferably 0.1 to 5 % solid carrier: 99.9 to 90 %, preferably 99.9 to 99 %
  • Suspension concentrates active ingredient: 5 to 75 %, preferably 10 to 50 % water: 94 to 24 %, preferably 88 to 30 % surface-active agent: 1 to 40 %, preferably 2 to 30 %
  • Wettable powders active ingredient: 0.5 to 90 %, preferably 1 to 80 % surface-active agent: 0.5 to 20 %, preferably 1 to 15 % solid carrier: 5 to 95 %, preferably 15 to 90 %
  • Granules active ingredient: 0.1 to 30 %, preferably 0.1 to 15 % solid carrier: 99.5 to 70 %, preferably 97 to 85 %
  • Emulsifiable concentrates a) b) c) d) active ingredient 5% 10% 25% 50% calcium dodecylbenzenesulfonate 6% 8% 6% 8% castor oil polyglycol ether 4% - 4% 4%
  • Emulsions of any desired concentration can be obtained from such concentrates by dilution with water.
  • the solutions are suitable for use in the form of microdrops.
  • Wettable powders a) b) c) d) active ingredient 5% 25% 50% 80% sodium lignosulfonate 4% - 3% - sodium lauryl sulfate 2% 3% - 4% sodium diisobutylnaphthalene- sulfonate - 6% 5% 6% octylphenol polyglycol ether - 1 % 2% -
  • the active ingredient is mixed thoroughly with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording wettable powders which can be diluted with water to give suspensions of any desired concentration.
  • the finely ground active ingredient is uniformly applied, in a mixer, to the carrier moistened with polyethylene glycol.
  • Non-dusty coated granules are obtained in this manner.
  • the active ingredient is mixed and ground with the adjuvants, and the mixture is moistened with water.
  • the mixture is extruded and then dried in a stream of air.
  • Ready-to-use dusts are obtained by mixing the active ingredient with the carriers and grinding the mixture in a suitable mill.
  • Suspension concentrates a) b) C) d) active ingredient 3% 10% 25% 50% ethylene glycol 5% 5% 5% nonylphenol polyglycol ether - 1 % 2% -
  • the invention relates also to a method for the selective control of grasses and weeds in crops of useful plants, wherein the useful plants or the area of cultivation or locus thereof is treated with the compounds of formula I.
  • Useful plant crops in which the composition according to the invention can be used include especially cereals, cotton, soybeans, sugar beet, sugar cane, plantation crops, rape, maize and rice.
  • Crops are to be understood as also including those crops which have been rendered tolerant to herbicides or classes of herbicides (e.g. ALS-, GS-, EPSPS-, PPO- and HPPD- inhibitors) by conventional methods of breeding or by genetic engineering.
  • herbicides or classes of herbicides e.g. ALS-, GS-, EPSPS-, PPO- and HPPD- inhibitors
  • An example of a crop that has been rendered tolerant to imidazolinones, e.g. imazamox, by conventional methods of breeding is Clearfield® summer rape (canola).
  • crops that have been rendered tolerant to herbicides by genetic engineering methods include e.g. glyphosate- and glufosinate-resistant maize varieties commercially available under the trade names Round
  • the weeds to be controlled may be both monocotyledonous and dicotyledonous weeds, for example Stellaria, Nasturtium, Agrostis, Digitaria, Avena, Setaria, Sinapis, Lolium, Solanum, Echinochloa, Scirpus, Monochoria, Sagittaria, Bromus, Alopecurus, Sorghum, Rottboellia, Cyperus, Abutilon, Sida, Xanthium, Amaranthus, Chenopodium, Ipomoea, Chrysanthemum, Galium, Viola and Veronica.
  • Stellaria Nasturtium, Agrostis, Digitaria, Avena, Setaria, Sinapis, Lolium, Solanum, Echinochloa, Scirpus, Monochoria, Sagittaria, Bromus, Alopecurus, Sorghum, Rottboellia, Cyperus, Abutilon, Sida, Xanthium, Amaranthus
  • Crops are also to be understood as being those which have been rendered resistant to harmful insects by genetic engineering methods, for example Bt maize (resistant to European corn borer), Bt cotton (resistant to cotton boll weevil) and also Bt potatoes (resistant to Colorado beetle).
  • Bt maize are the Bt 176 maize hybrids of NK® (Syngenta Seeds).
  • the Bt toxin is a protein that is formed naturally by Bacillus thuringiensis soil bacteria.
  • Examples of toxins, or transgenic plants able to synthesise such toxins are described in EP-A-451 878, EP-A-374 753, WO 93/07278, WO 95/34656, WO 03/052073 and EP-A-427 529.
  • transgenic plants comprising one or more genes that code for an insecticidal resistance and express one or more toxins are KnockOut® (maize), Yield Gard® (maize), NuCOTIN33B® (cotton), Bollgard® (cotton), NewLeaf® (potatoes), NatureGard® and Protexcta®.
  • Plant crops or seed material thereof can be both resistant to herbicides and, at the same time, resistant to insect feeding ("stacked" transgenic events).
  • seed can have the ability to express an insecticidally effective Cry3 protein while at the same time being tolerant to glyphosate.
  • Crops are also to be understood as being those which are obtained by conventional methods of breeding or genetic engineering and contain so-called output traits (e.g. improved storage stability, higher nutritional value and improved flavour).
  • Areas under cultivation include land on which the crop plants are already growing and land intended for cultivation with those crop plants.
  • the precipitated silver bromide is filtered off and most of the acetone is distilled off under reduced pressure.
  • the aqueous phase that remains behind is extracted three times with ethyl acetate.
  • the organic extract is washed with water, dried over sodium sulfate and concentrated by evaporation.
  • the oily residue is purified by means of silica gel chromatography (eluant gradient: 3-50% ethyl acetate in hexane). 6.1 g of pure 3,4-dichloro-1 ,5-dimethyl-8- oxa-bicyclo[3.2.1]octa-3,6-dien-2-one are obtained in the form of a pale yellow solid.
  • Example P3 Preparation of 3-chloro-1.5-dimethyl-4-methoxy-8-oxa-bicvclo
  • the aqueous phase is then adjusted to pH 5 with dilute hydrochloric acid and extracted three times with fresh ethyl acetate.
  • the organic phase is dried over sodium sulfate and concentrated by evaporation under reduced pressure, there being obtained 1.04 g of technically pure 1 ,5- dimethyl-8-oxa-bicyclo[3.2.1]oct-6-ene-2,4-dione in the form of a yellowish product, which can be used in the next reaction step to form compounds of formula I without further purification.
  • reaction solution is then treated at a temperature of 0°C with a 10% sodium dihydrogen phosphate solution (20 ml) and water (30 ml) and extracted three times with ethyl acetate. Drying over sodium sulfate and concentration by evaporation are carried out.
  • the dark oil so obtained is purified by chromatography over silica gel with 5% ethyl acetate in hexane. 1.73 g of pure 3- bromo-1 ,5-dimethyl-4-isopropoxy-8-oxa-bicyclo[3.2.1]octa-3,6-dien-2-one are isolated.
  • a sodium glycolate solution is prepared by stirring 124 mg (5.4 mmol) of metallic sodium in 2.7 ml (42.42 mmol) of anhydrous ethylene glycol at ambient temperature and, when the sodium has completely dissolved, 1.5 ml of tetrahydrofuran are added. To the resulting monosodium glycolate solution there is then added dropwise a solution of 1 g (3.6 mmol) of 3,4-dibromo-bicyclo[3.2.1]octa-3,6-dien-2-one (prepared according to Organic Lett. 4(12), 1997 (2002)) dissolved in 5 ml of tetrahydrofuran.
  • reaction mixture is then stirred at ambient temperature for 90 minutes with TLC monitoring (mobile phase: hexane/ethyl acetate 4:1 ).
  • the reaction mixture is then treated with 8 ml of 10% sodium dihydrogen phosphate solution and extracted with ethyl acetate (3x).
  • the organic phase is washed with water to remove ethylene glycol, then dried and concentrated by evaporation. 930 mg of 3- bromo-4,4-ethylenedioxy-bicyclo[3.2.1]oct-6-en-2-one are obtained in the form of a white solid.
  • a degassed solution of 920 mg (3.55 mmol) of 3-bromo-4,4-(1',2'-ethyIenedioxy)-bicyclo- [3.2.1]oct-6-en-2-one in 90 ml of toluene is treated at boiling temperature in succession with a catalytic amount (30 mg) of AIBN and with 2.35 ml (8.88 mmol) of tributyltin hydride.
  • the reaction mixture is stirred under reflux for a further 20 minutes, with TLC monitoring (mobile phase: hexane/ethyl acetate 1 :1), to complete the reaction.
  • the reaction mixture is then concentrated by evaporation under reduced pressure.
  • reaction mixture When, after 2 hours, brominated starting material can no longer be detected, the reaction mixture is heated continuously to a temperature of 95°C. After a further 2 hours, according to TLC monitoring all reference material 4,4-(1 ',2'-ethylenedioxy)-bicyclo[3.2.1]oct-6-en-2-one has been reacted.
  • the reaction mixture is filtered and concentrated in vacuo. The residue is treated with saturated sodium hydrogen carbonate solution and extracted three times with ethyl acetate.
  • the alkaline aqueous phase is adjusted to pH 3-4 with dilute hydrochloric acid and extracted three times with fresh ethyl acetate. After drying of the organic phase over sodium sulfate and subsequent concentration by evaporation, 45 mg of technically pure bicyclo- [3.2.1 ]oct-6-ene-2,4-dione are obtained.
  • the residue is taken up in 15 ml of anhydrous acetonitrile, and then 0.112 g (0.12 ml; 1.32 mmol; 1.0 eq.) of acetone cyanohydrin and 0.201 g (0.28 ml; 1.98 ml; 1.5 eq.) of anhydrous triethylamine are added. After being stirred for 16 hours at ambient temperature, the reaction mixture is concentrated under reduced pressure and the resulting residue is purified by flash chromatography on silica gel (toluene/ethanol/dioxane/triethylamine/water; 100/40/20/20/5). The oil so obtained is treated with aqueous hydrochloric acid (pH 1).
  • aqueous phase is then extracted three times with ethyl acetate, the combined organic phases are washed twice with water and then twice with saturated sodium chloride solution and then dried over sodium sulfate. After filtration and concentration of the filtrate under reduced pressure, 0.205 g of 3-(4-methylsulfonyl-2-nitro-benzoyl)-bicyclo[3.2.1]oct-6-ene- 2,4-dione is obtained in the form of a yellowish solid.
  • aqueous phase is then extracted three times with ethyl acetate, the combined organic phases are washed twice with water and then twice with saturated sodium chloride solution and then dried over sodium sulfate. After filtration and concentration of the filtrate under reduced pressure, 0.125 g of 3-(4-methyl- sulfonyl-2-nitro-benzoyl)-1 -methyl-8-oxa-bicyclo[3.2.1]oct-6-ene-2,4-dione is obtained.
  • Example B1 Herbicidal action prior to emergence of the plants (pre-emerqence action) onocotyledonous and dicotyledonous test plants are sown in standard soil in seed trays.
  • the test compounds in the form of an aqueous suspension (prepared from a wettable powder (Example F3, b) according to WO 97/34485) or in the form of an emulsion (prepared from an emulsifiable concentrate (Example F1 , c) according to WO 97/34485), are applied by spraying in a concentration of 125 g or 250 g/ha.
  • the test plants are then grown in a greenhouse under optimum conditions.
  • Example B2 Herbicidal action after emergence of the plants (post-emergence herbicidal action)
  • test plants Monocotyledonous and dicotyledonous test plants are sown in standard soil in seed trays.
  • the test compounds in the form of an aqueous suspension (prepared from a wettable powder (Example F3, b) according to WO 97/34485) or in the form of an emulsion (prepared from an emulsifiable concentrate (Example F1 , c) according to WO 97/34485), are applied by spraying in a concentration of 125 g or 250 g/ha.
  • the test plants are then grown on in a greenhouse under optimum conditions.
  • Table B2 Ex. No. g/ha Echinochloa Xanthium Ipomea Chenopodium Kochia Sinapis Stellaria 1.002 250 7 8 9 10 9 9 9 9 1.013 250 7 7 7 8 9 7 8 1.020 250 8 8 9 8 9 8 9 8 1.025 250 7 8 8 9 7 9 8 1.029 250 7 8 5 8 8 8 8 1.030 250 7 7 7 9 8 9 8 1.031 250 7 7 9 10 8 8 1.057 250 8 9 9 10 10 10 10 1.060 250 8 4 9 8 8 7 9
  • the compounds of formula I differ from the known compounds, such as, for example, those known from US 5,801 ,120, by a double bond at the 6,7-position of the bicyclo[3.2.1]oct-3-en- 2-ones. That new and innovative structural element has an extremely advantageous effect on the herbicidal action of the claimed compounds of formula I. It is entirely surprising and is on no account to be inferred from the prior art that supplementing the bicyclic cyclohexane- diones with a double bond at the 6,7-position of the bicyclo[3.2.1]oct-3-en-2-ones is able to bring about such an advantageous improvement in properties.
  • the compound according to the present invention exhibits a significant improvement in action against all tested weeds, and this is especially clear, for example, in the case of Digitaria: the compound from the prior art is totally unsatisfactory for use against Digitaria (rating: 2), whereas the compound according to the present invention provides very good control (rating: 7). In the case of Kochia too, the compound from the prior art exhibits only unsatisfactory control, whereas the compound according to the present invention surprisingly exhibits almost total control of that weed (rating: 9).

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Les composés de formule (I) dans laquelle les substituant sont tels que définis dans la revendication 1, conviennent à l'utilisation en tant qu'herbicides.
PCT/EP2005/006707 2004-06-22 2005-06-21 Bicyclooctenes substitues et leur utilisation en tant qu'herbicides WO2005123667A1 (fr)

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CH10502004 2004-06-22
CH01051/04 2004-06-22
CH10512004 2004-06-22
CH01050/04 2004-06-22

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WO2008145336A1 (fr) 2007-05-29 2008-12-04 Syngenta Limited Composés bicycliques de 1,3-dione actifs sur le plan herbicide
WO2009019005A2 (fr) 2007-08-08 2009-02-12 Syngenta Limited Nouveaux herbicides
WO2009030450A2 (fr) 2007-09-03 2009-03-12 Syngenta Limited Nouveaux herbicides
WO2010089211A1 (fr) 2009-02-04 2010-08-12 Syngenta Limited Nouveaux herbicides
JP2010535726A (ja) * 2007-08-09 2010-11-25 シンジェンタ リミテッド 新規の除草剤
WO2011035875A1 (fr) * 2009-09-25 2011-03-31 Bayer Cropscience Ag Dérivés benzoyliques 3-amino-2-nitro-substitués et leur utilisation comme herbicides
EP2527333A1 (fr) 2007-06-28 2012-11-28 Syngenta Limited Composés de pyrandione, thiopyrandione et cyclohexanetrione ayant des propriétés herbicides
JP2013500285A (ja) * 2009-07-29 2013-01-07 バイエル・クロップサイエンス・アーゲー ２−（３−アルキルチオベンゾイル）シクロヘキサンジオン類及び除草剤としてのそれらの使用
US8598365B2 (en) 2007-08-01 2013-12-03 Syngenta Limited Herbicides
US8680012B2 (en) 2006-12-14 2014-03-25 Syngenta Crop Protection Llc 4-phenyl-pyrane-3,5-diones,4-phenyl-thiopyrane-3,6-diones and cyclohexanetriones as novel herbicides
US8680339B2 (en) 2009-02-04 2014-03-25 Syngenta Limited Herbicides
US8865623B2 (en) 2009-01-15 2014-10-21 Syngenta Limited Herbicidally active cyclic diones and derivatives thereof, processes for their preparation, compositions, and method of controlling weeds
US8884034B2 (en) 2009-07-08 2014-11-11 Dermira (Canada), Inc. TOFA analogs useful in treating dermatological disorders or conditions
US8895761B2 (en) 2007-12-13 2014-11-25 Syngenta Limited 4-phenylpyrane-3,5-diones, 4-phenylthiopyrane-3,5-diones and 2-phenylcyclohexane-1,3,5-triones as herbicides
US8895474B2 (en) 2009-01-22 2014-11-25 Syngenta Limited Herbicidally active cyclopentanediones and derivatives thereof, and their use in controlling weeds
WO2016195384A1 (fr) * 2015-06-01 2016-12-08 한국화학연구원 Composé à base de benzoylcyclohexanedione, et herbicide le contenant
CN109180696A (zh) * 2018-10-11 2019-01-11 辽宁大学 环烯酮类化合物及其制备方法和应用

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WO2000037437A1 (fr) * 1998-12-21 2000-06-29 Syngenta Participations Ag Nouveaux herbicides
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US8680012B2 (en) 2006-12-14 2014-03-25 Syngenta Crop Protection Llc 4-phenyl-pyrane-3,5-diones,4-phenyl-thiopyrane-3,6-diones and cyclohexanetriones as novel herbicides
US9006429B2 (en) 2006-12-14 2015-04-14 Syngenta Crop Protection, Llc Herbicidal pyrandione, thiopyrandione, and cyclohexanetrione derivatives
EA020771B1 (ru) * 2007-05-29 2015-01-30 Зингента Лимитед Гербицидно активные бициклические 1,3-дионы
US8828908B2 (en) 2007-05-29 2014-09-09 Syngenta Limited Herbicidally active bicyclic 1,3-dione compounds
AU2008256487B2 (en) * 2007-05-29 2014-02-20 Syngenta Limited Herbicidally active bicyclic 1,3-dione compounds
WO2008145336A1 (fr) 2007-05-29 2008-12-04 Syngenta Limited Composés bicycliques de 1,3-dione actifs sur le plan herbicide
AP2521A (en) * 2007-05-29 2012-11-29 Syngenta Ltd Herbicidally active bicyclic 1,3-dione compounds
EP2527333A1 (fr) 2007-06-28 2012-11-28 Syngenta Limited Composés de pyrandione, thiopyrandione et cyclohexanetrione ayant des propriétés herbicides
US8598365B2 (en) 2007-08-01 2013-12-03 Syngenta Limited Herbicides
AU2008285937B2 (en) * 2007-08-08 2013-09-26 Syngenta Limited Tricyclic bridged cyclopentanedione derivatives as herbicides
JP2010535724A (ja) * 2007-08-08 2010-11-25 シンジェンタ リミテッド 新規除草剤
WO2009019005A3 (fr) * 2007-08-08 2009-12-10 Syngenta Limited Nouveaux herbicides
WO2009019005A2 (fr) 2007-08-08 2009-02-12 Syngenta Limited Nouveaux herbicides
US8754242B2 (en) 2007-08-08 2014-06-17 Syngenta Crop Protection Llc Herbicides
US8940913B2 (en) 2007-08-09 2015-01-27 Syngenta Crop Protection, Llc Herbicides
JP2010535726A (ja) * 2007-08-09 2010-11-25 シンジェンタ リミテッド 新規の除草剤
AU2008295040B2 (en) * 2007-09-03 2013-08-29 Syngenta Limited Novel herbicides
US8530667B2 (en) 2007-09-03 2013-09-10 Syngenta Limited Herbicides
WO2009030450A3 (fr) * 2007-09-03 2009-07-23 Syngenta Ltd Nouveaux herbicides
WO2009030450A2 (fr) 2007-09-03 2009-03-12 Syngenta Limited Nouveaux herbicides
JP2010537956A (ja) * 2007-09-03 2010-12-09 シンジェンタ リミテッド 新規の除草剤
CN101835781B (zh) * 2007-09-03 2013-07-24 辛根塔有限公司 除草剂
US8895761B2 (en) 2007-12-13 2014-11-25 Syngenta Limited 4-phenylpyrane-3,5-diones, 4-phenylthiopyrane-3,5-diones and 2-phenylcyclohexane-1,3,5-triones as herbicides
US8865623B2 (en) 2009-01-15 2014-10-21 Syngenta Limited Herbicidally active cyclic diones and derivatives thereof, processes for their preparation, compositions, and method of controlling weeds
US8895474B2 (en) 2009-01-22 2014-11-25 Syngenta Limited Herbicidally active cyclopentanediones and derivatives thereof, and their use in controlling weeds
US8680339B2 (en) 2009-02-04 2014-03-25 Syngenta Limited Herbicides
WO2010089211A1 (fr) 2009-02-04 2010-08-12 Syngenta Limited Nouveaux herbicides
US9102642B2 (en) 2009-02-04 2015-08-11 Syngenta Limited Herbicidally active cyclic diones and derivatives thereof, processes for their preparation, compositions, and methods of controlling weeds
US8884034B2 (en) 2009-07-08 2014-11-11 Dermira (Canada), Inc. TOFA analogs useful in treating dermatological disorders or conditions
US9434718B2 (en) 2009-07-08 2016-09-06 Dermira (Canada), Inc. TOFA analogs useful in treating dermatological disorders or conditions
US9782382B2 (en) 2009-07-08 2017-10-10 Dermira (Canada), Inc. TOFA analogs useful in treating dermatological disorders or conditions
JP2013500285A (ja) * 2009-07-29 2013-01-07 バイエル・クロップサイエンス・アーゲー ２−（３−アルキルチオベンゾイル）シクロヘキサンジオン類及び除草剤としてのそれらの使用
US8188002B2 (en) 2009-09-25 2012-05-29 Bayer Cropscience Ag 3-amino-2-nitro-substituted benzoyl derivatives and use thereof as herbicides
WO2011035875A1 (fr) * 2009-09-25 2011-03-31 Bayer Cropscience Ag Dérivés benzoyliques 3-amino-2-nitro-substitués et leur utilisation comme herbicides
WO2016195384A1 (fr) * 2015-06-01 2016-12-08 한국화학연구원 Composé à base de benzoylcyclohexanedione, et herbicide le contenant
CN109180696A (zh) * 2018-10-11 2019-01-11 辽宁大学 环烯酮类化合物及其制备方法和应用

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