SUBSTITUTED BICYCLOOCTENES AND THEIR USE AS HERBICIDES

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

wherein Y is oxygen, -N(R43)-, sulfur, sulfinyl, sulfonyl, -C(O)-, -C(=NR4b)-, -C(=CR6aR6b)- or a CrC4alkylene or C2-C4alkenylene chain which may be interrupted by oxygen, -N(R53)-, sulfur, sulfinyl, sulfonyl, -C(O)- or by -C(=NR5b)- and/or substituted one or more times by R6;

R43 and R5a are each independently of the other hydrogen, CrC6alkyl, d-Cehaloalkyl, cyano, formyl, CrC6alkylcarbonyl, Ci-C6alkoxycarbonyl, carbamoyl, d-Cealkylaminocarbonyl, di(CrC6alkylamino)carbonyl, di(C1-C6alkylamino)sulfonyl, C3-C6cycloalkylcarbonyl, C1-C6- alkylsulfonyl, phenylcarbonyl, phenylaminocarbonyl or phenylsulfonyl, wherein the phenyl groups may in turn be substituted one, two, three, four or five times by CrC6alkyl, CrC6- haloalkyl, CrC6alkoxy, CrC6haloalkoxy, halogen, cyano, hydroxy and/or by nitro; R4b and R5b are each independently of the other hydroxy, d-Cealkoxy, C3-C6alkenyloxy, C3-C6alkynyloxy or benzyloxy, wherein the phenyl group of the benzyl group may in turn be substituted one, two, three, four or five times by CrC6alkyl, CrC6haloalkyl, C-ι-C6alkoxy, CrC6haloalkoxy, halogen, cyano, hydroxy and/or by nitro;

R6a is hydrogen, CrC6alkyl, Ci-C6alkylcarbonyl or CVCβalkylcarbonyloxy; R6b is hydrogen or C-rC6alkyl; or R6a together with R6b is a C2-C5alkylene chain;

A1 is nitrogen or CR7;

A2 is nitrogen or CR8;

R-i, R2, Re, R7 and R8 are each independently of the others hydrogen, CrC6alkyl, C2-C6- alkenyl, C2-C6alkynyl, halogen, hydroxy, mercapto, nitro, cyano, CrC6alkoxycarbonyl, CrC6- alkylcarbonyl, formyl, hydroxyiminomethylene, d-C6alkoxyiminomethylene, CrC6alkoxy, Ci-C6haloalkoxy, C3-C6alkenyloxy, C3-C6alkynyloxy, CrC4alkoxy-Ci-C2alkoxy, CrC6alkoxy- carbonyloxy, CrC6alky!carbonyloxy, Ci-C6alkylthio, Ci-C6alkylsulfonyl, Ci-C6alkylsulfinyl, N(R9Ri0), tri(C1-C6alkyl)silyl, phenyl-di(CrC6alkyl)silyl, tri(CrC6alkyl)silyloxy, benzyloxy, U1 or -OU13;

or R1, R2, R6, R7 and R8 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, CrC6alkoxy, C3-C6alkenyloxy, C3-C6alkynyloxy, Ci-C6halo- alkoxy, C1 -C4BIkOXy-C1 -C2alkoxy, Ci-C4alkoxycarbonyloxy, CrC4alkylcarbonyloxy, C1-C4- alkoxycarbonyl, CrC4alkylcarbonyl, CrC6alkylthio, CrC6alkylsulfinyl, CrC6alkylsulfonyl, N(Ri2R13), C3-C6cycloalkyl, In(C1 -C6alkyl)silyl, phenyl-di(CrC6alkyl)silyl, tri(Ci-C6alkyl)silyloxy, U2 and/or by -OU2a;

or R1, R2, R6, R7 and R8 are each independently of the others a C2-C6alkyl, C3-C6alkenyl or C3-C6alkynyl group which is interrupted once or twice by oxygen, sulfur, sulfinyl, sulfonyl, -N(R15)- 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, CrC6alkoxy, C3-C6- alkenyloxy, C3-C6alkynyloxy, Ci-C6haloalkoxy, CrC4alkoxy-CrC2alkoxy, CrC4alkoxy- carbonyloxy, Ci-C4alkylcarbonyloxy, CrC4alkoxycarbonyl, C1-C4alkylcarbonyl, CrC6alkylthio, CrC6alkylsulfinyl, CrC6alkylsulfonyl, N(R16R17), C3-C6cycloalkyl, tri(CrC6alkyl)silyl, phenyl- di(CrC6alkyl)silyl, tri(CrC6alkyl)silyloxy, U4 and/or by -OU43; or two substituents R6 at the same carbon atom together form a C2-C5alkylene chain in which one or two carbon atoms of the C2-C5alkylene chain may have been replaced by oxygen, sulfur, sulfinyl and/or by sulfonyl and/or which may be substituted one or more times by R6c, with the proviso that two hetero atoms cannot be adjacent to one another;

or two substituents R6 at different carbon atoms together form an oxygen bridge or a d-C4alkylene chain which may in turn be substituted one or more times by R6d;

or R7 and R8 together form a -CH=CH-CH=CH- bridge or a C2-C4alkylene chain in which one or two carbon atoms of the C2-C4alkylene chain may have been replaced by oxygen, sulfur, sulfinyl and/or by sulfonyl and/or which may be substituted one or more times by R6e, with the proviso that two hetero atoms cannot be adjacent to one another;

Rg, Ri3, Ri5 and R17 are each independently of the others hydrogen, Ci-C6alkyl, CrC6halo- alkyl, CrC6alkylcarbonyl, CrC6alkoxycarbonyl, C-ι-C6alkylsulfonyl or U9; R10, Ri2 and Ri6 are each independently of the others hydrogen or Ci-C6alkyl;

Rβo, Red and R6e are each independently of the others CrC6alkyl or CrC6haloalkyl;

R3 is hydroxy, 0"M+, halogen, Ci-C8alkoxy, mercapto, CrC8alkylthio, CrC8alkylsulfinyl, Ci-C8alkylsulfonyl, Ci-C8haloalkylthio, CrC8haloalkylsulfinyl, CrC8haloalkylsulfonyl, CrC4- alkoxy-Ci-C4alkylthio, C1-C4alkoxy-CrC4alkylsulfinyl, Ci-C4alkoxy-CrC4alkylsulfonyl, C3-C8- alkenylthio, C3-C8alkynylthio, Ci-C4alkylthio-CrC4alkylthio, C3-C4alkenylthio-Ci-C4alkylthio, CrC4alkoxycarbonyl-Ci-C4alkylthio, Ci-C4alkoxycarbonyl-CrC4alkylsulfinyl, CrC4alkoxy- carbonyl-CrC4alkylsulfonyl, U3-S(O)nr, phenyl-CrC4alkylthio, phenyl-CrC4alkylsulfinyl or phenyl-CrC4alkylsulfonyl, wherein the phenyl-containing groups may in turn be substituted one, two, three, four or five times on the phenyl group by CrC3alkyl, CrC3haloalkyl, CrC3- alkoxy, CrC3haloalkoxy, CrC4alkoxycarbonyl, halogen, cyano, hydroxy and/or by nitro;

M+ is an alkali metal cation or ammonium cation; - A -

and wherein Q is a phenyl group having one, two, three or four identical or different R02 substituent(s);

each Ro2 independently of any other(s) is halogen, Ci-C6alkyl, Ci-C6haloalkyl, C2-C6alkenyl, C2-C6haloalkenyl, C2-C6alkynyl, C2-C6haloalkynyl, CrC6alkoxy, d-C6haloalkoxy, C3-C6- alkenyloxy, C3-C6haloalkenyloxy, C3-C6alkynyloxy, C3-C6haloalkynyloxy, CrC6alkoxy- Ci-C6alkoxy, cyano-CrC6alkoxy, cyano-CrC6alkenyloxy, d-C6alkoxycarbonyl-CrC6alkoxy, aminocarbonyl-Ci-Cealkoxy, CrC6alkylaminocarbonyl-CrC6alkoxy, di(CrC6alkyl)amino- carbonyl-CrC6alkoxy, d-C6alkylcarbonylamino-d-C6alkoxy, N-(C1 -C4alkyl)-d -C4alkyl- carbonylamino-Ci-C6alkoxy, [di(C1-C6alkyl)aminocarbonyl]amino-C1-C6alkoxy, N-(CrC4alkyl)- [di(CrC6alkyl)aminocarbonyl]amino-Ci-C6alkoxy, Ci-C6alkoxycarbonyloxy-CrC6alkoxy, CrC6alkoxycarbonylamino-CrC6alkoxy, N-(Ci-C4alkyl)-Ci-C6alkoxycarbonylamino-CrC6- alkoxy, CrC6alkylthio-CrC6alkoxy, d-Cealkylsulfinyl-d-Cealkoxy, CrC6alkylsulf OnVl-C1 -C6- alkoxy, Ci-C6alkylsulfonyloxy, CrC6haloalkylsulfonyloxy, d-C6alkylthio, Ci-C6alkylsulfinyl, d-C6alkylsulfonyl, d-C6haloalkylthio, CrCehaloalkylsulfinyl, CrCehaloalkylsulfonyl, CrC6- alkoxy-d-C6alkylthio, CrCealkoxy-Ci-Cealkylsulfinyl, Ci-Cealkoxy-d-Cealkylsulfonyl, C1-C6- aIkoxycarbonyl-CrC6alkylthio, d-Cealkoxycarbonyl-d-Cβalkylsulfinyl, CrCβalkoxycarbonyl- CrCδalkylsulfonyl, CrCealkoxycarbonyl, CrC6alkylcarbonyl, N(RO36Ro37), N(R03BRO39)S02, R019SO2N (R01 β)> nitro, cyano, hydroxy, formyl, CH(=NRO4o), hydroxy-CrCβalkyl, C-ι-C6alkoxy- CrC6alkyl, CrCehaloalkoxy-CrCealkyl, d-Cδalkylcarbonyloxy-d-Cealkyl, CrC6alkylcarbonyl- amino-CrC6alkyl, N-(C1-C4alkyl)-C1-C6alkylcarbonylamino-C1-C6alkyl, CrCealkoxycarbonyl- OXy-C1 -C6alkyl, d-Cealkoxycarbonylamino-d-Cealkyl, N-(C1-C4BIkVl)-(C1-C6BIkOXyCa^OnVl)- amino-Ci-C6alkyl, CrCealkylaminocarbonylamino-CrCealkyl, N-(C1-C4alkyl)-(C1-C6alkyl- aminocarbonyOamino-CrCealkyl, di(C1-C6alkyl)aminocarbonylamino-C1-C6alkyl, N-(CrC4- alkyl)-[di(CrC6alkyl)aminocarbonyl]amino-CrC6alkyl, d-Cealkylthio-d-Cealkyl, CrC6alkyl- sulfinyl-CrC6alkyl, d-Cealkylsulfonyl-CrCealkyl, R025S02N(Ro24)-CrC6alkyl, rhodano- d-C6alkyl, cyano-CrC6alkyl, Cs-Cealkenyloxy-CrCεalkyl, Cs-Cehaloalkenyloxy-CrCealkyl, C3-C6alkynyloxy-CrC6alkyl, Cs-Cehaloalkynyloxy-CrCεalkyl, d-C6alkoxy-CrC6alkoxy- CrC3alkyl, CrC6haloalkoxy-CrC6alkoxy-CrC3alkyl, CrC4alkoxy-CrC4alkoxy-CrC4alkoxy- d-C3alkyl, d-C4alkoxy-CrC4alkoxy-CrC4alkoxy-CrC4alkoxy-CrC3alkyl, CrC6alkylcarbonyl- oxy-CrC6alkoxy-CrC3alkyl, CrC6alkoxycarbonyl-CrC6alkoxy-CrC3alkyl, CrC6alkylthio- CrC6alkoxy-CrC3alkyl, CrC6alkoxycarbonyl-CrC6alkylthio-CrC3alkyl, CrC6alkoxycarbonyl- d-Cealkylsulfinyl-d-dialkyl or d-C6alkoxycarbonyl-CrC6alkylsulfonyl-CrC3alkyl; or each R02 independently of any other(s) is a three- to ten-membered monocyclic or bicyclic ring system which may be aromatic, partially saturated or fully saturated and may contain 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 may have been replaced by a carbonyl, thio- carbonyl, sulfinyl, sulfonyl or -C(=NR052)- group, and wherein the ring system is bonded to the group Q directly, by way of a -C(Ro46)=C(Ro47)-. -OC-, -C(O)-, -C(O)O-, -0-, -OC(O)-, -ON(R048)-, -ON=C(R053)-, -N(R049)-, -N(R050)C(O)-, -C(O)N(R051)-, -S-, -S(O)-, -SO2-, -SO2N(R04i)- or -N(R042)SO2 group or by way of a CrC4alkylene chain which may be interrupted by -C(R046a)=C(R047a)-, -OC-, -C(O)-, -C(O)O-, -0-, -OC(O)-, -ON(R0483)-, -ON=C(R0533)-, -N(R0493)-, -N(R0503)C(O)-, -C(O)N(R05Ia)-, -S-, -S(O)-, -SO2-, -SO2N(R043)- or by -N(R044)SO2- and substituted one or more times at a chain carbon atom by Ci-C3alkyl, and wherein the ring system itself may be substituted one, two or three times by halogen, CrC6alkyl, d-C6haloalkyl, C2-C6alkenyl, C2-C6haloalkenyl, C2-C6alkynyl, C2-C6haloalkynyl, CrC6alkoxy, CrC6haloalkoxy, C3-C6alkenyloxy, C3-C6haloalkenyloxy, C3-C6alkynyloxy, CrCealkylthio, CrC6haloalkylthio, C3-C6alkenylthio, C3-C6haloalkenylthio, C3-C6alkynylthio, C1 -C-^aIkOXy-C1 -C3alkylthio, Crdalkylcarbonyl-CrCjjalkylthio, CrC4alkoxycarbonyl-CrC3- alkylthio, cyano-C-rC3alkylthio, d-Cealkylsulfinyl, CrCβhaloalkylsulfinyl, Ci-C6alkylsulfonyl, CrCehaloalkylsulfonyl, aminosulfonyl, CrC4alkylaminosulfonyl, di(CrC4alkyl)aminosulfonyl, R028-Ci -C4alkylene wherein the alkylene chain may be interrupted by oxygen, sulfur, sulfinyl or by sulfonyl and substituted one or more times by CrC3alkyl, or N(R029R030), 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 CrC3alkyl, d-Cshaloalkyl, CrC3alkoxy, C-ι-C3haloalkoxy, 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;

or two substituents R02 at adjacent carbon atoms of the phenyl group, together with the two adjacent carbon atoms of the phenyl group, form a fused-on 4- to 10-membered mono- or bi¬ cyclic ring system which may be aromatic, partially saturated or fully saturated and may contain one, two or three hetero atoms selected from oxygen, sulfur and nitrogen and in which one, two or three atoms of the ring system may have been replaced by sulfinyl, sulfonyl, -N(R010)- and/or by -C(=X02)- and wherein the ring system may be substituted one or more times at carbon atoms by R011; Ro36 and R037 are each independently of the other hydrogen or d-C6alkyl;

Ro38> R019 and R025 are each independently of the others Ci-C6alkyl, CrC6haloalkyl, C2-C6- alkenyl, C2-C6haloalkenyl, C1-C2alkoxycarbonyl- or phenyl-substituted vinyl, or C2-C6alkynyl, C2-C6haloalkynyl, C3-C6allenyl, Ci-C4alkoxy-CrC3alkyl, C1-C4alkylthio-C1-C3alkyl, C1-C4- alkylsulfinyl-Ci-C3alkyl, Crdalkylsulfonyl-d-Csalkyl, cyano-CrC3alkyl, hydroxy-Ci-C3alkyl, CrC6alkylcarbonyloxy-CrC3alkyl, CrC4alkoxycarbonyl-CrC3alkyl, d-C4alkoxycarbonyloxy- Ci-C3alkyl, rhodano-CrC3alkyl, benzoyloxy-CrC3alkyl, Ci-C6alkylamino-d-C3alkyl, di(d-C6- alkyl)amino-CrC3alkyl, Ci-C4alkylthiocarbonyl-Ci-C3alkyl, f OmIyI-C1 -C3alkyl or N(R033Ro34), wherein the phenyl-containing radicals may in turn be substituted one, two, three, four or five times on the phenyl group by d-C4alkyl, C2-C4alkenyl, d-C4haloalkyl, d-C4alkoxy, C1-C4- haloalkoxy, halogen, -S(0)norR0i5, -SO2N(R016R017), cyano, d-C4alkoxycarbonyl, d-C4alkyl- carbonyl, cyclopropylcarbonyl or by nitro; R016, FW. R033 and R034 are each independently of the others hydrogen or d-C6alkyl;

R015 is d-C6alkyl;

R039 is hydrogen, d-C6alkyl, C2-C6alkenyl, C2-C6alkynyl, CrC6haloalkyI or d-C4a!koxy- d-C6alkyl;

R018 and R024 are each independently of the other hydrogen, CrC6alkyl, C2-C6alkenyl, C2-C6alkynyl, d-Cβhaloalkyl, C1 -C^aIkOXy-C1 -C6alkyl, 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-C4alkyl, d-C2haloalkyl, d-C2alkoxy, C1-C2haloalkoxy or by nitro;

R040 is d-C6alkoxy, C3-C6alkenyloxy, C3-C6alkynyloxy, d-C6haloalkoxy, benzyloxy, C1-C6- alkylamino, di(C1-C6alkyl)amino, phenylamino, N-(C-ι-C6alkyl)phenylamino or U7, wherein the phenyl-containing groups may in turn be substituted one, two, three, four or five times on the phenyl group by halogen, d-C4alkyl, d-Cahaloalkyl, d-C2alkoxy, d-C2haloalkoxy or by nitro;

Ro52 is hydroxy, d-C6alkoxy, C3-C6alkenyloxy, C3-C6alkynyloxy, benzyloxy, cyano or nitro; Ro46, Ro47> Ro48. R050, Ro5i> Ro46a. Ro47a. Ro48a, Ro5oa. Ro5ia, Ro53 and Ro53a are each independ¬ ently of the others hydrogen or d-C6alkyl;

Ro49 and R049a are each independently of the other Ci-C6alkyl, C-i-C6haloalkyl, C2-C6alkenyl, C2-C6haloalkenyl, C2-C6alkynyl, C2-C6haloalkynyl, C3-C6cycloalkyl, C3-C6cycloalkyl-d-C3alkyl, CrC4alkyl- sulfonyl-CrC3alkyl, cyano-CrC3alkyl, hydroxy-Ci-C3alkyl, d-C-ealkylcarbonyloxy-d-Csalkyl, C1-C4alkoxycarbonyl-C1-C3alkyl, C1-C4alkoxycarbonyloxy-C1-C3alkyl, rhodano-CrC3alkyl, CrC4alkylthiocarbonyl-CrC3alkyl or formyl-Ci-C3alkyl;

Ro4i, Ro42, Ro43 and R044 are each independently of the others hydrogen, CrC6alkyl, C2-C6- alkenyl, C2-C6alkynyl, d-Cehaloalkyl, C1-C4alkoxy-C1-C6alkyl, 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, C1-C4alkyl, CrC2haloalkyl, CrC2alkoxy, CrC2haloalkoxy or by nitro;

R028 is CrC6alkoxy, Ci-C3alkoxy-CrC3alkoxy, Ci-C6haloalkoxy, Ci-C4alkoxycarbonyl, C1-C6- alkylthio, CrC6alkylsulfinyl, d-C6alkylsulfonyl, 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 Ci-C3alkyl, CrC3haloalkyl, d-C3alkoxy, d-C3haloalkoxy, halogen, cyano or by nitro;

R02g and R03O are each independently of the other hydrogen or d-C6alkyl; or R02g together with R03O, 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(R07b)-; R07b being hydrogen, CrC6alkyl, d-C6haloalkyl, d-C4alkoxycarbonyl, d-C4alkylcarbonyl or di(CrC4alkyl)aminocarbonyl or phenyl, wherein the phenyl group may in turn be substituted one, two, three, four or five times by CrC4alkyl, d-C4haloalkyl, d-C4alkoxy, d-C4halo- alkoxy, d-C4alkylcarbonyl, d-C4alkoxycarbonyl, d-dialkylamino, di-Ci-C4alkylamino, C1-C4alkylthio, CrC4alkylsulfinyl, d-C4alkylsulfonyl, CrC4alkylsulfonyloxy, Ci-C4haloalkyl- thio, d-C4haloalkylsulfinyl, d-C4haloalkylsulfonyl, Ci-C4haloalkylsulfonyloxy, C1-C4alkyl- sulfonylamino, Λ/-(d-C4alkyl)-C1-C4alkylsulfonylamino, halogen, nitro or by cyano; Roio is hydrogen, CτC6alkyl, d-C6haloalkyl, C2-C6alkenyl, C2-C6haloalkenyl, C2-C6alkynyl, C2-C6haloalkynyl, CrC6alkoxy, d-C6alkylsulfonyl, CrC6haloalkylsulfonyl, N(ROi3Roi4), amino- sulfonyl, CrC4alkylaminosulfonyl, di(C1-C4alkyl)aminosulfonyl, formyl, cyano, CrC4alkyl- carbonyl, CτC4alkoxycarbonyl, aminocarbonyl, Ci-C4alkylaminocarbonyl, di(CrC4alkyl)- aminocarbonyl, ROaO-C1 -C4alkylene wherein the alkylene chain may be interrupted by oxygen, sulfur, sulfinyl or by sulfonyl and substituted one or more times by CrC3alkyl, or is U5a; Roi3 and R014 are each independently of the other hydrogen or CrC6alkyl;

R02O is CrC6alkoxy, CrC3alkoxy-Ci-C3alkoxy, C-|-C6haloalkoxy, Ci-C4alkoxycarbonyl, C1-C6- alkylthio, C^Cealkylsulfinyl, d-C6alkylsulfonyl, 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 CrC3alkyl, CrC3haloalkyl, CrC3alkoxy, CrC3haloalkoxy, halogen, cyano or by nitro;

X02 is oxygen, sulfur or NR012; R012 is hydroxy or CrC4alkoxy;

each Ron independently of any other(s) is halogen, C-|-C6alkyl, d-C6haloalkyl, C2-C6alkenyl, C2-C6haloalkenyl, C2-C6alkynyl, C2-C6haloalkynyl, CrC6alkoxy, Ci-C6haloalkoxy, C3-C6- alkenyloxy, C3-C6alkynyloxy, CrC6alkylthio, CrC6haloalkylthio, C3-C6alkenylthio, C3-C6halo- alkenylthio, C3-C6alkynylthio, C1 -C4alkoxy-d -C2alkylthio, d-C^alkylcarbonyl-CrCsialkylthio, d-dalkoxycarbonyl-d-C^alkylthio, cyano-CrC4alkylthio, CrCεalkylsulfinyl, d-C6haloalkyl- sulfinyl, CrC6alkylsulfonyl, CrC6haloalkylsulfonyl, N(Ro13aRoi4a), aminosulfonyl, CrC4alkyl- aminosulfonyl, di(d-C4alkyl)aminosulfonyl, R02Oa-C1 -C4alkylene wherein the alkylene chain may be interrupted by oxygen, sulfur, sulfinyl, sulfonyl or by -N(R04S)- and may be substituted one or more times by d-C3alkyl, or cyano, d-C4alkylcarbonyl, d-C4alkoxycarbonyl, amino¬ carbonyl, d-Czialkylaminocarbonyl, di(d-C4alkyl)aminocarbonyl, nitro, U5 or IVX03; R013a and R0-I43 are each independently of the other hydrogen or d-Cβalkyl; R02Oa is CrC6alkoxy, C1 -C3alkoxy-Ct -C3alkoxy, d-C6haloalkoxy, d-d.alkoxycarbonyl, d-C6alkylthio, d-C6alkylsulfinyl, d-C6alkylsulfonyl, 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-C3alkyl, d-C3haloalkyl, d-C3alkoxy, d-C3haloalkoxy, halogen, cyano or by nitro; R045 is hydrogen, d-C6alkyl, d-C6haloalkyl, C2-C6alkenyl, C2-C6haloalkenyl, C2-C6alkynyl, C2-C6haloalkynyl, Ci-C6alkoxy, CrC6alkylsulfonyl, CrC6haloalkylsulfonyl, N(Ro13bRoi4b), aminosulfonyl, CrC4alkylaminosulfonyl, di(Ci-C4alkyl)aminosulfonyl, formyl, cyano, C1-C4- alkylcarbonyl, C1-C4alkoxycarbonyl, aminocarbonyl, d-C4alkylaminocarbonyl, di(d-C4alkyl)- aminocarbonyl, R02Ob-Ci -C3alkylene wherein the alkylene chain may be interrupted by oxygen, sulfur, sulfinyl or by sulfonyl, or is U5b; R0i3b and R014b are each independently of the other hydrogen or CrC6alkyl; R02Ob is CrC6aIkoxy, d-Csalkoxy-d-dialkoxy, d-C6haloalkoxy, d-C4alkoxycarbonyl, d-C6alkylthio, d-C6alkylsulfinyl, d-C6alkylsulfonyl, 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-C3alkyl, d-C3haloalkyl, d-C3alkoxy, d-C3haloalkoxy, halogen, cyano or by nitro; X03 is oxygen, sulfur or NR0453; Ro4Sa is hydrogen or d-C6alkyl;

Ui, Uia, U2, U23, U3, U4, U4a> U5, U5a> U5b, U6, U7 and U9 are each independently of the others a three- to ten-membered, monocyclic or bicyclic ring system which may be aromatic, partially saturated or fully saturated and which may contain one, two, three or four hetero atoms selected from nitrogen, oxygen and sulfur and in which one, two, three or four carbon atoms of the ring system may have been replaced by -S(O)-, -SO2- and/or by -C(=X01)- and wherein the ring system may be bonded by way of a carbon atom or by way of a nitrogen atom, and each ring system may itself be substituted one or more times by d-C6alkyl, C1-C6- haloalkyl, C2-C6alkenyl, C2-C6haloalkenyl, C2-C6alkynyl, C2-C6haloalkynyl, d-C6alkoxy, Ci-C6haloalkoxy, C3-C6alkenyloxy, C3-C6alkynyloxy, mercapto, amino, hydroxy, d-C6alkyl- thio, d-C6haloalkylthio, C3-C6alkenylthio, C3-C6haloalkenylthio, C3-C6alkynylthio, C1-C3- alkoxy-C-|-C3alkylthio, d-dalkylcarbonyl-d-Csalkylthio, d-dalkoxycarbonyl-d-djalkylthio, cyano-Crdsalkylthio, C-ι-C6alkylsulfinyl, d-C6haloalkylsulfinyl, d-C6alkylsulfonyl, C1-C6- haloalkylsulfonyl, aminosulfonyl, d-C6alkylaminosulfonyl, di(CrC6alkyl)aminosulfonyl, di(Ci-C6alkyl)amino, halogen, cyano, nitro or by phenyl, wherein the phenyl group may in turn be substituted one, two, three, four or five times by hydroxy, d-C6alkylthio, d-C6haloalkyl- thio, C3-C6alkenylthio, C3-C6haloalkenylthio, C3-C6alkynylthio, d-Csalkoxy-d-dialkylthio, Ci-C4alkylcarbonyl-CrC3alkylthio, Crdalkoxycarbonyl-d-Csalkylthio, cyano-CrCsalkylthio, Ci-C6alkylsulfinyl, d-C6haloalkylsulfinyl, d-C6alkylsulfonyl, d-C6haloalkylsulfonyl, amino¬ sulfonyl, CrC4alkylaminosulfonyl, di(d-C4alkyl)aminosulfonyl, di(CrC4alkyl)amino, 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; Xoi is oxygen, sulfur or NR25; R25 is hydrogen, hydroxy, d-C^alky!, d-Cehaloalkyl, d-Cealkoxy, C-i-Cealkylcarbonyl, Ci-C6alkoxycarbonyl or CrC6alkylsulfonyl;

and to the agrochemically acceptable salts and all stereoisomers and tautomers of the compounds of formula I.

The 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.

Preferred 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, and 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. Preference is given to 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-C4HaIoalkyl 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-trichloroethyl, 1 ,1 ,2,2-tetrafluoroethyl, 2,2,3,3-tetrafluoropropyl, 2,2,3,3,3- pentafluoropropyl, 2,2,3,4,4,4-hexafluorobutyl; preferably fluoromethyl, difluoromethyl, difluorochloromethyl, dichlorofluoromethyl, trifluoromethyl, 2-chloroethyl, 2,2,2-trifluoroethyl, 2,2,3,3-tetrafluoropropyl, 2,2,3,3,3-pentafluoropropyl.

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. Preferably, halogen is especially fluorine and chlorine. As haloalkynyl groups there likewise come into consider¬ ation 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. The same applies also to 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.

Ro2 having the meaning of a three- to ten-membered monocyclic or bicyclic ring system which can be aromatic, partially saturated or fully saturated and may contain 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 may have been replaced by a carbonyl, thiocarbonyl, sulfinyl, sulfonyl or -C(=NR052)- group and wherein the ring system itself may be substituted, is to be understood in the context of the present invention as being, for example, phenyl, alpha- or befø-naphthyl, indan-5-yl, inden-3-yl, cyclopenten-3-yl, cyclohexen-3-yl or C3-C8- cycloalkyl, for example cyclopropylmethyl, cyclopentyl, or C3-C6oxacycloalkyl, C2-C5dioxa- cycloalkyl, C3-C6cycloalkyl-Ci-C3alkyl, C3-C6oxacycloalkyl-C1-C2alkyl or C3-C6dioxacycloalkyl- CrC2alkyl, or similar ring systems that contain one, two, three or four hetero atoms selected from nitrogen, oxygen and sulfur, especially three- to six-membered fully saturated ring systems containing one or two oxygen atoms, for example oxetan-3-yl, tetrahydrofuran-3-yl, tetrahydropyran-2-yl, 1 ,3-dioxacyclopent-2-yl, 1 ,3-dioxacyclopent-4-yl, 1 ,3-dioxacyclohex-2- yl, 1 ,3-dioxacyclohex-5-yl, oxiranyl-methyl, 3-oxetanyl-methyl, tetrahydrofuran-3-yl-methyl, tetrahydrofuran-2-yl-methyl, 1 ,3-dioxacyclopent-2-yl-methyl or cis- and/or trans-1 ,3-dioxa-4,5- dimethyl-cyclopent-2-yl-methyl, or three- to six-membered fully saturated ring systems that contain one or two sulfur atoms, for example 1 ,3-oxathio-cyclopent-2-yl, tetrahydrothien-2-yl- methyl, 1.S-oxathio-cyclopent^-yl-methyl or 1 ,3-dithiacyclopent-2-yl-methyl.

Ro2 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-triazol-1 -yl, 5-methyl-1 H-1 ,2,4-triazol-1 -yl or 4H-1 ,2,4-triazol-4-yl.

Ro2 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-methyl-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-furanyl, 5-methyl-2-furanyl, 3-furanyl, 5- methyl-2-thienyl, 2-thienyl, 3-thienyl, 1 -methyl-1 H-imidazol-2-yl, 1 H-imidazol-2-yl, 1 -methyl- 1 H-imidazol-4-yl, 1 -methyl-1 H-imidazol-5-yl, 4-methyl-2-oxazolyl, 5-methyl-2-oxazolyl, 2- oxazolyl, 2-methyl-5-oxazolyl, 2-methyl-4-oxazolyl, 4-methyl-2-thiazolyl, 5-methyl-2-thiazolyl, 2-thiazolyl, 2-methyl-5-thiazolyl, 2-methyl-4-thiazolyl, 3-methyl-4-isothiazolyl, 3-methyl-5- isothiazolyl, 5-methyl-3-isothiazolyl, 1 -methyl-1 H-1 ,2,3-triazol-4-yl, 2-methyl-2H-1 ,2,3-triazol- 4-yl, 4-methyl-2H-1 ,2,3-triazol-2-yl, 1 -methyl-1 H-1 ,2,4-triazol-3-yl, 1 ,5-dimethyl-1 H-1 ,2,4- triazol-3-yl, 4,5-dimethyl-4H-1 ,2,4-triazol-3-yl, 4-methyl-4H-1 ,2,4-triazol-3-yl, 5-methyl-1 ,2,3- oxadiazol-4-yl, 1 ,2,3-oxadiazol-4-yl, 3-methyl-1 ,2,4-oxadiazol-5-yl, 5-methyl-1 ,2,4-oxadiazol- 3-yl, 5-methyl-1 ,2,3-thiadiazol-4-yl, 1 ,2,3-thiadiazol-4-yl, 3-methyl-1 ,2,4-thiadiazol-5-yl, 5- methyl-1 ,2,4-thiadiazol-3-yl, 4-methyl-1 ,2,5-thiadiazol-3-yl, 5-methyl-1 ,3,4-thiadiazol-2-yl, 2- pyridinyl, 6-methyl-2-pyridinyl, 4-pyridinyl, 3-pyridinyl, 6-methyl-3-pyridazinyl, 5-methyl-3- pyridazinyl, 3-pyridazinyl, 4,6-dimethyl-2-pyrimidinyl, 4-methyl-2-pyrimidinyl, 2-pyrimidinyl, 2- methyl-4-pyrimidinyl, 2-chloro-4-pyrimidinyl, 2,6-dimethyl-4-pyrimidinyl, 4-pyrimidinyl, 2- methyl-5-pyrimidinyl, 6-methyl-2-pyrazinyl, 2-pyrazinyl, 4,6-dimethyl-1 ,3,5-triazin-2-yl, 4,6- dichloro-1 ,3,5-triazin-2-yl, 1 ,3,5-triazin-2-yl, 4-methyl-1 ,3,5-triazin-2-yl, 3-methyl-1 ,2,4-triazin- 5-yl or 3-methyl-1 ,2,4-triazin-6-yl, or an aromatic 5- or 6-membered heteroaryl group bonded via a N atom, which may contain an oxygen, a sulfur and/or one, two or three nitrogen atoms, for example 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-trifluoromethy!-1 H-pyrazol-1-yl, 3-methyl-1 H-1 ,2,4-triazol-1-yl, 5-methyl- 1 H-1 ,2,4-triazoM -yl, 4H-1 ,2,4-triazol-4-yl.

Ro2 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,

wherein X4 is oxygen or sulfur and preferably independently from each other each R25, R26> R27, R31 and R34 are CrC3alkyl, especially methyl, R28 is hydrogen or CrC3alkyl, R29, R30 and R33 are amino, CrC3alkyl, CrC3haloalkyl, cyclopropyl, methoxymethyl or CrC3alkoxy, R32 is preferably hydrogen, chlorine, bromine, Ci-C3alkyl, CrC3haloalkyl, cyclopropyl, CVC-salkoxy, CrC3alkylthio, and r = 0, 1 , 2 or up to 8.

U-i, U1a, U2, U23, U3, U4, U4a, U5, U53, U5b, U6, U7 and U9 having the meaning of a three- to ten- membered, monocyclic or bicyclic ring system which may be aromatic, partially saturated or fully saturated and which may contain one, two, three or four hetero atoms selected from nitrogen, oxygen and sulfur and in which one, two, three or four carbon atoms of the ring system may have been replaced by -S(O)-, -SO2- and/or by -C(=Xoi)-, and which ring system may itself be substituted one or more times, is to be understood as being, for example, phenyl, alpha- or befa-naphthyl, indan-5-yl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopenten-3-yl, cyclohexen-3-yl or the above-mentioned examples of three- to ten- membered ring systems selected as examples of the group R02.

Q having the meaning of a phenyl group substituted three or four times by R02, wherein two substituents R02 at adjacent carbon atoms of the phenyl group, together with the two adjacent carbon atoms of the phenyl group, form a fused-on 4- to 10-membered mono- or bi¬ cyclic ring system which may be aromatic, partially saturated or fully saturated and may contain one, two or three hetero atoms selected from oxygen, sulfur and nitrogen and in which one, two or three atoms of the ring system may have been replaced by sulfinyl, sulfonyl, -N(ROio)- and/or by -C(=Xo2)- and wherein the ring system may be substituted one or more times at the carbon atoms by ROn is to be understood as being, for example, a heterocyclic group such as, for example, a group Qi to Q9

(Qi), (Q2), (Q3),

wherein preferably independently from each other each Rom, R0113, Ron4 is CrC3alkyl; R0112 is CrC3alkyl or CrC3alkoxy-CrC2alkyl; R0122 is hydrogen, CrC4alkyl, C3-C4alkenyl, C3- C4alkynyl, C1-C4haloalkyl, C1-C3alkoxy-Ci-C2alkyl, d-C3haloalkoxy-d-C2alkyl or benzyl; R0201, Ro2o4 are halogen, CrC3haloalkyl, CrC3a!kylthio, d-C3alkylsulfinyl, CrC3alkylsulfonyl, CrC3haloalkoxy or cyano; R0202 is halogen, Ci-C3alkyl, Ci-C3haloalkyl, d-C3alkoxy, C1- C2BIkOXy-C1 -C2alkoxy, CrC3alkylthio, CrC3alkylsulfinyl or d-C3alkylsulfonyl; X5 is oxygen, sulfur, sulfinyl, sulfonyl or a group -C(=O)-, -CRoIi5(ORoIIe)- or wherein R0H5 is hydrogen, CrC3alkyl or CrC3alkoxy, R0116 is CrC3alkyl or R0115 together with OR0116 is - OCH2CH2O-, R0117 is CrC4alkoxy; X7 is oxygen, sulfur or NR0123; R0123 is hydrogen, d- dalkyl, C3-C4alkenyl, C3-C4alkynyl, CrC4haloalkyl, CrC3alkoxy-CrC2alkyl, d-C3haloalkoxy- CrC2alkyl or benzyl; t is 0, 1 or 2; u is 1 or 2; and v is 0, 1 , 2, 3, 4, 5 or 6.

In the context of the present invention, ring systems wherein two oxygen atoms, or an oxygen atom and a sulfur atom, or a hetero atom, selected from nitrogen, oxygen and sulfur, and a sulfinyl group, or a -C(=O)-, -C(=S)-, -C(=NR25)-, -C(=NR012)- or -C(=NR052)- group and a sulfinyl or sulfonyl group, are adjacent to one another, are excluded.

In general, alkylene chains which may in addition be interrupted by oxygen, sulfur, sulfinyl or by sulfonyl, for example d-C4alkylene chains which may in addition be interrupted by oxygen, sulfur, sulfinyl or by sulfonyl, such as -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH2CH2CH2CH2-, -OCH2-, -CH2O-, -OCH2CH2-, -CH2CH2O-, -CH2OCH2-, -CH2OCH2CH2-, -CH2OCH2OCH2-, -CH2OCH2CH2OCH2-, -SCH2CH2-, -CH2SCH2-, -CH2S(O)CH2- or -CH2SO2CH2-, such as, for example, in R020-Ci -C4alkylene, in R020a-Ci-C4alkylene and in Ro28-CrC4alkylene, may be substituted one or more times by C^Csalkyl groups, especially by methyl groups. Preferably, however, such alkylene chains are unsubstituted.

In general, Ci-C4alkylene chains which may in addition be interrupted by -C(RO46a)=C(Ro47a)-, -OC-, -C(O)-, -C(O)O-, -0-, -OC(O)-, -ON(R0483)-, -ON=C(R0533)-, -N(R0493)-, -N(R0503)C(O)-, -C(O)N(R0513)-, -S-, -S(O)-, -SO2-, -SO2N(R043)- or -N(R044)SO2-, such as, for example, -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH2CH2CH2CH2-, -CH=CHCH2-, -C=CCH2-, -C(O)CH2-, -CH2C(O)O-, -OCH2-, -CH2O-, -OCH2CH2-, -CH2CH2O-, -CH2OCH2-, -CH2OCH2CH2-, -CH2OCH2OCH2-, -CH2OCH2CH2OCH2CH2-, -CH2OC(O)-, -CH2ON(CH3)-, -CH2ON=CH-, -CH2ON=C(CH3)-, -CH2N(COOCH3)-, -CH2C(O)N(CH3)-, -SCH2CH2-, -CH2SCH2-, -CH2S(O)CH2-, -CH2SO2CH2-, -CH2SO2N(CH3)- or -N(CH3)SO2-, such as, for example, in three- to ten-membered ring systems R02 bonded by way of a C-|-C4alkylene chain, may be substituted one or more times at a chain carbon atom by C-|-C3alkyl groups, especially by methyl groups, such as, for example, -C≡CCH(CH3)-, -CH(CH3)CH2O-, -CH2CH(CH3)O-, -CH2OCH(CH3)CH2- or -CH2OCH(CH3)OCH2-. Preferably, however, such alkylene chains are unsubstituted.

In general, alkylene chains in cycloalkyl groups, for example C3-C8cycloalkyl, such as cyclopentyl or cyclohexenyl, or in cycloalkyl groups interrupted by oxygen, sulfur and/or by nitrogen, for example C3-C8cycloalkyl interrupted by oxygen, sulfur and/or by nitrogen, such as C3-C5oxacycloalkyl, for example oxiranyl or oxetanyl, C3-C5thiacycloalkyl, C3-C4dioxa- cycloalkyl, C3-C4dithiacycloalkyl, C3-C4oxathiacycloalkyl or morpholino, may be substituted one or more times by CrC3alkyl groups, especially by methyl groups, for example 4-methyl- [1 ,3]dioxolan-2-yl, cis- and trans-4,5-dimethyl-[1 ,3]dioxolan-2-yl or cis-2,6-dimethylmorpholin- 4-yl. Preferably, however, such cyclic cycloalkyl groups and cycloalkyl groups interrupted by oxygen, sulfur and/or by nitrogen are unsubstituted.

In the context of the present invention, the phrase "substituted one or more times" which appears in the above definitions of substituents, such as, for example, in the definition of the substituents Y, R1, R2, R6, R7 and R8, typically denotes substitution from one to eight times, preferably from one to five times, more especially once, twice or three times.

In general, phenyl groups as substituents, for example in the substituent definitions for R4a, R5a and R038, are substituted one, two, three, four or five times by substituents, such as, for example, d-C6alkyl, halogen or cyano; such phenyl groups are preferably substituted once, twice or three times. It should be mentioned here that 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 R3 is hydroxy by formulae I1, 1", I"1, liv, lv, lvi and lvli , the forms I1, 1", lv and lvi being preferred as isolated forms, and formula I" also representing a rotameric form of lvι, and formula I' being a preferred rotameric form of lv" and formula lv being a preferred rotameric form of l".

When there is a C=C or C=N double bond in compounds of formula I, such as, especially, in the group Y, XOi, X02. R02 or R011, the compounds of formula I may, when asymmetry exists, be in the 1E' 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, A1, A2 or in the substituents R1, R2, R02, Ron, then chiral 1R' and 'S' forms forms may also occur. Furthermore, because, for example, Ri and R2 as well as R7 and R8 may, as a result of the spatial arrangement of A1 and A2, 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. Moreover, the substituent R3 may be located on the bridging member, as already indicated above in formulae I" and lvι wherein R3 is hydroxy. The invention therefore relates also to all those constitutional isomeric forms in respect of the spatial arrangement of A1 and A2 and the substituents R1 and R2 with respect to the substituent R3, as shown generally by formulae l", lv and lvι.

I I" lv IVl

The same applies also to the spatial arrangement of the bridging member Y in respect of the carbon atoms carrying R1 and R2 when Y is a CrC4alkylene or C2-C4alkenylene chain which may be interrupted by oxygen, -N(R53)-, sulfur, sulfinyl, sulfonyl, -C(O)- or by -C(=NR5b)- and/or substituted one or more times by R6.

The present invention therefore relates also to all stereoisomeric, rotameric, tautomeric and constitutional isomeric forms of compounds of formula I. Those arrangements of A1, A2, Q, Y and the substituents R1, R2 and R3 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 ammon¬ ium bases. Suitable salt formers are described, for example, in WO 98/41089. Among the 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 espe¬ cially the hydroxides of sodium and potassium. Examples of amines suitable for ammonium salt formation include ammonia as well as primary, secondary and tertiary CrC18alkylamines, d-C4hydroxyalkylamines and C2-C4alkoxyalkylamines, 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, ethylbutylamine, ethylheptylamine, ethyloctylamine, hexylheptylamine, hexyloctyl- amine, dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, di- n-amylamine, diisoamylamine, dihexylamine, diheptylamine, dioctylamine, ethanolamine, n- propanolamine, isopropanolamine, N,N-diethanolamine, N-ethylpropanolamine, N-butyl- ethanolamine, allylamine, n-butenyl-2-amine, n-pentenyl-2-amine, 2,3-dimethylbutenyl-2- amine, dibutenyl-2-amine, n-hexenyl-2-amine, propylenediamine, trimethylamine, triethyl- amine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, triisobutylamine, tri-sec-butyl- amine, tri-n-amylamine, 2-methoxyethylamine and 2-ethoxyethylamine; heterocyclic amines such as e.g. 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 corres¬ pond e.g. to the formula [+N(RaRbRcRd) "OH] wherein Ra, Rb, Rc and Rd are each independ¬ ently of the others d-C4alkyl. Other suitable tetraalkylammonium bases with other anions can be obtained, for example, by anion exchange reactions.

Preference is given to compounds wherein R6a is hydrogen, CrC6alkyl or CrC6alkylcarbonyl; and each R02 independently of any other(s) is halogen, CrC6alkyl, CrC6haloalkyl, C2-C6- alkenyl, C2-C6haloalkenyl, C2-C6alkynyl, C2-C6haloalkynyl, CrC6alkoxy, CrC6haloalkoxy, C3-C6alkenyloxy, C3-C6haloalkenyloxy, C3-C6alkynyloxy, C3-C6haloalkynyloxy, d-C6alkoxy- Ci-C6alkoxy, cyano-C-ι-C6alkoxy, cyano-CrC6alkenyloxy, d-Cβalkoxycarbonyl-d-Cealkoxy, aminocarbonyl-Ci -C6alkoxy, C1 -Cβalkylaminocarbonyl-Ci -C6alkoxy, d-C6alkylcarbonylamino- CrC6alkoxy, di(C1-C6alkyl)aminocarbonyl-C1-C6alkoxy, d-Cealkoxycarbonyloxy-d-Cealkoxy, CrCealkoxycarbonylamino-d-Cealkoxy, N-(CrC4alkyl)-Ci-C6alkoxycarbonylamino-Ci-C6- alkoxy, d-Cealkylthio-d-Cealkoxy, d-Cealkoxy-d-Cealkylthio, CrCealkylsulfinyl-CrCe- alkoxy, Ci-Cealkylsulfonyl-CrCealkoxy, d-C6alkylsulfonyloxy, Ci-C6haloalkylsulfonyloxy, Ci-C6alkylthio, d-C6alkylsulfinyl, CrC6alkylsulfonyl, d-C6haloalkylthio, CrC6haloalkyl- sulfinyl, CrC6haloalkylsulfonyl, CrCealkoxycarbonyl-CrCealkylthio, d-C6alkoxycarbonyl- CrC6alkylsulfinyl, Ci-C6alkoxycarbonyl-CrC6alkylsulfonyl, C-,-C6alkoxycarbonyl, d-C6alkyl- carbonyl, N(R036RoS?), N(R038RoSg)SO2, R0I9SO2N(R018), nitro, cyano, hydroxy, formyl, CH(=NR040), hydroxy-d-C6alkyl, d-C6alkoxy-CrC6alkyl, d-Cehaloalkoxy-d-C6alkyl, C1-C6- alkylcarbonyloxy-CrC6alkyl, d-Cealkylcarbonylamino-d-Cealkyl, N-(d -C4alkyl)-d -C6alkyl- carbonylamino-CrC6alkyl, d-Cealkoxycarbonyloxy-d-Cβalkyl, d-C6alkoxycarbonylamino- Ci-C6alkyl, N-(C1-C4alkyl)-(Ci-C6alkoxycarbonyl)amino-C1-C6alkyl, C-ι-C6alkylaminocarbonyl- amino-CrCealkyl, N-(d-C4alkyl)-(d-C6alkylaminocarbonyl)amino-C1-C6alkyl, di(CrC6alkyl)- aminocarbonylamino-d-C-ealkyl, N-(d-C4alkyl)-[di(C1-C6alkyl)aminocarbonyl]amino-d-C6- alkyl, d-Cealkylthio-d-Cealkyl, d-Cealkylsulfinyl-d-Cealkyl, d-Cealkylsulfonyl-d-Cealkyl, Ro25S02N(R024)-CrC6alkyl, rhodano-d-C6alkyl, cyano-d-C6alkyl, C3-C6alkenyloxy-d-C6- alkyl, di-Cehaloalkenyloxy-Ci-Cealkyl, C3-C6alkynyloxy-d-C6alkyl, C3-C6haloalkynyloxy- CrC6alkyl, d-Cealkoxy-CrCealkoxy-d-Csalkyl, d-Cehaloalkoxy-d-Cealkoxy-Ci-Csalkyl, d-C^lkoxy-d-C^lkoxy-CrC/talkoxy-CrCsalkyl, C1-C4alkoxy-C1-C4alkoxy-C1-C4alkoxy- C1-C4alkoxy-C1-C3alkyl, CrC6alkylcarbonyloxy-Ci-C6alkoxy-CrC3alkyl, CrCealkoxycarbonyl- CrCealkoxy-CrCsalkyl, d-C6alkylthio-CrC6alkoxy-Ci-C3alkyl, CrCealkoxycarbonyl-CrCe- alkylthio-d-C3alkyl, CrCealkoxycarbonyl-d-Cealkylsulfinyl-CrCsalkyl or C^Cealkoxy- carbonyl-Ci-C6alkylsulfonyl-d-C3alkyl; or each R02 independently of any other(s) is a three- to ten-membered monocyclic or bicyclic ring system which may be aromatic, partially saturated or fully saturated and may contain 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 may have been replaced by a carbonyl, thiocarbonyl, sulfinyl, sulfonyl or -C(=NR052)- group, and wherein the ring system is bonded to the group Q directly, by way of a -C≡C-, -C(O)-, -C(O)O-, -O-, -OC(O)-, -ON(R048)-, -ON=C(R053)-, -N(R049)-, -N(R050)C(O)-, -C(O)N(R051)-, -S-, -S(O)-, -SO2-, -SO2N(R04I)- or -N(R042)SO2 group or by way of a C1- C4alkylene chain which may be interrupted by -C(R046a)=C(R047a)-, -C≡C-, -C(O)-, -C(O)O-, -0-, -OC(O)-, -ON(R0483)-, -ON=C(R0533)-, -N(R0493)-, -N(R0503)C(O)-, -C(O)N(R0513)-, -S-, -S(O)-, -SO2-, -SO2N(R043)- or by -N(R044)SO2- and substituted one or more times at a chain carbon atom by CrC3alkyl, and wherein the ring system itself may be substituted one, two or three times by halogen, d-C6alkyl, d-C6haloalkyl, C2-C6alkenyl, C2-C6haloalkenyl, C2-C6- alkynyl, C2-C6haloalkynyl, CrC6alkoxy, d-C6haloalkoxy, C3-C6alkenyloxy, C3-C6haloalkenyl- oxy, C3-C6alkynyloxy, d-C6alkylthio, d-C6haloalkylthio, C3-C6alkenylthio, C3-C6haloalkenyl- thio, C3-C6alkynylthio, C1 -C4alkoxy-d -C3alkylthio, d-dalkylcarbonyl-d-Csalkylthio, C1-C4- alkoxycarbonyl-d-C3alkylthio, cyano-d-C3alkylthio, d-C6alkylsulfinyl, d-C6haloalkylsulfinyl, CrC6alkylsulfonyl, d-C6haloalkylsulfonyl, aminosulfonyl, CrC4alkylaminosulfonyl, di(CrC4- alkyl)aminosulfonyl, R028-Ci-C4alkylene wherein the alkylene chain may be interrupted by oxygen, sulfur, sulfinyl or by sulfonyl and substituted one or more times by CrC3alkyl, or N(R029R030), 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 Ci-C3alkyl, d-C3haloalkyl, d-C3alkoxy, CrC3haloalkoxy, 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; or two substituents R02 at adjacent carbon atoms of the phenyl group, together with the two adjacent carbon atoms of the phenyl group, form a fused-on 4- to 10-membered mono- or bi¬ cyclic ring system which may be aromatic, partially saturated or fully saturated and may contain one, two or three hetero atoms selected from oxygen, sulfur and nitrogen and in which one, two or three atoms of the ring system may have been replaced by sulfinyl, sulfonyl, -N(R0I0)- and/or by -C(=X02)- and wherein the ring system may be substituted one or more times at carbon atoms by R011.

Preferred compounds of formula I are also those wherein Q is a phenyl group having two or three identical or, preferably, different R02 substituents, which phenyl group is preferably substituted once in the ortho-position to the carbonyl group.

Preference is also given to compounds of formula I wherein Q is a phenyl group Q0,

which is substituted at least twice or at least three times, and wherein R0202 is halogen, Ci-C4alkyl, C1-C4haloalkyl, C2-C4alkenyl, C2-C4haloalkenyl, C2-C4alkynyl, C2-C4haloalkynyl, CrC4alkoxy, CrC4haloalkoxy, C3-C4alkenyloxy, C3-C4haloalkenyloxy, C3-C4alkynyloxy, C1 -CSaIkOXy-C1 -C3alkoxy, cyano-CrC∑salkoxy, d-C3alkylthio-d-C3alkoxy, CrC4alkylthio, CrC4alkylsulfinyl, d-C4alkylsulfonyl, CrC4haloalkylthio, CrC4haloalkylsulfinyl, C1-C4IIaIo- alkylsulfonyl, N(R036R037), N(R038R039)SO2, Ro19SO2N(R0I8), nitro, cyano, CrC3alkoxy- Ci-C3alkyl, d-C3haloalkoxy-d-C3alkyl, Ci-C3alkylthio-Ci-C3alkyl, d-C3alkylsulfinyl- Ci-C3alkyl, d-Csalkylsulfonyl-d-C-isalkyl, cyano-C-ι-C3alkyl, C-3-C4alkenyloxy-d-C3alkyl, C3-C4alkynyloxy-CrC3alkyl, d-Csalkoxy-d-dialkoxy-d-Csalkyl, d-C3haloalkoxy-d-C3- alkoxy-CrC3alkyl, d-C3alkoxy-d-C3alkoxy-CrC3alkoxy-d-C3alkyl, C1-CSaIkOXy-C1-C3- alkoxy-d-C3alkoxy-d-C3alkoxy-d-C3alkyl, R025Sθ2N(Ro24)-Ci-C3alkyl, or R0202 is a three- to ten-membered monocyclic or bicyclic ring system which is bonded to Q0 directly or by way of a CrC3alkylene chain, which ring system may be aromatic, partially saturated or fully saturated and may contain 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 may have been replaced by a carbonyl, thiocarbonyl, sulfinyl, sulfonyl or -C(=NR052)- group, and wherein the ring system itself may be substituted one, two or three times by halogen, d-C3alkyl, C1-C3- haloalkyl, C2-C3alkenyl, C2-C3alkynyl, CrC3alkoxy, d-C3haloalkoxy, C3-C4alkenyloxy, C3-C4- alkynyloxy, CrC3alkylthio, d-C3haloalkylthio, CrC3alkylsulfinyl, CrC3alkylsulfonyl, C1-C3- alkylaminosulfonyl, di(C1-C3alkyl)aminosulfonyl, R028-C1 -C3alkylene, N(R029R03o), cyano, nitro or by phenyl; and R0203 is hydrogen or has the definition of a single substituent R02; R0204 is hydrogen, halogen, d-C3haloalkyl, d-C3alkylthio, CrC3alkylsulfinyl, C-i-C3alkylsulfonyl, CrC3haloalkoxy, C-|-C3alkylsulfonyloxy, CrC3alkylsulfonylamino, d-C3haloalkylsulfonyl- amino, 4H-1 ,2,4-triazol-4-yl, nitro or cyano; and R0206 is hydrogen, fluorine, chlorine, bromine or methyl.

Especially preferred compounds of formula I are also those wherein Q is a phenyl group of formula Q0 wherein R0203 is d-C4alkylthio, CrC4alkylsulfinyl, CrC4alkylsulfonyl, CrC4alkoxy- CrC4alkylthio, C1-C4alkoxy-C1-C4alkylsulfinyl, d-dalkoxy-d-dalkylsulfonyl or cyano, especially d-C4alkylthio or Crdalkoxy-d-dsalkylthio or cyano.

Also especially preferred are compounds of formula I wherein Q is a phenyl group of formula Q0 wherein R0204 is d-C3haloalkyl, nitro or cyano, especially trifluoromethyl, difluoromethyl or cyano.

Also especially preferred are compounds of formula I wherein Q is a phenyl group of formula Q0 wherein R0202 is chlorine, bromine, CrC3alkyl, CrC3haloalkyl, d-C3alkoxy-d-C3alkyl, d-C2alkoxy-d-C2alkoxy-d-C2alkyl, CrC3alkoxy, C1 -CSaIkOXy-C1 -C2alkoxy, d-C3alkylthio, d-C3alkylsulfinyl, d-C3alkylsulfonyl, cyano or nitro; R0203 is hydrogen, halogen, d-C4alkyl, d-C4haloalkyl, C2-C4alkenyl, C2-C4haloaikenyl, C2-C4alkynyl, C2-C4haloalkynyl, CrC6alkoxy, CrC6haloalkoxy, C3-C6alkenyloxy, C3-C6haloalkenyloxy, C3-C6alkynyloxy, CrC4alkoxy- CrC3alkoxy, cyano-d-C3alkoxy, d-dalkoxycarbonyl-d-Csalkoxy, d-C4alkylaminocarbonyl- d-C3alkoxy, di(C1-C4alkylamino)carbonyl-C1-C3alkoxy, d-C^alkoxycarbonyloxy-d-Csalkoxy, C1-C4alkylcarbonylamino-C1-C4alkoxy, N-(C1-C4alkyl)-C1-C4alkylcarbonylamino-C1-C4alkoxy, CrC^lkoxycarbonylamino-d-Csalkoxy, N-(CrC4alkyl)-CrC4alkoxycarbonylamino-Ci-C3- alkoxy, d-Csalkylthio-d-Csalkoxy, CrC3alkylsulfinyl-C-i-C3alkoxy, d-C3alkylsulfonyl- Ci-C3alkoxy, CrC4alkylsulfonyloxy, Ci-C4haloalkylsulfonyloxy, C-ι-C4alkylthio, d-C4alkyI- sulfinyl, d-C4alkylsulfonyl, d-C4haloalkylthio, Ci-C4haloalkylsulfinyl, d-Oihaloalkylsulfonyl, CrC4alkoxy-CrC4alkylthio, Crdalkoxy-d-dalkylsulfinyl, d-Cialkoxy-d-dalkylsulfonyl, Ci-C4alkoxycarbonyl, CrC4alkylcarbonyl, N(R036R03?). N(R038R039)SO2, R0IgSO2N(R0I8), cyano, formyl, hydroxy-CrC3alkyl, Ci-C4alkoxy-d-C3alkyl, d-C4haloalkoxy-CrC3aIkyl, d-C^alkylcarbonyloxy-d-C-salkyl, d-dalkylcarbonylamino-d-Csalkyl, N-(C1 -C4alkyl)- d-C4alkylcarbonylamino-CrC3alkyl, d-dalkoxycarbonyloxy-C^Csalkyl, CrC4alkoxy- carbonylamino-Ci-C3alkyl, N-(C1-C4alkyl)-C1-C4alkoxycarbonylamino-C1-C3alkyl, C1-C4- alkylaminocarbonylamino-Ci-C3alkyl, N-(d-C4alkyl)-d-C4alkylaminocarbonylamino- Ci-C3alkyl, di(C1-C4alkylamino)carbonylamino-C1-C3alkyl, N-(Ci-C4alkyl)-di(Ci-C4aIkyl- amino)carbonylamino-C1-C3alkyl, CrC4alkylthio-Ci-C3alkyl, CrC4alkylsulfinyl-C1-C3alkyl, d-C^lkylsulfonyl-CrCsalkyl, rhodano-CrC3alkyl, cyano-CrC3alkyl, C3-C4alkenyloxy- d-C3alkyl, 05-043IkVHyIoXy-C1-CSaIkVl, Ci-Csalkoxy-d-Cjsalkoxy-d-Csalkyl, d-C3haloalkoxy- C1 -CSaIkOXy-C1 -C3alkyl , C1 -C3alkoxy-d -CSaIkOXy-C1 -CSaIkOXy-C1 -C3alkyl , C1 -C3alkoxy- CrCsalkoxy-d-Csalkoxy-C-i-Csalkoxy-CrCsalkyl, C1-C4alkylcarbonyloxy-C1-C3alkoxy- d-Csalkyl, CrC^lkoxycarbonyl-CrCsalkoxy-CrCsalkyl, d-C3alkylthio-d-C3alkoxy- d-C3alkyl, CrC^lkoxycarbonyl-C-i-Csalkylthio-d-Csalkyl, C1 -C4BIkOXyCa^oHyI-C1 -C3alkyl- sulfinyl-CrCsalkyl, Crdalkoxycarbonyl-d-Csalkylsulfonyl-d-Csalkyl or R02SSO2N (R024)- d-C3alkyl, or R0203 is a three- to ten-membered monocyclic or bicyclic ring system which is bonded to Q0 directly, by way of an oxygen, sulfur, sulfinyl, sulfonyl or nitrogen bridge or by way of a d-C3alkylene chain which may be interrupted especially by oxygen, which ring system may be aromatic, partially saturated or fully saturated and may contain one, two, three or four hetero atoms selected from nitrogen, oxygen and sulfur, and in which one, two, three or four carbon atoms of the ring system may have been replaced by a carbonyl, thiocarbonyl, sulfinyl, sulfonyl or -C(=NR052)- group, and wherein the ring system itself may be substituted one, two or three times by halogen, CrC3alkyl, d-Cshaloalkyl, C2-C3alkenyl, C2-C3alkynyl, CrC3alkoxy, CrCshaloalkoxy, C3-C4alkenyloxy, C3-C4alkynyloxy, d-C3alkyl- thio, d-C3haloalkylthio, d-C3alkylsulfinyl, CrC3alkylsulfonyl, d-Csalkylaminosulfonyl, R028-C1 -C3alkylene, N(R029R030), cyano, nitro or by phenyl; R0204 is halogen, d-C3haloalkyl, CrC3alkylsulfinyl, CrC3alkylsulfonyl, d-C3haloalkoxy, nitro or cyano; and R0206 is hydrogen. Very special preference is given also to compounds of formula I wherein Q is a phenyl group of formula Q0 wherein R02o2 is chlorine, bromine, Ci-C3alkyl, CrC3alkylsulfonyl or nitro; R0203 is hydrogen, CrC6alkoxy, d-Cβhaloalkoxy, C3-C6alkenyloxy, C3-C6alkynyloxy, Ci-C4alkoxy- CrC3alkoxy, Ci-C4alkylcarbonylamino-C1-C3alkoxy, CrC4alkoxycarbonylamino-Ci-C3alkoxy, CrC4alkylthio, d-dalkoxy-Crdsalkylthio, d-C4alkoxycarbonyl, cyano, d-C-4alkoxy-d-C3- alkyl or CrC4haloalkoxy-Ci-C3a!kyl, or R0203 is a five- or six-membered monocyclic ring system which is bonded to Q0 directly or by way of a CrC3alkylene chain which may be interrupted especially by oxygen, which ring system may be aromatic, partially saturated or fully saturated and may contain 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 may have been replaced by a carbonyl, thiocarbonyl, sulfinyl or sulfonyl group, and wherein the ring system itself may be substituted one, two or three times by halogen, CrC3alkyl, C-ι-C3haloalkyl, C2-C3alkenyl, C2-C3alkynyl, CrCsalkoxy, d-C3haloa!koxy, C3-C4alkenyloxy, C3-C4alkynyloxy, Ci-C3alkylthio, CrC3haloalkylthio, C-|-C3alkylsulfinyl, CrC3alkylsulfonyl, Ci-C3alkylamino- sulfonyl, di(C1-C3alkyl)aminosulfonyl, Ro28-Ci-C3alkylene, N(Ro29RO3o), cyano, nitro or by phenyl; R02O4 is halogen, d-C3haloalkyl, Ci-C3alkylsulfonyl, nitro or cyano; and R02Oe is hydrogen.

Very special preference is also given to compounds of formula I wherein Q is a phenyl group of formula Q0 wherein R0202 is chlorine, bromine, Ci-C3alkyl, Ci-C3alkylsulfonyl or nitro; R02O3 is hydrogen, Ci-C6alkoxy, CrC6haloalkoxy, C3-C6alkenyloxy, C3-C6alkynyloxy, d-C4alkoxy- CrC3alkoxy, d-dalkylcarbonylamino-d-Csalkoxy, Ci-C4alkoxycarbonylamino-d-C3alkoxy, CrC4alkylthio, d-C4alkoxy-d-C3alkylthio, CrC4alkoxycarbonyl, cyano, d-C4alkoxy-d-C3- alkyl or d-C4haloalkoxy-d-C3alkyl; R0204 is halogen, CrC3haloalkyl, d-C3alkylsulfonyl, nitro or cyano; and R0206 is hydrogen.

Very special preference is also given to compounds of formula I wherein Q is a phenyl group of formula Q0 wherein R0202 is chlorine, bromine, Ci-C3alkyl, d-C3alkylsulforiyl or nitro; R0203 is hydrogen, CrC6alkoxy, d-C6haloalkoxy, C3-C6alkenyloxy, C3-C6alkynyloxy, d-C4alkoxy- Ci-C3alkoxy, CrC4alkylcarbonylamino-Ci-C3alkoxy, CrC4alkoxycarbonylamino-d-C3alkoxy, Ci-C4alkylthio, CrC4alkoxy-Ci-C3alkylthio, d-C4alkoxycarbonyl or cyano; R0204 is halogen, Ci-C3haloalkyl, d-C3alkylsulfonyl or cyano; and R0206 is hydrogen. Further preferred compounds of formula I are those wherein Q is a phenyl group substituted at least twice or at least three times by R02, wherein two substituents R02 in the ortho-meta- position to the carbonyl group, together with the two carbon atoms of the phenyl group to which they are linked, form a fused-on 4- to 10-membered mono- or bi-cyclic ring system which may be aromatic, partially saturated or fully saturated and may contain one, two or three hetero atoms selected from oxygen, sulfur and nitrogen and in which one, two or three carbon atoms of the ring system may have been replaced by sulfinyl, sulfonyl, -N(R010)- and/or by -C(=X02)- and wherein the ring system may be substituted one or more times at carbon atoms by R011; special preference is given to the above-mentioned groups of formulae Qi to Qg, and very special preference is given to the above-mentioned groups of formulae Q1, Q2, Q3, Q7 and Q8.

Further preferred compounds of formula I are those wherein Q is a phenyl group substituted at least three times by R02, which phenyl group is substituted in the ortho-position to the carbonyl group by a substituent having the definition of a single R02, and wherein two further substituents R02 in the meta-para-position to the carbonyl group, together with the two carbon atoms of the phenyl group to which they are linked, form a fused-on 4- to 10-membered mono- or bi-cyclic ring system which may be aromatic, partially saturated or fully saturated and may contain one, two or three hetero atoms selected from oxygen, sulfur and nitrogen and in which one, two or three carbon atoms of the ring system may have been replaced by sulfinyl, sulfonyl, -N(R010)- and/or by -C(=X02)- and wherein the ring system may be substit¬ uted one or more times at carbon atoms by R011; special preference is given to the groups of formulae Q4a, Q5a and Q6a

(Q63), wherein R0H8 is Ci-C3alkyl; R02Os is halogen, CrC3alkyl, CrC3haloalkyl, CrC3alkoxy, C1-C2- alkoxy-CrC2alkoxy, Ci-C3alkylthio, Ci-C3alkylsulfiny! or d-C3alkylsulfonyl; R0206 is hydrogen, fluorine, chlorine or methyl; X6 is oxygen, sulfur, sulfinyl, sulfonyl or a group -C(=O)-, -CR0119(OR0120)- or -(C=NR0121)-, wherein R0119 is hydrogen, CrC3alkyl or CrQjalkoxy, R0-I20 is Ci-C3alkyl or R0119 together with OR0120 is -OCH2CH2O-, R0121 is CrC6alkoxy; and V1 is O, 1 or 2; V2 = 0, 1 or 2.

Furthermore, independently of Q, preference is given to those compounds of formula I wherein Y is oxygen, -C(=CR6aR6b)- or a C-ι-C2alkylene chain which may be substituted one or more times by R6; A1 is CR7; A2 is CR8; R6a is hydrogen, CrC6alkyl or CrC6alkyl- carbonyloxy; R6b is hydrogen or CrC6alkyl; R1, R2, R6, R7 and R8 are each independently of the others hydrogen, halogen, CrC6alkyl, CrC6alkoxy or CrC6alkoxycarbonyl; or two substituents R6 at the same carbon atom together form a C2-C5alkylene chain; and R3 is hydroxy.

Special preference is also given to those compounds wherein Y is oxygen or a CrC2alkylene chain which may be substituted once or twice by R6; the substituents R6 therein being espe¬ cially hydrogen, methyl and/or methoxycarbonyl, more especially hydrogen.

Special preference is also given to those compounds wherein A1 is CR7, A2 is CR8 and R1, R2, R7 and R8 are each independently of the others hydrogen, methyl or methoxy; more especially, R1, R2, R7 and R8 are each independently of the others hydrogen or methyl.

Very special mention should be made of those compounds wherein Y is methylene, A1 and A2 are both methine, and R1, R2, Re, R7 and R8 are each hydrogen.

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 Ia,

(Ia), wherein A1, A2, R1, R2, R02 and Y are as defined for formula I and p is 1 , 2, 3 or 4.

Preference is given to a process wherein either a) a compound of formula Qa

wherein R02 and p are as defined above, and E1 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

wherein A1, A2, R1, R2 and Y are as defined for formula I, to form a compound of formula Ma and/or Hb

which is/are then isomerised in the presence of a base and a catalytic amount of an acylating agent, for example dimethyiaminopyridine (DMAP), or catalytic amounts of a source of cyanide ions, for example acetone cyanohydrin, sodium cyanide, potassium cyanide or trimethylsilyl cyanide; or b) a compound of formula Qb

wherein R02 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 Ha 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.

The intermediates of formulae Ha and lib are novel and the present invention therefore relates likewise thereto.

The compounds of formula Qa used as starting materials and their corresponding acids Qb are known in some cases or they can be prepared by generally known methods.

Some of the starting materials of formula III are likewise known, for example the 8-oxa- bicyclo[3.2.1]oct-6-ene-2,4-dione described in Tetrahedron Letters, 2004, 45, 2093 and the compounds of formula Da (as designated in accordance with WO 04/58712) disclosed in WO 04/58712.

The preparation of the compounds of formula Ia is illustrated in greater detail in the reaction schemes below. Reaction Scheme 1 (route a):

Reaction Scheme 2 (route b):

For the preparation of the compounds of formula Ia, for example, in accordance with Reaction Scheme 1 (route a), the starting materials used are carboxylic acid derivatives of formula Qa wherein E1 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

corresponding carboxylic acid) or from N-ethyl-N'-(3-dimethyl-

aminopropyl)-carbodiimide (EDC) and the corresponding carboxylic acid ). They are reacted with the diones of formula III, or the previously formed salts thereof, in an inert, organic solvent, such as a halogenated hydrocarbon, for example dichloromethane, a nitrile, for example acetonitrile, or an aromatic hydrocarbon, for example toluene, and in the presence of a base, such as an alkylamine, for example triethylamine or diisopropylamine (Hϋnig's base), an aromatic amine, for example pyridine or 4-dimethylaminopyridine (DMAP), or a carbonate, for example potassium carbonate, to form the isomeric enol ester(s) of formula Ha and/or Hb. Those esterification reactions can be carried out at temperatures of from 00C to 1100C, preferably from 100C to 40°C.

The isomerisation of the enol ester derivatives of formulae Ha and Hb or mixtures thereof to form the compounds of formula Ia is known and can be carried out, for example, analogously to EP-A-O 353 187, EP-A-O 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. The two reaction steps can be carried out in situ, without isolation of the intermediates of formula Ha and/or lib, espe¬ cially 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.

In accordance with Reaction Scheme 2 (route b), the desired compounds of formula Ia can be obtained, for example, analogously to E. Haslem, Tetrahedron, 2409-2433, 36, 1980, by first preparing enol esters of formula Ha 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 triethyl¬ amine, 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 Ia. That reaction takes place, depending upon the solvent used, at temperatures of from 00C to 1100C, preferably at temperatures of from 1O0C to 4O0C, and first yields, as described under Reaction Scheme 1 (route a), the isomeric enol ester(s) of formula Ma and/or lib, which are then isomerised to form the desired compounds of formula Ia 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.

The activated carboxylic acid derivatives of formula Qa in Reaction Scheme 1 (route a) wherein E1 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 E1.

Compounds of formula I wherein R3 is other than hydroxy or halogen can be prepared, in accordance with conversion methods generally known from the literature, by nucleophilic substitution reactions of chlorides of formula I wherein R3 is chlorine, which can be obtained from compounds of formula I wherein R3 is hydroxy, likewise in accordance with known methods, by reaction with a chlorinating agent, such as phosgene, thionyl chloride or oxalyl chloride. In that process, for example, 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.

Compounds of formula I wherein the substituent R3 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. In the process, the degree of oxidation at the sulfur atom (-S(O)- or -SO2-) can be controlled by the amount of oxidising agent. Other sulfur-containing groups, for example those in the definitions of R-i, R2, Re. R7, Rs, R02, Ron or Y, or in sulfur-interrupted alkylene chains or cycloalkyl groups, as may occur, for example, in R02, can be oxidised with a suitable oxidising agent, such as m-CPBA or sodium periodate, to form the corresponding sulfone and/or sulfine (sulfoxido) groups both directly on compounds of formula I and on intermediates of formulae Ha, lib, III and IV, V and Vl (in accordance with formulae herein- below). The resulting derivatives of formula I wherein R3 is other than hydroxy may also occur in various isomeric forms which can, if desired, also be isolated in pure form, for example the formulae I, ,ii ,v ,Vl and I shown above.

The compounds of formula III used as starting materials

can be prepared, for example, by treating a compound of formula IV

wherein A1, A2, Ri, R2 and Y are as defined for formula I, and Xa is chlorine or bromine and Ya is hydroxy or d-C8alkoxy, using a suitable reducing agent, for example tributyltin hydride, or iron or zinc in acetic acid, and subjecting the resulting compound of formula Ilia

wherein A1, A2, R1, R2, R3 and Y are as defined above, to aftertreatment, optionally, when Ya is CrCsalkoxy, 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 IHa wherein A1, A2, R1, R2 and Y are as defined above, and Ya is hydroxy, in the tautomeric form IHb of the compound of formula III.

Some of the compounds of the above formula IV are likewise known from WO 04/58712 and the compounds of formula IV wherein R1 and R2 are each hydrogen or methyl, A1 and A2 are each methylene, Y is oxygen, methylene or ethylene, R3 is chlorine, bromine or hydroxy and Xa is chlorine or bromine are known from Organic Letters 2002, 4, 1997; Archiv der Pharm- azie 1987, 320, 1138; J. Amer. Chem. Soc. 1968, 90 2376 and from US-A-3,538,117 and can be prepared in accordance with the methods described therein.

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 Vl

wherein A1, A2, R-i, R2 and Y are as defined above, in an inert solvent, such as dichloro- methane, 1 ,2-dichloroethane, toluene or chlorobenzene, and optionally at elevated temp¬ erature and/or under elevated pressure, in a reaction similar to a Diels-Alder reaction with a cyclopropene of formula XII

wherein Xa is hydrogen, chlorine, bromine or iodine, Xb and Xc are halogen and Za is halogen, CrC-6alkoxy, phenoxy, CrC6alkylthio, CrC6alkylsulfinyl, Ci-C6alkylsulfonyl, phenylthio, phenylsulfinyl or phenylsulfonyl, or preferably Xa, Xb, Xc and Za are all simultaneously chlorine or bromine (formula XIIa), and then hydrolysing the resulting bicyclic compound of formula V

and/or its tautomeric form V

wherein A-i, A2, Ri, R2. 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

and/or its tautomeric form IVc

wherein A1, A2, Ri, R2, 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

and/or its tautomeric form IV

wherein Ai, A2, R1, R2 and Y are as defined above and, depending upon the reaction conditions, Ya is hydroxy (formula IVa), CrCsalkoxy (formula IVc), chlorine or bromine (formula IVd), which is/are then reduced to form the compounds of formula Ilia

wherein A1, A2, R1, R2 and Y are as defined above, and Ya is hydroxy or C-i-Csalkoxy, and/or hydrolysed directly to a compound of formula III

and/or its tautomeric form of formula UIb wherein A1, A2, Ri, R2 and Y are as defined above.

For example, compounds of formula V and/or V1 can thus be hydrolysed further, in the presence of 90-98% sulfuric acid at elevated temperature of about 80-1000C, to form the compounds of formula IVa, that is to say the compounds of formula IV and/or IV1 wherein Ya is hydroxy and Xa is chlorine or bromine, as described in detail in J. Amer. Chem. Soc. 1968, 90, 2376.

It is also possible for compounds of formula V to be converted into compounds of formula IVd wherein Xc and Xa are chlorine or bromine, in the presence of 90% trifluoro- acetic acid at boiling temperature or in the presence of aqueous silver nitrate at ambient temperature, as described in Archiv der Pharmazie 1987, 320, 1138 and in Organic Letters 2002, 4, 1997.

Compounds of formula IVd can then be converted with good yields, at ambient temperatures, into compounds of formula IVc wherein Ya is Ci-C8alkoxy and Xa is chlorine or bromine in the presence of alcoholates of formula R3aO'M+, wherein R3a is d-C8alkyl and M3+ is an alkali metal cation, in a solvent, such as an alcohol RβaOH, toluene or ether, for example tetra- hydrofuran or dimethoxyethane.

Furthermore, compounds of formula IVc wherein Xa is chlorine or bromine and Ya is hydroxy or CrCsalkoxy 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 reduct¬ ion 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 ). Moveover, compounds of formula Ilia wherein Ya is CrC8alkoxy, 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 com¬ pounds of formula III or their tautomeric form IHb, there advantageously being formed in the latter case a lithium, sodium or potassium salt of formula Ilia wherein Ya is 0"M+ and M+ is the relevant alkali metal ion, that salt being formed directly for the coupling in accordance with route a).

The compounds of formula XlI wherein Xa, Xb, Xc and Za are all simultaneously chlorine or bromine, that is to say the compound of formula XIIa

are known, e.g. from J. Amer. Chem. Soc, 1966, 88, 2478 and from J. Amer. Chem. Soc, 1968, 90, 2376. According to Synthesis, 1986, 260, for example the tetrachlorocyclopropene can be prepared from the pentachlorocyclopropane XIIIa

wherein Xa is chlorine, by slowly heating that compound to 9O0C in the presence of an aqueous potassium hydroxide solution in the form of a two-phase mixture; and the tetra- bromocyclopropene, formula XIIa wherein Xa is bromine, can be obtained from the tetra¬ chlorocyclopropene, formula XIIa wherein Xa is chlorine, by treatment with boron tribromide at 6O0C in accordance with J. Amer. Chem. Soc, 1966, 88, 2481. The pentachlorocyclo¬ propane (formula XIlIa 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. The general reaction sequences by which compounds of formulae III and IHb are prepared, via intermediates of formulae IVd, IVc, IVa and HIa, from compounds of formula V obtained by way of formulae Vl and XII are illustrated in greater detail in the following scheme:

Reaction Scheme 3:

(XIII) (XlI) (Vl) (V) (XIIIa) (XIIa)

Hvdrolvsis: Hvdrolvsis: e.g . 6% CFj ,COOH e.g. 95% H2SO4 in AcOH/dioxane/H2O y or 30% NaOH

Reduction: Hvdrolvsis: Reduction: e.g. Zn / AcOH e.g. AcOH/H2O e.g. Zn / AcOH

(llla) Ya = OR3a (lllb) Ya = OH, 0"M+ (III)

In the reaction of compounds of formula IV wherein A1, A2, R1, R2, Xa and Y are as defined above, and Ya is CrCsalkoxy, chlorine or bromine (formulae IVc and IVd), with alcoholates of formula R3aO"Ma+ there may also be obtained compounds of formula VII

wherein A1, A2, R1, R2, Xa and Y are as defined above and R3a is C1-C6BlRyI or, when glycol is used, two R3a together are -CH2CH2-. These compounds too can be reacted under the reaction conditions mentioned above, for example with tributyltin hydride, or with iron or zinc in the presence of acetic acid, by way of a compound of formula VIII

wherein A1, A2, R1, R2, R3a 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

and/or their tautomeric form IHb

(IHb) wherein A1, A2, Ri, R2 and Y are as defined above, as illustrated generally in Reaction Scheme 4 below.

Reaction Scheme 4:

In a further process, a compound of formula III can also be prepared by converting either a compound of formula IX

wherein A1, A2, R1, R2 and Y are as defined above, and Rb is in each case d-Cealkyl or two Rb together are -CH2CH2-, by hydrolysis, for example by treatment with an aqueous acid (route c); or a compound of formula X

wherein A1, A2, R1, R2 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 Xl

wherein A1, A2, R1, R2 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

wherein A1, A2, R-i, R2 and Y are as defined above. Such processes are also known perse to the person skilled in the art; the compounds can be prepared, according to the functionality of groups A1, A2, Ri, R≥ and Y, in accordance with general reaction routes shown in the following scheme:

In that process there are especially readily obtainable those compounds of formula IX wherein Y is an R6-substituted C2alkylene chain, wherein R6 is, for example, CrCβalkoxy, C-ι-C6benzyloxy, CrC6alkylcarbonyl, CrC6alkoxycarbonyl, CrC6alkylthio or Ci-C6alkyl- sulfonyl.

Methods of obtaining the starting compounds of formula IX used in the above-mentioned process (route c) are known, for example, from Ace. Chem. Res. 2002, 856; J. O. C. 2002, 67, 6493; Org. Lettr. 2002, 2477; Synlett, 2002, 1520; Chem. Commun. 2001 , 1624; Synlett, 2000, 421 ; THL, 1999, 8431 ; J.O.C. 1999, 64, 4102; J.A.C.S. 1998, 129, 13254; THL, 1998, 659; Synlett, 1997, 1351. Methods of obtaining the starting materials of formula X are described, for example, in Org. Lettr. 2002, 2063; Synthetic Commun. 2001 , 707; J.A.C.S. 2001 , 123, 1569; Synlett, 1999, 225; Synlett, 1997, 786; THL, 1996, 7295; Synthesis, 1995, 845. Compounds of formula Xl are known, for example, from Synthesis, 2000, 850.

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 200C to 12O0C. The carbene insertion by means of diazomethane is preferably effected at from -4O0C to 5O0C in a solvent, such as dichloro- methane 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 -150C to 250C.

In principle, however, the compounds of formulae III, Ilia, IV, IV1, IVa, IVc, IVc1, IVd, V, V1, Vl, VII, VIII, IX, X and Xl used as starting materials and as intermediates can be prepared, in dependence upon the substituent pattern A1, A2, R-i, R2 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.

A large number of known standard methods are available for the preparation of all further compounds of formula I functionalised in accordance with the definitions of A1, A2, R1, R2, Y and Q, for example alkylation, halogenation, acylation, amidation, oximation, oxidation and reduction, the choice of a suitable preparation method being governed by the properties (reactivities) of the substituents in question in the respective intermediates of formulae III, Ilia, IV, IV1, IVa, IVc, IVc1, IVd, V and V1, and especially the starting materials of formulae Vl, IX and X, and Qa and Qb.

The reactions to form compounds of formula I are advantageously carried out in aprotic, inert organic solvents. Such 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 aceto- nitrile or propionitrile, amides, such as N,N-dimethylformamide, diethylformamide or N- methylpyrrolidinone. The reaction temperatures are preferably from -200C to +1200C. 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. It is also possible, however, to use as 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 hyd¬ rogen 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.

Furthermore, the person skilled in the art will be familiar with the sequence in which the reactions should be carried out in order as far as possible to avoid secondary reactions, such as e.g. in accordance with Reaction Scheme 3, formulae IVd and IVc to give IVa, or in accordance with Reaction Scheme 4, formula VII via formula VIII or via formula IVb to give formula III. Unless the synthesis is specifically aimed at the isolation of pure isomers, the product may be obtained in the form of a mixture of two or more isomers, for example chiral centres in the case of alkyl groups or cis/trans isomerism in the case of alkenyl groups or 1E' or 1Z' forms. All such isomers can be separated by methods known per se, for example chromatography, crystallisation, or produced in the desired form by means of a specific reaction procedure.

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. Such a process for the preparation of compounds of formula IVa

wherein Xa is hydrogen, chlorine, bromine or iodine, and Ai, A2, Y, Ri and R2, are as defined for formula I, Xa preferably being hydrogen, chlorine or bromine, comprises a) converting a compound of formula XIII

wherein Xa is hydrogen, chlorine, bromine or iodine; Xb, Xc and Xd are halogen and Za is halogen, CrC6alkoxy, phenoxy, CrC6all<ylthio, C-|-C6alky!sulfinyl, C-rC6alkylsulfonyl, phenyl-

thio, phenylsulfinyl or phenylsulfonyl, Xa preferably being hydrogen, chlorine or bromine; Xb, Xc, Xd preferably being chlorine or bromine; and Za preferably being chlorine, bromine, C-rCεalkoxy, d-Cβalkylsulfinyl or phenylsulfinyl; in the presence of an inert solvent under anhydrous conditions, with an alkali metal hydroxide into a compound of formula XII

wherein Xa, Xb, Xc and Za are as defined for formula XIII, b) then reacting that compound, without isolation, directly with a compound of formula Vl

wherein Ai, A2, Y, Ri and R2 are as defined for formula I, to form a compound of formula V1

wherein A1, A2, Y, R1 and R2 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.

Process step a): 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 00C to the boiling temperature of the solvent used. Temperatures of from 200C to 900C, especially from 700C 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 dichloro- methane, 1 ,2-dichloroethane, toluene, chlorobenzene, dimethoxyethane, tetrahydrofuran and, preferably, dioxane.

Process step b): The reaction of the compound of formula XII with the compound of formula Vl to form the compound of formula V1 is preferably carried out at a temperature of from ambient tempera¬ ture to 1100C. A temperature range of from 800C to 900C is preferred, however. The com¬ pound of formula Vl 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 espec¬ ially in an amount of 4 equivalents.

Process step c): As the 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 1000C, preferably in a temperature range of from 80 to 900C.

In a preferred embodiment of the process according to the invention, the same alkali metal hydroxide is used in Process steps a) and c).

The basic hydrolysis of the compound of formula V1 to form the compound of formula IVa (Process step c) 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 V1 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 V1 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 XIIa obtained from Process step a), which has low stability, can be reacted directly with the dienophile of formula Vl or, in a preferred variant, of formula Via according to Process step b) without further isolation and purification.

In compounds of formula IVa, Xa is preferably hydrogen, chlorine or bromine; Ai is preferably CR7; A2 is preferably CR8; Y is preferably oxygen or a CrC2alkylene chain which may be substituted one or more times by R6; R1, R2, R7 and R8 are each independently of the others preferably hydrogen, CrC6alkyl, trialkylsilyloxy or C1-C6SIkOXy; and R6 is preferably hydrogen, C-rC6alkyl, CrC6alkoxy, tri(CrC6alkyl)silyl or phenyl-di(CrC6alkyl)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 methyl¬ ene. The process according to the invention is also preferably used for the preparation of those compounds wherein R1, R2, R6, R7 and R8 are each independently of the others hydrogen, C-ι-C3alkyl or CrC3alkoxy, 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 R1, R2, R6, R7 and R8 are each hydrogen.

In accordance with the preferred meanings of formula IVa, the starting materials used are preferably compounds of formula Via wherein A1 is preferably CR7; A2 is preferably CR8; Y is preferably oxygen or a CrC2alkylene chain which may be substituted one or more times by R6; R1, R2, R7 and R8 are each independently of the others preferably hydrogen, CrC6alkyl, trialkylsilyloxy or C1-C6BIkOXy; and R6 is preferably hydrogen, CrC6alkyl, CrC6alkoxy, tri(CrC6alkyl)silyl or phenyl-di(CrC6alkyl)silyl; and in accordance with the preferred meanings of formula IVa there are used the preferred starting materials of formula Va1 wherein A1 is preferably CR7; A2 is preferably CR8; Y is preferably oxygen or a CrC2alkylene chain which may be substituted one or more times by R6; R1, R2, R7 and R8 are each independently of the others preferably hydrogen, CrC6alkyl, trialkylsilyloxy or CrC6alkoxy; and R6 is preferably hydrogen, Ci-C6alkyl, CrCealkoxy, tri(C1-C6alkyl)silyl or phenyl- di(CrC6alkyl)silyl.

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 XlIIa above.

The process according to the invention for the preparation of preferred oxabicyclo[3.2.1]- octene-, bicyclo[3.2.1]octene- and bicyclo[3.2.2]nonene-1 ,3-diones of formulae IV, IVa, III and Ilia wherein R3 is preferably hydroxy or 0"M+, and their tautomeric forms IVb and IHb, is illustrated in the following Preparation Examples PA1 to PA4 and hereinbelow in PA6:

Example PA1 : Preparation of 2,3.4,4-tetrachloro-bicvclor3.2.11octa-2,6-diene:

204 g (0.857 mol, 1 eq.) of pentachlorocyclopropane are added at ambient temperature to a suspension of 60.1 g (0.107 mmol, 1.3 eq.) of powdered anhydrous potassium hydroxide in 3616 ml of toluene. After 30 minutes' stirring at ambient temperature, a solution of 226.5 g (3.427 mol, 4 eq.) of freshly prepared cyclopentadiene in 180 ml of toluene is added drop- wise thereto. The reaction mixture is then stirred at a temperature of 700C for one hour and then for a further 18 hours at a temperature of 85°C. The reaction mixture is then concen¬ trated 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.

Example PA2: Preparation of 2.3.4.4-tetrachloro-bicyclo|'3.2.21nona-2,6-diene:

1.55 g (28 mmol) of anhydrous, finely powdered potassium hydroxide are added to 9.9 g (46 mmol) of pentachlorocyclopropane in 20 ml of toluene and the mixture is slowly heated to a temperature of 700C. Then, at from 70 to 750C, a further 3.55 g (63 mmol) of anhydrous, powdered potassium hydroxide is added in portions. After a total of 2 hours, the reaction mixture is filtered through a frit containing silica gel (packing level 2 cm). 18 ml of 1 ,3-cyclo- hexanediene are added to the filtrate and the reaction mixture is stirred for 18 hours at reflux temperature. When cool, the reaction mixture is again filtered through silica gel (frit packing level 2 cm) and concentrated under reduced pressure. Addition of n-hexane yields 2,3,4,4- tetrachloro-bicyclo[3.2.2]nona-2,6-diene in crystalline form having a melting point of 108.5-1100C; 1H-NMR (300 MHz; CDCI3) 6.54 ("t", 1 H); 6.54 (T, 1 H); 6.33, m, 1 H, 3.58 (m, 1 H); 3.36 (m, 1 H); 2.45 (m, 1 H); 2.18 (m, 1 H); 1.9 to 1.70 (m, 2H).

Example PΔ3: Preparation of 3-chloro-4-hvdroxy-bicvclo[3.2.1locta-3,6-dien-2-one:

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 900C, 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. The organic phase is washed twice with saturated sodium chloride solution and dried over sodium sulfate. After filtering and reducing in volume under reduced pressure, 2.3 g (99 %) of 3-chloro-4-hydroxy-bicyclo[3.2.1]octa-3,6-dien-2-one are obtained in the form of a brown powder.

Example PA4: Preparation of 3-chloro-4-hvdroxy-bicvclof3.2.1locta-3,6-dien-2-one (one-pot process): 0.260 g (1.09 mmol, 1 eq.) of pentachlorocyclopropane is added at ambient temperature to a suspension of 0.074 g (1.31 mmol, 1.2 eq.) of powdered anhydrous potassium hydroxide in 10 ml of dioxane. The reaction mixture is then stirred at ambient temperature for 30 minutes and then heated to a temperature of 600C. 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 then added together with 5.5 ml (10.9 mmol, 10 eq.) of 2N sodium hydroxide solution and stirring is carried out for a further 2 hours at a temperature of 85°C. After the reaction mixture has cooled to ambient temperature, 15 ml of water and 20 ml of ethyl acetate are added. The 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. For example, by hydrogenation with hydrogen in the presence of a suitable catalyst, e.g. 5% palladium/carbon, the compound of formula XV

wherein A1, A2, Ri, R2 and Y are as defined for formula IVa, and Xa is especially hydrogen, can be obtained; and by reduction of compounds of formula IVa wherein Xa is chlorine, bromine or iodine, for example reduction by means of iron or zinc in acetic acid, compounds of formula IVa wherein'Xa is hydrogen can be obtained, that is to say the compounds of formula III

wherein, in particular, A1 is preferably CR7, A2 is preferably CRs, Y is preferably oxygen or an unsubstituted or R6-substituted C1-C2alkylene chain, R1, R2, R7 and R8 are each independ¬ ently of the others preferably hydrogen, Ci-C6alkyl, halogen, trialkylsilyloxy or d-Cβalkoxy, and R6 is preferably hydrogen, Ci-C6alkyl, halogen, CrCβalkoxy, tri(C1-C6alkyl)silyl or phenyl- di(CrC6alkyl)silyl, as also used, for example, in WO 04/58712. Those processes, which can also be carried out especially advantageously in the form of one-pot processes, are explained in greater detail in the following scheme and in Examples PA5 and PA6 below:

Reaction Scheme 6:

(XIII ) Xa = H1 CI, Br, I, espec. (XII), espec. (Vl), espec. (V1), (Va1) and/or (XIIIa) Xa=Xb=Xc-Xd=CI (XIIa) (Via) tautomer (V), (Va)

aq. NaOH or KOH

(XV ) Xa = H, Cl, Br, I (IVa) Xa = H, Cl, Br, I (III) and/or (XVa) Xa = H and/or tautomer (IVa1) tautomer (1Mb) and/or tautomer (XVb) and/or tautomer (IVb)

Example PA5: Preparation of bicvclor3.2.1loctane-2,4-dione (one-pot process):

0.260 g (1.09 mmol, 1 eq.) of pentachlorocyclopropane is added at ambient temperature to a suspension of 0.074 g (1.31 mmol, 1.2 eq.) of powdered anhydrous potassium hydroxide in 10 ml of dioxane. The reaction mixture is then stirred at ambient temperature for 30 minutes and then heated to a temperature of 600C. 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. Then 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. After cooling to ambient temperature, 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. The 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. 0.10 g of bicyclo[3.2.1]octane-2,4-dione is obtained in the form of a brown oil which is purified by filtration through silica gel (eluant: CH2CVMeOH 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.

Example PA6: Preparation of bicyclor3.2.11oct-6-ene-2,4-dione (one-pot process):

0.5 g (2.1 mmol, 1 eq.) of pentachlorocyclopropane is added at ambient temperature to a suspension of 0.14 g (2.52 mmol, 1.2 eq.) of powdered anhydrous potassium hydroxide in 19 ml of dioxane. The reaction mixture is then stirred at ambient temperature for 30 minutes and then heated to a temperature of 600C. A solution of 0.56 g (8.4 mmol, 4 eq.) of freshly prepared cyclopentadiene in 4.5 ml of dioxane is then added and the reaction mixture is stirred for 3 hours at a temperature of 85°C. Then 6.7 ml of water are added together with 10.5 ml (21 mmol, 10 eq.) of a 2N sodium hydroxide solution and stirring is continued for a further 2 hours at a temperature of 85°C. After cooling to ambient temperature, the reaction mixture is adjusted to pH 4 to 5 with 16.8 ml (294 mmol, 140 eq.) of concentrated acetic acid. Powdered zinc (0.41 g, 6.3 mmol, 3 eq.) is then introduced and the reaction mixture is stirred at ambient temperature for 2 hours. After filtration through Celite, the filtration residue is washed with ethyl acetate and water. The filtrate is then concentrated by evaporation under reduced pressure. The residue is taken up in ethyl acetate and washed twice with saturated sodium hypochloride solution. The aqueous phase is then acidified with 2N hydrochloric acid and extracted three times with ethyl acetate. The combined phases are then dried over sodium sulfate. After filtration and concentration under reduced pressure, 0.196 g of bicyclo[3.2.1]oct-6-ene-2,4-dione is obtained in the form of a brown oil which is purified by filtration through silica gel (eluant: hexane / ethyl acetate 4/1 ; 1/1 ). 0.13 g of pure bicyclo- [3.2.1]oct-6-ene-2,4-dione is thus obtained in the form of a yellowish oil.

Using the process according to the invention it is possible for bicyclic diones of formula IVa having a double bond at the 6,7-position to be prepared in an especially simple manner and in high yields and good quality. A considerable advantage is that the compound of formula XIIa, which has only low storage stability, is formed in situ during the process and can be further reacted immediately without loss of quality or yield. It is also possible to carry out the entire process without isolation of intermediates, which is especially advantageous for use on a large scale. Furthermore, the hydrolysis according to Process step c) can be carried out under basic conditions, whereas processes known in the literature describe reaction under acidic conditions with hot, concentrated sulfuric acid (J. Amer. Chem. Soc. 1968, 90, 2376 ) or in the presence of silver nitrate (J. Org. Chem. 2004, 69, 406), which not only is expensive but also gives rise to ecological concerns. Basic hydrolysis surprisingly results in consider¬ ably higher yields and better product purity in comparison with acid hydrolysis, as known, for example, from Tetrahedron Letters 45, (2004), 2093-2096.

Compounds of formula IVa may also be in the tautomeric form IVa'

and/or form IVb:

wherein Xa, A1 , A2, Y, R1 and R2, are as defined for formula IVa. The preparation of the tautomeric form IVa1 and/or the tautomeric form IVb is therefore included in the present process.

The intermediates of formula V1 can also be in the tautomeric form V:

wherein A1, A2, Y, R1 and R2 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 V1 and Va1 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.

It is also possible for tautomeric salt forms to occur, such as the tautomeric salt forms IVa1, IVa" and IVa'", which are illustrated below (Mi+ is especially an alkali metal ion, for example the lithium, sodium or potassium ion):

Xa, A1, A2, Y, Ri and R2 in formulae IVa', IVa" and IVa"' are as defined for formula IVa. The preparation of those forms and salts is therefore included in the present process.

For the use according to the invention of the compounds of formula I, or of compositions comprising them, there come into consideration all methods of application customary in agriculture, for example pre-emergence application, post-emergence application and seed dressing, and also various methods and techniques such as, for example, the controlled release of active ingredient. For that purpose a solution of the active ingredient is applied to mineral granule carriers or polymerised granules (urea/formaldehyde) and dried. If required, it is additionally possible to apply a coating (coated granules), which allows the active ingred¬ ient to be released in metered amounts over a specific period of time.

The invention therefore relates also to 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 unmod¬ ified 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. The formulations can be in various physical forms, e.g. in the form of dusting powders, gels, wettable powders, water-dispersible granules, water-dispers- ible tablets, effervescent pellets, emulsifiable concentrates, microemulsifiable concentrates, oil-in-water emulsions, oil-flowables, aqueous dispersions, oily dispersions, suspo-emulsions, capsule suspensions, emulsifiable granules, soluble liquids, water-soluble concentrates (with water or a water-miscible organic solvent as carrier), impregnated polymer films or in other forms known e.g. from the Manual on Development and Use of FAO Specifications for Plant Protection Products, 5th Edition, 1999. Such formulations can either be used directly or they are diluted prior to use. The dilutions can be made, for example, with water, liquid fertilisers, micronutrients, biological organisms, oil or solvents.

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, cellul¬ ose, 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. Alternatively, 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.

The formulation adjuvants that are suitable for the preparation of the compositions according to the invention are known per se. As 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, dipropylene glycol, dipropylene glycol methyl ether, dipropylene glycol dibenzoate, diproxitol, alkylpyrrolidone, ethyl acetate, 2-ethylhexanol, ethylene carbonate, 1 ,1 ,1-trichloroethane, 2-heptanone, alpha- pinene, d-limonene, ethyl lactate, ethylene glycol, ethylene glycol butyl ether, ethylene glycol methyl ether, gamma-butyrolactone, glycerol, glycerol acetate, glycerol diacetate, glycerol triacetate, hexadecane, hexylene glycol, isoamyl acetate, isobornyl acetate, isooctane, isophorone, isopropylbenzene, isopropyl myristate, lactic acid, laurylamine, mesityl oxide, methoxypropanol, methyl isoamyl ketone, methyl isobutyl ketone, methyl laurate, methyl octanoate, methyl oleate, methylene chloride, m-xylene, n-hexane, n-octylamine, octa- decanoic acid, octylamine acetate, oleic acid, oleylamine, o-xylene, phenol, polyethylene glycol (PEG400), propionic acid, propyl lactate, propylene carbonate, propylene glycol, propylene glycol methyl ether, p-xylene, toluene, triethyl phosphate, triethylene glycol, xylenesulfonic acid, paraffin, mineral oil, trichloroethylene, perchloroethylene, ethyl acetate, amyl acetate, butyl acetate, propylene glycol methyl ether, diethylene glycol methyl ether, methanol, ethanol, isopropanol, and alcohols of higher molecular weight, such as amyl alcohol, tetrahydrofurfuryl alcohol, hexanol, octanol, ethylene glycol, propylene glycol, glycerol, N-methyl-2-pyrrolidone and the like. 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 of fatty acids, such as polyethylene glycol stearate; block copolymers of ethylene oxide and propylene oxide; and salts of mono- and di-alkylphosphate esters; and also further substances described e.g. in "McCutcheon's Detergents and Emulsifiers Annual" MC Publishing Corp., Ridgewood New Jersey, 1981.

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.

The 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. For example, 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® (Rhδne-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 emulsif- iers and pH modifiers. Especially preferred oil additives comprise alkyl esters of C8-C22 fatty acids, thre being important especially the methyl derivatives of C12-Ci8 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. Examples of 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 C12-C22 fatty alcohols having a degree of ethoxylation of from 5 to 40. Examples of commercially available surfactants are the Genapol types (Clariant AG). Also preferred are silicone surfactants, especially polyalkyl-oxide-modified heptamethyltriloxanes which are commercially available e.g. as Silwet L-77®, and also perfluorinated surfactants. The concentration of the surface- active substances in relation to the total additive is generally from 1 to 30 % by weight. Examples of 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).

If desired, it is also possible for the mentioned surface-active substances to be used in the formulations on their own, that is to say without oil additives.

Furthermore, the addition of an organic solvent to the oil additive/surfactant mixture 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).

In addition to the oil additives listed above, for the purpose of enhancing the action of the compositions according to the invention it is also possible for formulations of alkyl- pyrrolidones (e.g. Agrimax®) to be added to the spray mixture. Formulations of synthetic latices, e.g. polyacrylamide, polyvinyl compounds or poly-1 -p-menthene (e.g. Bond®, Courier® or Emerald®) may also be used. It is also possible for solutions that contain propionic acid, for example Eurogkem Pen-e-trate®, to be added to the spray mixture as action-enhancing agent.

The 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). It is also possible for a composition according to the invention to 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), iprodione (428), isoprothiolane (432), kasugamyc (438), kresoxim-methyl (439), spiroxamine (441), mepronil (466), myclobutanil (505), nuarimol (528), pefurazoate (554), pencycuron (556), phthalide (576), probenazole (590), prochloraz (591) propiconazole (607), pyrazophos (619), pyroquilone (633), quinoxyfen (638), quintozene (639), tebuconazole (678), tetraconazole (695), thiabendazole (701), thifluzamide (705), triadimefon (720), triadimenol (721 ), tricyclazole (734), tridemorph (736), triflumizole (738), triforine (742), triticonazole (745) or vinclozolin (751). The number in brackets after each active ingredient refers to the entry number of that active ingredient in the Pesticide Manual, eleventh ed., British Crop Protection Council, 1997.

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 formula¬ tion adjuvant which preferably includes from 0 to 25 % by weight of a surface-active subst¬ ance. Whereas 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 accord¬ ing to the invention are generally applied at a rate of from 1 to 2000 g/ha.

Preferred formulations have especially the following compositions (% = percent by weight):

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 %

The following Examples further illustrate, but do not limit, the invention.

Formulation Examples for herbicides of formula I (% = % by weight)

F1. 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% (36 mol of ethylene oxide) octylphenol polyglycol ether 4 % 2 % (7-8 mol of ethylene oxide) NMP 10 % 20 % arom. hydrocarbon mixture 85 % 78 % 55 % 16 %

Emulsions of any desired concentration can be obtained from such concentrates by dilution with water. F2. Solutions a) b) c) d) active ingredient 5% 10 o/ 50 % 90 % 1 -methoxy-3-(3-methoxy- propoxy)-propane _ 20 20 % - polyethylene glycol MW 400 20% 10 - - NMP _ 30 % 10 % arom. hydrocarbon mixture 75 % 60 %

The solutions are suitable for use in the form of microdrops.

F3. 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% - (7-8 mol of ethylene oxide) highly dispersed silicic acid 1 % 3%" ' 5% 10% kaolin 88% 62% 35% _ 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.

F4. Coated granules a) b) c) active ingredient 0.1 % 5% 15' highly dispersed silicic acid 0.9 % 2% 2% > inorganic carrier 99.0% 93% 83' (diameter 0.1 - 1 mm) e.g. CaCO3 or SiO2 The active ingredient is dissolved in methylene chloride and applied to the carrier by spraying, and the solvent is then evaporated off in vacuo. F5. Coated granules a) b) c) active ingredient 0.1 % 5% 15% polyethylene glycol MW 200 1.0 % 2% 3% highly dispersed silicic acid 0.9 % 1 % 2% inorganic carrier 98.0% 92% 80% (diameter 0.1 - 1 mm) e.g. CaCO3 or SiO2 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.

F6. Extruder qranules a) b) C) d) active ingredient 0.1 % 3% 5% 15% sodium lignosulfonate 1.5 % 2% 3% 4% carboxymethylcellulose 1.4 % 2% 2% 2% kaolin 97.0 % 93% 90% 79% 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.

F7. Dusts a) b) c) active ingredient 0.1 °/c » 1 °/c > 5°/c ) talcum 39. ,9' Vo 49 ' Vo 35' Vo kaolin 60. ,0' Vo 50' Vo 60' Vo Ready-to-use dusts are obtained by mixing the active ingredient with the carriers and grinding the mixture in a suitable mill.

F8. Suspension concentrates a) b) C) d) active ingredient 3% 10% 25% 50% ethylene glycol 5% 5% 5% 5% nonylphenol polyglycol ether - 1 % 2% - (15 mol of ethylene oxide) sodium lignosulfonate 3% 3% 4% 5% carboxymethylcellulose 1 % 1 % 1 % 1 % 37 % aqueous formaldehyde 0.2 % 0.2 % 0.2 % 0.2 % solution silicone oil emulsion 0.8 % 0.8 % 0.8 % 0.8 % water 87% 79% 62% 38% The finely ground active ingredient is intimately mixed with the adjuvants, giving a suspens¬ ion concentrate from which suspensions of any desired concentration can be obtained by dilution with water.

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 render¬ ed 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. 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). Examples of 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 RoundupReady® and Liberty Link®.

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.

Crops are also to be understood as being those which have been rendered resistant to harm¬ ful 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). Examples of 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. Examples of 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). For example, 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 following Examples further illustrate, but do not limit, the invention.

Example P1 : Preparation of 2,3A4-tetrachloro-1 ,5-dimethyl-8-oxa-bicvclo[^3■2.1^octa-2,6- diene:

6.49 g (67.48 mmol) of 2,5-dimethylfuran and 10 g (56.23 mmol) of tetrachlorocyclopropene are heated at boiling temperature in 70 ml of toluene for 16 hours. The toluene and excess 2,5-dimethylfuran are then removed under reduced pressure. The product, 14.77 g of 2,3,4,4-tetrachloro-1 ,5-dimethyl-8-oxa-bicyclo[3.2.1]octa-2,6-diene, which remains behind in the form of an oil, can be transferred directly to the next reaction step without further purification.

1H-NMR (300 MHz; CDCI3) δ 6.50 (d, 1H); 6.15 (d, 1 H); 1.82 (s, 3H); 1.63 (s, 3H). Example P2: Preparation of 3,4-dichloro-1 ,5-dimethyl-8-oxa-bicyclor3.2.nocta-3,6-dien-2- one:

14 g (51.1 mmol) of unpurified 2,3,4,4-tetrachloro-1 ,5-dimethyl-8-oxa-bicyclo[3.2.1]octa-2,6- diene and 17.36 g (102.2 mmol) of silver nitrate are dissolved in 500 ml of an acetone/water 1 :1 mixture and the solution is heated for 15 hours at a temperature of 65-700C until the reactants have fully reacted (thin-layer chromatography (TLC) monitoring (mobile phase: hexane/ethyl acetate 4:1). When the reaction mixture has cooled to ambient temperature, solid sodium hydrogen carbonate is stirred in, in portions, to neutralise the nitric acid. 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 concen¬ trated 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.

1H NMR (300 MHz; CDCI3) δ 6.65 (d, 1 H); 6.23 (d, 1 H); 1.72 (s, 3H); 1.61 (s, 3H).

Example P3: Preparation of 3-chloro-1 ,5-dimethyl-4-methoxy-8-oxa-bicvclo|'3.2.1'|octa-3,6- dien-2-one and 3-chloro-4,4-dimethoxy-1.δ-dimethyl-δ-oxa-bicvclofS^.πoct -θ-en^-one:

6.0 g (27.39 mmol) of 3,4-dichloro-1,5-dimethyl-8-oxa-bicyclo[3.2.1]octa-3,6-dien- 2-one are introduced into 39 ml of anhydrous methanol. At a temperature of O0C, the reaction mixture is further diluted dropwise with a solution of 15.2 ml of 5.4M sodium methanolate (82.17 mmol) and treated with 10 ml of absolute methanol. The reaction mixture is then allowed to rise to ambient temperature with 35 minutes' stirring. Complete reaction of the starting material is determined by means of thin-layer chromatography (hexane/ethyl acetate 8:2). The reaction solution is then concentrated under reduced pressure. The residue is then extracted using carbon tetrachloride against water. The aqueous phase is extracted a further three times with fresh carbon tetrachloride. The combined organic extracts are dried over sodium sulfate and concentrated by evaporation under reduced pressure, the oil product that remains behind crystallising out, with ice cooling, as a -1 :1 mixture. The mixture is separated by means of column chromatogaphy on silica gel (eluant: gradient of 1-5% ethyl acetate/hexane). 3.1 g of pure 3-chloro-1 ,5-dimethyl-4-methoxy-8-oxa-bicyclo[3.2.1]octa-3,6-dien-2-on e are isolated.

1H NMR (300 MHz; CDCI3) δ 6.48 (d, 1 H); 6.24 (d, 1 H); 4.24 (s, 3H);1.60 (s, 3H); 1.56 (s, 3H).

A second fraction yields 3.17 g of pure 3-chloro-4,4-dimethoxy-1 ,5-dimethyl-8-oxa-bicyclo- [3.2.1 ]oct-6-en-2-one.

1H NMR (300 MHz; CDCI3) δ 6.25 (d, 1 H); 6.05 (d, 1 H); 5.15 (s, 1 H); 3.48 (s, 3H); 3.46 (s, 3H); 1.53 (s, 3H); 1.51 (s, 3H).

Example P4: Preparation of 4,4-dimethoxy-1 ,5-dimethyl-8-oxa-bicvclo[3.2.11oct-6-en-2-one:

2.2 g (8.92 mmol) of 3-chloro-4,4-dimethoxy-1 ,5-dimethyl-8-oxa-bicyclo[3.2.1]oct-6-en-2-one in 240 ml of toluene are degassed with heating at reflux temperature, and then a catalytic amount of 66 mg of azaisobutyronitrile (AIBN) and a solution of 5.9 ml (22.3 mmol) of tributyltin hydride are added in succession thereto. The reaction mixture is maintained at reflux temperature for a further 20 minutes to complete the reaction (TLC monitoring: hexane/ethyl acetate 4:1). The reaction mixture is then concentrated by evaporation under reduced pressure. The residue is then taken up in acetonitrile and the tin-containing residues are extracted using hexane. The acetonitrile phase is concentrated by evaporation in vacuo, there remaining behind 1.56 g of 4,4-dimethoxy-1 ,5-dimethyl-8-oxa-bicyclo[3.2.1]oct-6-en-2- one in the form of a yellow oil, which can be used for the next reaction step without further purification. 1H NMR (300 MHz; CDCI3) δ 6.22 (d, 1 H); 5.90 (d, 1 H); 3.41 (s, 3H); 3.25 (s, 3H); 2.92 and 2.84 (AB syst., 2H, J = 16.5 Hz); 1.55 (s, 3H); 1.45 (s, 3H).

Example P5: Preparation of I .S-dimethyl-δ-oxa-bicvclors^.itoct-θ-ene^^-dione:

1.61 g (7.59 mmol) of 4,4-dimethoxy-1 ,5-dimethyl-8-oxa-bicyclo[3.2.1]oct-6-en-2-one and 0.432 g (2.28 mmol) of p-toluenesulfonic acid are dissolved in a 2:1 mixture of acetone and water and the mixture is heated for 50 minutes at a temperature of 700C (TLC monitoring: hexane/ethyl acetate 9:1 ). The acetone is then removed under reduced pressure. The aqueous phase is then adjusted to pH 9 with saturated sodium hydrogen carbonate solution and extracted three times with ethyl acetate to remove neutral components. 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.

Example P6: Preparation of S-bromo-i ^-dimethvM-isopropoxy-δ-oxa-bicvclofS^.iiocta-S.e- dien-2-one

A solution of 5.4 ml (10.7 mmol) of 2M lithium isopropanolate is diluted with 10 ml of tetra- hydrofuran and, at ambient temperature, a solution of 2.74 g (8.9 mmol) of 3,4-dibromo-1 ,5- dimethyl-8-oxa-bicyclo[3.2.1]octa-3,6-dien-2-one (prepared according to Organic Lett. 4(12), 1997 (2002)) dissolved in 10 ml of tetrahydrof uran is added dropwise thereto. Stirring is carried out for 3 hours at ambient temperature until the starting material has fully reacted (TLC monitoring: hexane/ethyl acetate/hexane 4:1 ). The reaction solution is then treated at a temperature of 00C 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 concen¬ tration by evaporation are carried out. For further purification, 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.δ-dimethyl^-isopropoxy-δ-oxa-bicyclop^.iJocta-S.β -dien^-one are isolated.

1H NMR (300 MHz; CDCI3) δ 6.46 (d, 1H); 6.23 (d, 1H); 5.54 (hept., 1 H); 1.58 (d, 6H); 1.40 (d, 3H); 1.25 (d, 3H).

Example P7: Preparation of 3-bromo-4,4-(1 ',2'-ethylenedioxy)-bicvclor3.2.1loct-6-en-2-one:

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. The 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.

1H NMR (300 MHz; CDCI3) δ 6.38 (m, 1 H); 6.25 (m, 1 H); 5.46 (s, 1 H); 4.25 (m, 2H); 4.04 (m, 2H); 3.38 (m, 1 H); 2.98 (m, 1 H); 2.40 (m, 1 H); 2.25 (m, 1 H). Example P8: Preparation of 4,4-(1',2'-ethvlenedioxv)-bicvclo[3.2.noct-6-en-2-one:

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. The residue is taken up in a small amount of acetonitrile and extracted five times with a small amount of hexane to remove tin- containing secondary products. The acetonitrile phase is then again concentrated by evap¬ oration. 800 mg of 4,4-(1 ',2'-ethylenedioxy)-bicyclo[3.2.1]oct-6-en-2-one are obtained in the form of a yellow oil, which can be transferred directly to the next reaction step without further purification.

1H NMR (300 MHz; CDCI3) δ 6.30 (m, 1 H); 6.12 (m, 1 H); 4.02-3.90 (m, 2 x 2H); 3.10 (m, 1 H); 3.06 (d, 1 H); 2.83 (m, 1 H); 2.45 (d, 1 H); 2.40-2.25 (m, 2 x 1 H).

Example P9: Preparation of bicyclof3.2.1loct-6-ene-2,4-dione:

a) 640 mg (3.55 mmol) of 4,4-(1 ',2'-ethylenedioxy)-bicyclo[3.2.1]oct-6-en-2-one are heated in the presence of 200 mg of p-toluenesulfonic acid in a 2:1 mixture of acetone and water for 16 hours at a temperature of 700C. After complete hydrolysis (TLC monitoring: ethyl acetate / hexane 1 :1), the acetone is distilled off under reduced pressure and the aqueous phase is adjusted to pH 9 with saturated sodium hydrogen carbonate solution. After extraction of the aqueous phase three times with ethyl acetate, acidification to pH 5 is effected with dilute hydrochloric acid. Extraction is carried out three times with fresh ethyl acetate, followed by drying over sodium sulfate and concentration by evaporation in vacuo. 364 mg of pure bicyclo[3.2.1]oct-6-ene-2,4-dione are obtained in the form of a yellow oil.

1H-NMR (300 MHz; CDCI3) δ 6.22 (m, 2H); 3.50 (d, 1 H); 3.45 (m, 2H); 3.22 (d, 1H); 2.60-2.45 (m, 2 x 1 H).

b) One-pot process: 100 mg (0.39 mmol) of 3-bromo-4,4-(1',2'-ethylenedioxy)-bicyclo[3.2.1]- oct-6-en-2-one are taken up in concentrated acetic acid and treated at ambient temperature with 80 mg (1.16 mmol) of zinc powder. The progress of the reaction is monitored by means of thin-layer chromatography (mobile phase: hexane/ethyl acetate 1:1). 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.

Example P10: Preparation of 3-chloro-bicyclo[3.2.2]non-6-ene-2.4-dione:

0.7 g (2.7 mmol) of 2,3,4,4-tetrachloro-bicyclo[3.2.2]nona-2,6-diene are heated for 18 hours at a temperature of 700C in a mixture of 1 ml of trifluoroacetic acid, 4 ml of acetic acid and 1 ml of water. The cooled reaction solution is then taken up in diethyl ether and extracted first against water and then against saturated sodium chloride solution. After purification by chromatography (ethyl acetate/hexane 1 :4), 0.33 g of 3-chloro-bicyclo[3.2.2]non-6-ene-2,4- dione is obtained in the form of a mixture of tautomeric forms IVa and IVb. 1H-NMR (300 MHz; CDCI3) δ 8.58 (br, 1 H); 6.38 (m, 2H); 3.78 (m, 2H); 3.48 (m, 2H); 2.05 to 1.80 (m, 4H). Example P11 : Preparation of bicvclo[3.2.21non-6-ene-2,4-dione:

0.19 g (1 mmol) of 3-chloro-bicyclo[3.2.2]non-6-ene-2,4-dione are treated with 0.27 g (4 mmol) of zinc in the presence of 4 ml of acetic acid and heated at a temperature of 95°C for 3 hours. When cold, the reaction mixture is extracted with ethyl acetate against water and washed once with saturated sodium chloride solution. 0.14 g of amorphous bicyclo[3.2.2]- non-6-ene-2,4-dione, mostly in the form of the tautomeric form III, is obtained.

1H-NMR (300 MHz; CDCI3) δ 6.22 (m, 2H); 3.58 to 3.51 (m, 2H); 2.12 (m, 2H); 1.92 (m, 2H);

Example P12: Preparation of 5-bromo-7,8-dioxo-bicyclof2.2.21oct-5-ene-2-carboxylic acid methyl ester:

3 g (9.4 mmol) of 5-bromo-8,8-dimethoxy-7-oxo-bicyclo[2.2.2]oct-5-ene-2-carbox ylic acid methyl ester (J.Org.Chem. (202), 67, 6493) are stirred for 12 hours at ambient temperature in a mixture of 15 ml of trif luoroacetic acid and 1 ml of water. Extraction is then carried out with dichloromethane against water. The organic phase is dried over sodium sulfate and yields, after removal of the solvent, 5-bromo-7,8-dioxo-bicyclo[2.2.2]oct-5-ene-2-carboxylic acid methyl ester in the form of an orange-coloured oil and as a pure isomer;

1H-NMR (300 MHz; CDCI3) δ 6.62 (d, 1 H); 3.97 (d, 1 H); 3.80 (s, 3H); 3.70 (m, 1 H); 3.20 (d, 1 H); 2.63 (m 1 H); 2.40 (m, 1 H). Example P13: Preparation of 8-bromo-2,4-dioxo-bicyclor3.2.21non-8-ene-6-carboxylic acid methyl ester:

4.2 ml of trimethylsilyl-diazomethane are added dropwise at a temperature of -100C , in the presence of 0.089 ml (0.7 mmol) of boron trifluoride etherate, to 1.91 g (7 mmol) of 5-bromo- 7,8-dioxo-bicycIo[2.2.2]oct-5-ene-2-carboxylic acid methyl ester dissolved in 20 ml of dichloromethane. The reaction mixture is allowed to rise to ambient temprature and is stirred for 4 hours. The reaction mixture is then washed against water. After the organic phase has been dried over sodium sulfate, concentration by evaporation is carried out using a rotary evaporator and the residue that remains behind is purified by chromatography on silica gel. There is thus obtained, as main component, one isomer of 8-bromo-2,4-dioxo-bicyclo- [3.2.2]non-8-ene-6-carboxylic acid methyl ester.

1H-NMR (300 MHz; CDCI3) δ 6.42 (d, 1 H); 3.86 (d, 1 H); 3.75 (d, 1 H); 3.68 (s, 3H); 3.65 (m, 1 H); 3.43 (d, 1 H); 3.10 (m, 1 H); 2.52 (m, 1 H); 2.34 (m, 1 H); tautomeric form Da.

Example P14: Preparation of 3-(4-methylsulfonyl-2-nitro-benzoyl)-bicyclo[3.2.noct-6-ene- 2,4- dione:

0.194 g (0.21 mmol, 1.1 eq.) of 1-chloro-2-methyl-propenyl)-dimethylamine are added at ambient temperature to a solution of 0.324 g (1.32 mmol, 1 eq.) of 4-methylsulfonyl-2-nitro- benzoic acid in 12 ml of anhydrous methylene chloride. The reaction mixture is then stirred for 2 hours at ambient temperature and, after cooling to a temperature of 00C, 0.201 g (0.28 ml, 1.98 mmol, 1.5 eq.) of anhydrous triethylamine is added. Stirring is continued for a further 2 hours at ambient temperature and the reaction mixture is then concentrated in vacuo. 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). The 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.

Example P15: Preparation of 3-(4-methylsulfonyl-2-nitro-benzoyl)-1 -methyl-8-oxa-bicvclo- [3.2.1 loct-6-ene-2,4-dione: 0.2 g (0.969 mmol, 1 eq.) of N,N'-dicyclohexylcarbodiimide and 10 ml of anhydrous methylene chloride are added at ambient temperature to a solution of 0.134 g (0.881 mmol, 1 eq.) of 1-methyl-8-oxa-bicyclo[3.2.1]oct-6-ene-2,4-dione and 0.216 g (0.881 mmol, 1 eq.) of 4-methylsulfonyl-2-nitro-benzoic acid in 19 ml of anhydrous acetonitrile and the reaction mixture is stirred at ambient temperature for 2.5 hours. 0.134 g (0.18 ml, 1.32 mmol, 1.5 eq.) of anhydrous triethylamine and 0.075 g (0.08 ml, 0.881 mmol, 1.5 eq.) of acetocyanohydrin are then added and the mixture is stirred for a further 18 hours. The reaction mixture is then filtered and the filtration residue is washed with ethyl acetate. The filtrate is then concen¬ trated under reduced pressure and the oily 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). The 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.

Compounds of formula I can be prepared generally in accordance with the above processes. In this way it is also possible to prepare the compounds of formula I listed in the Table below, wherein compounds defined as oil, resin, wax or amorphous solid have been characterised, at least in pure form, by means of 1H-NMR (nuclear resonance spectroscopy) and/or MS (mass spectrometry).

Table 1 : Compounds of formula Ib:

No. A2 A, Y Ri R2 Rθ2O2 Ro2O3 Rθ2O4 Physical

1.001 CH CH CH2 H H Cl H SO2CH3 1.002 CH CH CH2 H H NO2 H SO2CH3 solid (P14) 1.003 CH CH CH2 H H SO2CH3 H CF3 1.004 CH CH CH2 H H NO2 H CF3 1.005 CH CH CH2 H H Cl OCH3 SO2CH3 1.006 CH CH CH2 H H Br OCH3 SO2CH3 1.007 CH CH CH2 H H CH3 OCH3 SO2CH3 1.008 CH CH CH2 H H Cl OCH3 Cl 1.009 CH CH CH2 H H Br OCH3 Br 1.010 CH CH CH2 H H CH3 OCH3 Cl 1.011 CH CH CH2 H H CH3 OCH3 Br 1.012 CH CH CH2 H H CH3 OCH3 I 1.013 CH CH CH2 H H CH3 OCH3 CF3 resin 1.014 CH CH CH2 H H Cl OCH2CH3 SO2CH3 1.015 CH CH CH2 H H Cl OCH2CH=CH2 SO2CH3 1.016 CH CH CH2 H H Cl OCH2CCH SO2CH3 1.017 CH CH CH2 H H Cl OCH2CH2F SO2CH3 1.018 CH CH CH2 H H Cl OCH2CH2CI SO2CH3 1.019 CH CH CH2 H H Cl OCH2CF3 SO2CH3 1.020 CH CH CH2 H H Cl OCH2CH2OCH3 SO2CH3 resin 1.021 CH CH CH2 H H Cl OCH2CH2OCH2CH3 SO2CH3 1.022 CH CH CH2 H H Cl SCH3 SO2CH3 1.023 CH CH CH2 H H Cl SCH2CH3 SO2CH3 No. A2 A1 Y Ri R2 Roao2 Rθ2O3 Rθ2O4 Physical

1.024 CH CH CH2 H H Cl SCH2CH2OCH3 SO2CH3 1.025 CH CH CH2 H H Cl SCH2CH2OCH2CH3 SO2CH3 resin 1.026 CH CH CH2 H H Br OCH2CH3 Br 1.027 CH CH CH2 H H Br OCH2CH=CH2 Br 1.028 CH CH CH2 H H Br OCH2CCH Br 1.029 CH CH CH2 H H Br OCH2CH2OCH3 Br resin 1.030 CH CH CH2 H H Br OCH2CH2OCH2CH3 Br resin 1.031 CH CH CH2 H H Br OCH2CH2NHC(O)O Br resin CH3 1.032 CH CH CH2 H H Br OCH2NHC(O)CH3 Br 1.033 CH CH CH2 H H Cl OCH2NHC(O)CH3 SO2CH3 1.034 CH CH CH2 H H CH3 OCH2CH3 SO2CH3 1.035 CH CH CH2 H H CH3 OCH2CH=CH2 SO2CH3 1.036 CH CH CH2 H H CH3 OCH2CCH SO2CH3 1.037 CH CH CH2 H H CH3 OCH2CH2F SO2CH3 1.038 CH CH CH2 H H CH3 OCH2CH2CI SO2CH3 1.039 CH CH CH2 H H CH3 OCH2CF3 SO2CH3 1.040 CH CH CH2 H H CH3 OCH2CH2OCH3 SO2CH3 1.041 CH CH CH2 H H CH3 OCH2CH2OCH2CH3 SO2CH3 1.042 CH CH CH2 H H Br OCH2- Br tetrahydrofuran-2-yl 1.043 CH CH CH2 H H Cl OCH2- SO2CH3 tetrahydrofuran-2-yl 1.044 CH CH CH2 H H CH3 OCH2- SO2CH3 tetrahydrofuran-2-yl 1.045 CH CH CH2 H H Br OCH2-dioxazol-2-yl Br 1.046 CH CH CH2 H H Cl OCH2-dioxazol-2-yl SO2CH3 1.047 CH CH CH2 H H C! CH2OCH3 SO2CH3 1.048 CH CH CH2 H H CH3 CH2OCH3 SO2CH3 1.049 CH CH CH2 H H Cl CH2OCH2CF3 SO2CH3 1.050 CH CH CH2 H H CH3 CH2OCH2CF3 SO2CH3 1.051 CH CH CH2 H H Cl CH2OCH2- SO2CH3 tetrahydrofuran-2-yl 1.052 CH CH CH2 H H CH3 CH2OCH2- SO2CH3 tetrahydrofuran-2-yl 1.053 CH CH CH2 H H Cl COOCH3 SO2CH3 1.054 CH CH CH2 H H CH3 COOCH3 SO2CH3 1.055 CH CH CH2 H H Cl CN SO2CH3 1.056 CH CH CH2 H H CH3 CN SO2CH3 1.057 CH CH CH2 H H Cl 4,5-dihydro-isoxazol- SO2CH3 solid 3-yl No. A2 A1 Y Ri R2 R0202 R0203 Rθ2O4 Physical data 1.058 CH CH CH2 H H CH3 4,5-dihydro-isoxazol- SO2CH3 3-yl 1.059 CH CH O H H NO2 H SO2CH3 resin 1.060 CH CH O CH3 CH3 NO2 H SO2CH3 solid 1.061 CH CH CH2CH2 H H NO2 H SO2CH3 1.062 CH CH CH2CH2 H H CH3 OCH3 SO2CH3 1.063 CH CH CH2CH2 H H Cl OCH3 SO2CH3 1.064 CH CH CH2CH2 H H CH3 OCH2CH2OCH3 SO2CH3 1.065 CH CH CH2CH2 H H Cl OCH2CH2OCH3 SO2CH3 1.066 CBr CH CH2CH(COOCH3) H H CH3 CH2OCH2- SO2CH3 tetrahydrofuran-2-yl 1.067 CH CH CH2CH(COOCH3) H H CH3 CH2OCH2- SO2CH3 tetrahydrofuran-2-yl 1.068 CBr CH CH2CH(COOCH3) H H Cl CH2OCH2- SO2CH3 resin; tetrahydrofuran-2-yl NEt3.salt 1.069 CH CH CH2CH(COOCH3) H H Cl CH2OCH2- SO2CH3 tetrahydrofuran-2-yl

1.070 CH CH CH2CH2 H H Cl CH2OCH2- SO2CH3 tetrahydrofuran-2-yl 1.071 CH CH O CH3 H NO2 H SO2CH3 resin (P15) 1.072 CH CH CH2 H H CH3 OCH3 CN 1.073 CH CH CH2 H H CH3 OCH3 NO2 m.p. 155- 1580C

Table 2: Intermediates of formulae III. HIa, IV and IVb

(III) and (IVb)1 (Ilia) and (IV)

No. A, A2 Y Ri R2 Ya Xa Physical data, remarks 2.001 CH CH CH2 H H OH H Preparation Example PA6 and P9; tautomer III 2.002 CH CH CH2 H H OCH3 H 2.003 CH CH CH2 H H OCH2CH3 H 2.004 CH CH CH2 H H OC(CHs)2 H 2.005 CH CH CH2CH2 H H OH H Preparation Example P11 No. A1 A2 Y R1 R2 Ya Xa Physical data, remarks 2.006 CH CH CH2CH2 H H OCH3 H 2.007 CH CH CH2CH2 H H OCH2CH3 H 2.008 CH CH CH2CH2 H H OC(CHg)2 H 2.009 CH CH O H H OH H 1H-NMR (300 MHz; CDCI3) δ 6.35 (s, 2H); 5.66 (s, 1 H); 3.78 (d, 1 H); 3.43 (d, 1 H); tautomer lll 2.010 CH CH O H H OCH3 H 2.011 CH CH O H H OCH2CH3 H 2.012 CH CH O H H OC(CH3)2 H 2.013 CH CH NSO2CH3 H H OH H 2.014 CH CH NSO2CH3 H H OCH3 H 2.015 CH CH NSO2CH3 H H OCH2CH3 H 2.016 CH CH NSO2CH3 H H OC(CHs)2 H 2.017 CH CH NC(O)C(CHs)3 H H OH H 2.018 CH CH NC(O)C(CHs)3 H H OCH3 H 2.019 CH CH NC(O)C(CHs)3 H H OCH2CH3 H 2.020 CH CH NC(O)C(CHs)3 H H OC(CH3)2 H 2.021 CH CH CH2 H H OH Cl Preparation Example PA3 and PA4 2.022 CH CH CH2 H H OCH3 Cl 2.023 CH CH CH2 H H OCH2CH3 Cl 2.024 CH CH CH2 H H OC(CH3)2 Cl 2.025 CH CH CH2CH2 H H OH Cl Preparation Example P10 2.026 CH CH CH2CH2 H H OCH3 Cl 2.027 CH CH CH2CH2 H H OCH2CH3 Cl 2.028 CH CH CH2CH2 H H OC(CHs)2 Cl 2.029 CH CH O H H OH Cl 2.030 CH CH O H H OCH3 Cl 2.031 CH CH O H H OCH2CH3 Cl 2.032 CH CH O H H OC(CHs)2 Cl 2.033 CH CH NSO2CH3 H H OH Cl 2.034 CH CH NSO2CH3 H H OCH3 Cl 2.035 CH CH NSO2CH3 H H OCH2CH3 Cl 2.036 CH CH NSO2CH3 H H OC(CHs)2 Cl 2.037 CH CH NC(O)C(CH3)S H H OH Cl 2.038 CH CH NC(O)C(CHa)3 H H OCH3 Cl 2.039 CH CH NC(O)C(CHS)3 H H OCH2CH3 Cl 2.040 CH CH NC(O)C(CH3)S H H OC(CHs)2 Cl 2.041 CH CH CH2 H H OH Br 2.042 CH CH CH2 H H OCH3 Br resin 2.043 CH CH CH2 H H OCH2CH3 Br No. A2 Ri R2 Ya Xa Physical data, remarks 2.044 CH CH CH2 H H OC(CHa)2 Br 2.045 CH CH CH2CH2 H H OH Br 2.046 CH CH CH2CH2 H H OCH3 Br 2.047 CH CH CH2CH2 H H OCH2CH3 Br 2.048 CH CH CH2CH2 H H OC(CHs)2 Br 2.049 CH CH O H H OH Br 2.050 CH CH O H H OCH3 Br 2.051 CH CH O H H OCH2CH3 Br 2.052 CH CH O H H OC(CHs)2 Br 2.053 CH CH NSO2CH3 H H OH Br 2.054 CH CH NSO2CH3 H H OCH3 Br 2.055 CH CH NSO2CH3 H H OCH2CH3 Br 2.056 CH CH NSO2CH3 H H OC(CHs)2 Br 2.057 CH CH NC(O)C(CH3)S H H OH Br 2.058 CH CH NC(O)C(CHs)3 H H OCH3 Br 2.059 CH CH NC(O)C(CHs)3 H H OCH2CH3 Br 2.060 CH CH NC(O)C(CH3)3 H H OC(CHs)2 Br 2.061 CH CH CH2 H CH3 OH H 1H-NMR (300 MHz; CDCI3) δ 6.30 (m, 1 H); 6.10 (m, 1 H); 3.73 (d, 1 H); 3.44 (d, 1 H); 1.62 (s,3H); tautomer III 2.062 CH CH CH2 H CH3 OCH3 H 2.063 CH CH CH2 H CH3 OCH2CH3 H 2.064 CH CH CH2 H CH3 OC(CHs)2 H 2.065 CH CH CH2CH2 H CH3 OH H 2.066 CH CH CH2CH2 H CH3 OCH3 H 2.067 CH CH CH2CH2 H CH3 OCH2CH3 H 2.068 CH CH CH2CH2 H CH3 OC(CH3)2 H 2.069 CH CH O H CH3 OH H 1H-NMR (300 MHz; CDCI3) δ 6.3 (dxm, 1 H); 6.1 (d, 1 H); 5.16 (s, 1 H); 3.76-3.40 (dxd, 2H); 1.62 (s, 3H); tautomer III 2.070 CH CH O H CH3 OCH3 H 2.071 CH CH O H CH3 OCH2CH3 H 2.072 CH CH O H CH3 OC(CH3)2 H 2.073 CH CH NSO2CH3 H CH3 OH H 2.074 CH CH NSO2CH3 H CH3 OCH3 H 2.075 CH CH NSO2CH3 H CH3 OCH2CH3 H 2.076 CH CH NSO2CH3 H CH3 OC(CHs)2 H 2.077 CH CH NC(O)C(CH3)S H CH3 OH H 2.078 CH CH NC(O)C(CHs)3 H CH3 OCH3 H 2.079 CH CH NC(O)C(CHa)3 H CH3 OCH2CH3 H No. Ai A2 Ri R2 Ya Xa Physical data, remarks 2.080 CH CH NC(O)C(CHs)3 H CH3 OC(CHs)2 H 2.081 CH CH CH2 H CH3 OH Cl 2.082 CH CH CH2 H CH3 OCH3 Cl 2.083 CH CH CH2 H CH3 OCH2CH3 Cl 2.084 CH CH CH2 H CH3 OC(CHs)2 Cl 2.085 CH CH CH2CH2 H CH3 OH Cl 2.086 CH CH CH2CH2 H CH3 OCH3 Cl 2.087 CH CH CH2CH2 H CH3 OCH2CH3 Cl 2.088 CH CH CH2CH2 H CH3 OCH(CHs)2 Cl 2.089 CH CH O H CH3 OH Cl resin 2.090 CH CH O H CH3 OCH3 Cl 2.091 CH CH O H CH3 OCH2CH3 Cl 2.092 CH CH O H CH3 OCH(CHs)2 Cl 2.093 CH CH NSO2CH3 H CH3 OH Cl 2.094 CH CH NSO2CH3 H CH3 OCH3 Cl 2.095 CH CH NSO2CH3 H CH3 OCH2CH3 Cl 2.096 CH CH NSO2CH3 H CH3 OCH(CHs)2 Cl 2.097 CH CH NC(O)C(CHs)3 H CH3 OH Cl 2.098 CH CH NC(O)C(CHs)3 H CH3 OCH3 Cl 2.099 CH CH NC(O)C(CHs)3 H CH3 OCH2CH3 Cl 2.100 CH CH NC(O)C(CHs)3 H CH3 OCH(CHs)2 Cl 2.101 CH CH CH2 H CH3 OH Br 2.102 CH CH CH2 H CH3 OCH3 Br 2.103 CH CH CH2 H CH3 OCH2CH3 Br 2.104 CH CH CH2 H CH3 OCH(CHs)2 Br 2.105 CH CH CH2CH2 H CH3 OH Br 2.106 CH CH CH2CH2 H CH3 OCH3 Br 2.107 CH CH CH2CH2 H CH3 OCH2CH3 Br 2.108 CH CH CH2CH2 H CH3 OCH(CHs)2 Br 2.109 CH CH O H CH3 OH Br 2.110 CH CH O H CH3 OCH3 Br 2.111 CH CH O H CH3 OCH2CH3 Br 2.112 CH CH O H CH3 OCH(CHs)2 Br 2.113 CH CH NSO2CH3 H CH3 OH Br 2.114 CH CH NSO2CH3 H CH3 OCH3 Br 2.115 CH CH NSO2CH3 H CH3 OCH2CH3 Br 2.116 CH CH NSO2CH3 H CH3 OCH(CHs)2 Br 2.117 CH CH NC(O)C(CH3)3 H CH3 OH Br 2.118 CH CH NC(O)C(CH3)3 H CH3 OCH3 Br No. Ai A2 Y Ri R2 Ya Xa Physical data, remarks 2.119 CH CH NC(O)C(CHa)3 H CH3 OCH2CH3 Br 2.120 CH CH NC(O)C(CH3)S H CH3 OCH(CHs)2 Br 2.121 CH CH CH2 CH3 CH3 OH H 2.122 CH CH CH2 CH3 CH3 OCH3 H 2.123 CH CH CH2 CH3 CH3 OCH2CH3 H 2.124 CH CH CH2 CH3 CH3 OCH(CHs)2 H 2.125 CH CH CH2CH2 CH3 CH3 OH H 2.126 CH CH CH2CH2 CH3 CH3 OCH3 H 2.127 CH CH CH2CH2 CH3 CH3 OCH2CH3 H 2.128 CH CH CH2CH2 CH3 CH3 OCH(CHs)2 H 2.129 CH CH O CH3 CH3 OH H Preparation Example P5 2.130 CH CH O CH3 CH3 OCH3 H 2.131 CH CH O CH3 CH3 OCH2CH3 H 2.132 CH CH O CH3 CH3 OCH(CHs)2 H 2.133 CH CH NSO2CH3 CH3 CH3 OH H 2.134 CH CH NSO2CH3 CH3 CH3 OCH3 H 2.135 CH CH NSO2CH3 CH3 CH3 OCH2CH3 H 2.136 CH CH NSO2CH3 CH3 CH3 OCH(CH3)2 H 2.137 CH CH NC(O)C(CHa)3 CH3 CH3 OH H 2.138 CH CH NC(O)C(CHs)3 CH3 CH3 OCH3 H 2.139 CH CH NC(O)C(CHs)3 CH3 CH3 OCH2CH3 H 2.140 CH CH NC(O)C(CHs)3 CH3 CH3 OCH(CHs)2 H 2.141 CH CH CH2 CH3 CH3 OH Cl 2.142 CH CH CH2 CH3 CH3 OCH3 Cl 2.143 CH CH CH2 CH3 CH3 OCH2CH3 Cl 2.144 CH CH CH2 CH3 CH3 OCH(CHs)2 Cl 2.145 CH CH CH2CH2 CH3 CH3 OH Cl 2.146 CH CH CH2CH2 CH3 CH3 OCH3 Cl 2.147 CH CH CH2CH2 CH3 CH3 OCH2CH3 Cl 2.148 CH CH CH2CH2 CH3 CH3 OCH(CHs)2 Cl 2.149 CH CH O CH3 CH3 OH Cl amorphous solid 2.150 CH CH O CH3 CH3 OCH3 Cl Preparation Example P3 2.151 CH CH O CH3 CH3 OCH2CH3 Cl 2.152 CH CH O CH3 CH3 OCH(CHs)2 Cl 2.153 CH CH NSO2CH3 CH3 CH3 OH Cl 2.154 CH CH NSO2CH3 CH3 CH3 OCH3 Cl 2.155 CH CH NSO2CH3 CH3 CH3 OCH2CH3 Cl 2.156 CH CH NSO2CH3 CH3 CH3 OCH(CHs)2 Cl 2.157 CH CH NC(O)C(CHs)3 CH3 CH3 OH Cl No. A1 Ap Y Ri R2 Ya Xa Physical data, remarks 2.158 CH CH NC(O)C(CHs)3 CH3 CH3 OCH3 Cl 2.159 CH CH NC(O)C(CHs)3 CH3 CH3 OCH2CH3 Cl 2.160 CH CH NC(O)C(CHs)3 CH3 CH3 OCH(CHs)2 Cl 2.161 CH CH CH2 CH3 CH3 OH Br 2.162 CH CH CH2 CH3 CH3 OCH3 Br 2.163 CH CH CH2 CH3 CH3 OCH2CH3 Br 2.164 CH CH CH2 CH3 CH3 OCH(CHs)2 Br 2.165 CH CH CH2CH2 CH3 CH3 OH Br 2.166 CH CH CH2CH2 CH3 CH3 OCH3 Br 2.167 CH CH CH2CH2 CH3 CH3 OCH2CH3 Br 2.168 CH CH CH2CH2 CH3 CH3 OCH(CHs)2 Br 2.169 CH CH O CH3 CH3 OH Br 2.170 CH CH O CH3 CH3 OCH3 Br 2.171 CH CH O CH3 CH3 OCH2CH3 Br 2.172 CH CH O CH3 CH3 OCH(CHs)2 Br Preparation Example P6 2.173 CH CH NSO2CH3 CH3 CH3 OH Br 2.174 CH CH NSO2CH3 CH3 CH3 OCH3 Br 2.175 CH CH NSO2CH3 CH3 CH3 OCH2CH3 Br 2.176 CH CH NSO2CH3 CH3 CH3 OCH(CHs)2 Br 2.177 CH CH NC(O)C(CH3)S CH3 CH3 OH Br 2.178 CH CH NC(O)C(CHs)3 CH3 CH3 OCH3 Br 2.179 CH CH NC(O)C(CHa)3 CH3 CH3 OCH2CH3 Br 2.180 CH CH NC(O)C(CHs)3 CH3 CH3 OCH(CHs)2 Br

2.182 CH CH H H OH H 1H-NMR (300 MHz; CDCI3) δ 6.30 (sxm, 2H); 3.60 (d, 1 H); 3.23 (d, 1 H); 2.82 (s, 1 H); 0.75 (m,4H); tautomer III 2.183 CH CH C(=C(CH3)2) H H OH Cl resin 2.184 CH CH C(=C(CH3)2) H H OH H 1H-NMR (300 MHz; CDCI3) δ 6.82 (sxm, 2H); 4.14 (sxm, 2H); 3.60 (d, 1 H); 3.13 (d, 1 H); 1.75 (s, 6H); tautomer III 2.185 CBr CH CH2CH(COOCH3) H H OH H Preparation Example P13 2.186 CH CH CH2CH(COOCHs) H H OH H 2.187 CH CH CH(Si(CHs)3) H H Cl Cl 2.188 CH CH CH(Si(CHs)3) H H OH Cl m.p.: 126-128°C 2.189 CH CH CH(Si(CHs)3) H H OH H m.p.: 61-63°C 2.190 CH CH CH(Si(CH3);,Drιenvl) H H Cl Cl 1H-NMR (300 MHz; CDCI3) δ 7.40- 7.25 (m, 5H); 6.6 (m, 1 H); 6.1 (m, 1 H); 3.5 (d, 1 H); 3.39 (d, 1 H); 2.60 (s, No. A1 A2 Y Ri R2 Ya Xa Physical data, remarks 1 H); 0.21 (s, 3H); 0.20 (s, 3H) 2.191 CH CH CH(Si(CH3)2phenyl) H H OCH(CHs)2 Cl resin 2.192 CH CH CH(Si(CH3)2phenyI) H H OH Cl 2.193 CH CH CH(Si(CH3)2phenyl) H H OH H 2.194 CH CH CH(OH) H H OH Cl 2.195 CH CH CH(OH) H H OH H 2.196 CH CH CH(OCH3) H H OH Cl 2.197 CH CH CH(OCH3) H H OH H 2.198 CH CH3 CH2 H H OH Cl resin 2.199 CH CH3 CH2 H H OH H resin 2.200 CH CH CH2 H H Cl Cl 1H-NMR (300 MHz; CDCI3) δ 6.8 (m, 1 H); 6.3 (m, 1 H); 3.6 (m, 2H); 2.7 (m, 1 H); 2.5 (m, 1 H) 2.201 CH CH H H Cl Cl 1H-NMR (300 MHz; CDCI3) δ 6.86 (m, 1 H); 6.36 (m, 1 H); 3.0 (m, 1 H); 2.95 (m, 1 H); 0.90-0.65 (mxm, 4H) 2.202 CH CH CH2 H H Br Br 1H-NMR (300 MHz; CDCI3) δ 6.83 (m, 1 H); 6.3 (m, 1 H); 3.8 (m, 1 H); 3.63 (m, 1 H); 2.7 (m, 1 H); 2.45 (m, 1 H) 2.203 CH CH O CH3 CH3 Cl Cl 1H-NMR (300 MHz; CDCI3) δ 6.64 (d, 1 H); 6.20 (d, 1 H); 1.72 (s, 3H); 1.59 (s, 3H) 2.204 CH CH O H H Br Br 1H-NMR (300 MHz; CDCI3) δ 7.0 (m, 1 H); 6.56 (m, 1 H); 5.39 (s, 1 H); 5.27 (s, 1 H) 2.205 CH CH O CHs H Br Br 1H-NMR (300 MHz: CDCI3) isomer I: δ 6.94 (dxd, 1H); 6.30 (d, 1 H); 5.35 (d, 1 H); 1.62 (s, 3H); isomer II: 6.75 (d, 1 H); 6.48 (dxd, 1 H); 5.18 (d, 1 H); 1.82 (s, 3H) 2.206 CH CH O CH3 CH3 Br Br

Table 3: Intermediates of formulae VIl and VIlI:

No. Ai Ri R2 R3a R33 Y Xa Physical data, remarks 3.000 CH CH H H CH3 CH3 CH2 H 3.001 CH CH H H CH2CH3 CH2CH3 CH2 H 3.002 CH CH H H -CH2CH2- CH2 H Preparation Example P8 No. Ai A2 Ri R2 R3a Rβa Y Xa Physical data, remarks 3.003 CH CH H H CH3 CH3 O H 3.004 CH CH H H CH2CH3 CH2CH3 O H 3.005 CH CH H H -CH2CH2- O H 3.006 CH CH H H CH3 CH3 NSO2CH3 H 3.007 CH CH H H CH2CH3 CH2CH3 NSO2CH3 H 3.008 CH CH H H -CH2CH2- NSO2CH3 H 3.009 CH CH H H CH3 CH3 NC(O)C(CHs)3 H 3.010 CH CH H H CH2CH3 CH2CH3 NC(O)C(CHs)3 H 3.011 CH CH H H -CH2CH2- NC(O)C(CH3)3 H 3.012 CH CH H H CH3 CH3 CH2CH2 H 3.013 CH CH H H CH2CH3 CH2CH3 CH2CH2 H 3.014 CH CH H H -CH2CH2- CH2CH2 H 3.015 CH CH H H CH3 CH3 CH2 Cl 3.016 CH CH H H CH2CH3 CH2CH3 CH2 Cl 3.017 CH CH H H -CH2CH2- CH2 Cl 1H-NMR (300 MHz; CDCI3) δ 6.4 (m, 1 H); 6.25 (m, 1 H); 5.30 (s, 1H); 4.3-3.9 (2xm, 2x2H); 3.35 (m, 1 H); 2.95 (m, 1 H); 2.4 (m, 1 H); 2.24 (m, 1 H) 3.018 CH CH H H CH3 CH3 O Cl 3.019 CH CH H H CH2CH3 CH2CH3 O Cl 3.020 CH CH H H -CH2CH2- O Cl 3.021 CH CH H H CH3 CH3 NSO2CH3 Cl 3.022 CH CH H H CH2CH3 CH2CH3 NSO2CH3 Cl 3.023 CH CH H H -CH2CH2- NSO2CH3 Cl 3.024 CH CH H H CH3 CH3 NC(O)C(CHs)3 Cl 3.025 CH CH H H CH2CH3 CH2CH3 NC(O)C(CHs)3 Cl 3.026 CH CH H H -CH2CH2- NC(O)C(CHs)3 Cl 3.027 CH CH H H CH3 CH3 CH2CH2 Cl 3.028 CH CH H H CH2CH3 CH2CH3 CH2CH2 Cl 3.029 CH CH H H -CH2CH2- CH2CH2 Cl 3.030 CH CH H H CH3 CH3 CH2 Br 3.031 CH CH H H CH2CH3 CH2CH3 CH2 Br 3.032 CH CH H H -CH2CH2- CH2 Br Preparation Example P7 3.033 CH CH H H CH3 CH3 O Br 3.034 CH CH H H CH2CH3 CH2CH3 O Br 3.035 CH CH H H -CH2CH2- O Br 3.036 CH CH H H CH3 CH3 NSO2CH3 Br 3.037 CH CH H H CH2CH3 CH2CH3 NSO2CH3 Br 3.038 CH CH H H -CH2CH2- NSO2CH3 Br No. A1 A2 Ri R2 R3a R3 Xa Physical data, remarks 3.039 CH CH H H CH3 CH3 NC(O)C(CHs)3 Br 3.040 CH CH H H CH2CH3 CH2CH3 NC(O)C(CHs)3 Br 3.041 CH CH H H -CH2CH2- NC(O)C(CHs)3 Br 3.042 CH CH H H CH3 CH3 CH2CH2 Br 3.043 CH CH H H CH2CH3 CH2CH3 CH2CH2 Br 3.044 CH CH H H -CH2CH2- CH2CH2 Br 3.045 CH CH H CH3 CH3 CH3 CH2 H 3.046 CH CH H CH3 CH2CH3 CH2CH3 CH2 H 3.047 CH CH H CH3 -CH2CH2- CH2 H 3.048 CH CH H CH3 CH3 CH3 O H 3.049 CH CH H CH3 CH2CH3 CH2CH3 O H 3.050 CH CH H CH3 -CH2CH2- O H 3.051 CH CH H CH3 CH3 CH3 NSO2CH3 H 3.052 CH CH H CH3 CH2CH3 CH2CH3 NSO2CH3 H 3.053 CH CH H CH3 -CH2CH2- NSO2CH3 H 3.054 CH CH H CH3 CH3 OCH3 NC(O)C(CHs)3 H 3.055 CH CH H CH3 CH2CH3 CH2CH3 NC(O)C(CH3)3 H 3.056 CH CH H CH3 -CH2CH2- NC(O)C(CH3)S H 3.057 CH CH H CH3 CH3 CH3 CH2CH2 H 3.058 CH CH H CH3 CH2CH3 CH2CH3 CH2CH2 H 3.059 CH CH H CH3 -CH2CH2- CH2CH2 H 3.060 CH CH H CH3 CH3 CH3 CH2 Cl 3.061 CH CH H CH3 CH2CH3 CH2CH3 CH2 Cl 3.062 CH CH H CH3 -CH2CH2- CH2 Cl 3.063 CH CH H CH3 CH3 CH3 O Cl 3.064 CH CH H CH3 CH2CH3 CH2CH3 O Cl 3.065 CH CH H CH3 -CH2CH2- O Cl 3.066 CH CH H CH3 CH3 CH3 NSO2CH3 Cl 3.067 CH CH H CH3 CH2CH3 CH2CH3 NSO2CH3 Cl 3.068 CH CH H CH3 -CH2CH2- NSO2CH3 Cl 3.069 CH CH H CH3 CH3 CH3 NC(O)C(CHs)3 Cl 3.070 CH CH H CH3 CH2CH3 CH2CH3 NC(O)C(CHs)3 Cl 3.071 CH CH H CH3 -CH2CH2- NC(O)C(CHs)3 Cl 3.072 CH CH H CH3 CH3 CH3 CH2CH2 Cl 3.073 CH CH H CH3 CH2CH3 CH2CH3 CH2CH2 Cl 3.074 CH CH H CH3 -CH2CH2- CH2CH2 Cl 3.075 CH CH H CH3 CH3 CH3 CH2 Br 3.076 CH CH H CH3 CH2CH3 CH2CH3 CH2 Br 3.077 CH CH H CH3 -CH2CH2- CH2 Br No. A1 A2 R1 R2 R3a R3a Y Xa Physical data, remarks 3.078 CH CH H CH3 CH3 CH3 O Br 3.079 CH CH H CH3 CH2CH3 CH2CH3 O Br 3.080 CH CH H CH3 -CH2CH2- O Br 3.081 CH CH H CH3 CH3 CH3 NSO2CH3 Br 3.082 CH CH H CH3 CH2CH3 CH2CH3 NSO2CH3 Br 3.083 CH CH H CH3 -CH2CH2- NSO2CH3 Br 3.084 CH CH H CH3 CH3 CH3 NC(O)C(CHs)3 Br 3.085 CH CH H CH3 CH2CH3 CH2CH3 NC(O)C(CHs)3 Br 3.086 CH CH H CH3 -CH2CH2- NC(O)C(CH3)3 Br 3.087 CH CH H CH3 CH3 CH3 CH2CH2 Br 3.088 CH CH H CH3 CH2CH3 CH2CH3 C H2C H2 Br 3.089 CH CH H CH3 -CH2CH2- CH2CH2 Br 3.090 CH CH CH3 CH3 CH3 CH3 CH2 H 3.091 CH CH CH3 CH3 CH2CH3 CH2CH3 CH2 H 3.092 CH CH CH3 CH3 -CH2CH2- CH2 H 3.093 CH CH CH3 CH3 CH3 CH3 O H Preparation Example P4 3.094 CH CH CH3 CH3 CH2CH3 CH2CH3 O H 3.095 CH CH CH3 CH3 -CH2CH2- O H 3.096 CH CH CH3 CH3 CH3 CH3 NSO2CH3 H 3.097 CH CH CH3 CH3 CH2CH3 CH2CH3 NSO2CH3 H 3.098 CH CH CH3 CH3 NSO2CH3 H 3.099 CH CH CH3 CH3 CH3 CH3 NC(O)C(CHs)3 H 3.100 CH CH CH3 CH3 CH2CH3 CH2CH3 NC(O)C(CHs)3 H 3.101 CH CH CH3 CH3 -CH2CH2" NC(O)C(CHs)3 H 3.102 CH CH CH3 CH3 CH3 CH3 CH2CH2 H 3.103 CH CH CH3 CH3 CH2CH3 CH2CH3 CH2CH2 H 3.104 CH CH CH3 CH3 -CH2CH2- CH2CH2 H 3.105 CH CH CH3 CH3 CH3 CH3 CH2 Cl 3.106 CH CH CH3 CH3 CH2CH3 CH2CH3 CH2 Cl 3.107 CH CH CH3 CH3 -CH2CH2- CH2 Cl 3.108 CH CH CH3 CH3 CH3 CH3 O Cl Preparation Example P3 3.109 CH CH CH3 CH3 CH2CH3 CH2CH3 O Cl 3.110 CH CH CH3 CH3 -CH2CH2- O Cl 3.111 CH CH CH3 CH3 CH3 CH3 NSO2CH3 Cl 3.112 CH CH CH3 CH3 CH2CH3 CH2CH3 NSO2CH3 Cl 3.113 CH CH CH3 CH3 -CH2CH2- NSO2CH3 Cl 3.114 CH CH CH3 CH3 CH3 CH3 NC(O)C(CHs)3 Cl 3.115 CH CH CH3 CH3 CH2CH3 CH2CH3 NC(O)C(CHs)3 Cl 3.116 CH CH CH3 CH3 -CH2CH2- NC(O)C(CH3)S Cl No. A1 A2 Ri R2 F >3a H3a Y Xa Physical data, remarks 3.117 CH CH CH3 CH3 CH3 CH3 CH2CH2 Cl 3.118 CH CH CH3 CH3 CH2CH3 CH2CH3 CH2CH2 Cl 3.119 CH CH CH3 CH3 -CH2CH2- CH2CH2 Cl 3.120 CH CH CH3 CH3 CH3 CH3 CH2 Br - 3.121 CH CH CH3 CH3 CH2CH3 CH2CH3 CH2 Br 3.122 CH CH CH3 CH3 -CH2CH2- CH2 Br 3.123 CH CH CH3 CH3 CH3 CH3 O Br 3.124 CH CH CH3 CH3 ( DH2CH3 CH2CH3 O Br 3.125 CH CH CH3 CH3 -CH2CH2- O Br 3.126 CH CH CH3 CH3 CH3 CH3 NSO2CH3 Br 3.127 CH CH CH3 CH3 CH2CH3 CH2CH3 NSO2CH3 Br 3.128 CH CH CH3 CH3 -CH2CH2- NSO2CH3 Br 3.129 CH CH CH3 CH3 CH3 CH3 NC(O)C(CHs)3 Br 3.130 CH CH CH3 CH3 CH2CH3 CH2CH3 NC(O)C(CHs)3 Br 3.131 CH CH CH3 CH3 -CH2CH2- NC(O)C(CHs)3 Br 3.132 CH CH CH3 CH3 CH3 CH3 CH2CH2 Br 3.133 CH CH CH3 CH3 CH2CH3 CH2CH3 CH2CH2 Br 3.134 CH CH CH3 CH3 -CH2CH2- CH2CH2 Br 3.135 CH CH H H -CH2CH2- Cl amorphous crystals

3.136 CH CH H H -CH2CH2- <l H 3.137 CH CH H H -CH2CH2- CH(Si(CHs)2- Cl resin phenyl) 3.138 CH CH CH3 H -CH2CH2- O Br resin

3.139 CH CH CH3 H -CH2CH2- O H resin

Table 4: Intermediates of formula V and V1, wherein Xb, Xc and Za are as defined for Xa:

No. Ai A2 Ri R2 Y Xa Physical data 4.001 CH CH H H C(=CH(OAc)) Cl Isomer 1 : 1H-NMR (300 MHz; CDCI3) δ 7.12 (s, 1 H); 6.77 (dxd, 1H); 6.35 (dxd, 1 H); 4.02 (d, 1 H); 3.95 (d, 1 H); 2.18 (s, 3H). No. Ai A2 Ri R2 Y Xa Physical data 4.002 CH CH H H C(^CH(OAc)) Gl Isomer II: 1H-NMR (300 MHz; CDCI3) δ 7.14 (s, 1H); 6.84 (dxd, 1 H); 6.29 (dxd, 1H); 4.55 (d, 1 H); 3.54 (d, 1 H); 2.19 (s, 3H). 4.003 CH CH H H CH(Si(CH3)3) Cl resin 4.004 CH CH H H CH(Si(CH3)2phet Cl resin 4.005 CH CH H H CH2CH2 Cl m.p.: 108.5-11O0C; Preparation Example PA2 4.006 CH CH CH CH3 CH2 Cl resin, tautomer V (identical with 4.007, tautomer V1) 4.007 CH CH CH3 H CH2 Cl resin, tautomer V (identical with 4.006, tautomer V1) 4.008 CH C(CH3) H H CH2 Cl resin, tautomer V (identical with 4.009, tautomer V1) 4.009 C(CH3) CH H H CH2 Cl resin, tautomer V (identical with 4.008, tautomer V1) 4.010 CH CH H H CH2 Cl Preparation Example PA1 4.011 CH CH H H C(=C(CH3)2) Cl resin

Biological Examples

Example B1 : Herbicidal action prior to emergence of the plants (pre-emerqence action) Monocotyledonous and dicotyledonous test plants are sown in standard soil in seed trays. Immediately after sowing, 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. After a test duration of 4 weeks, the test is evaluated in accordance with a scale of ten ratings (10 = total damage, 0 = no action, nt = not tested). Ratings of from 10 to 6 (especially from 10 to 8) indicate good to very good herbicidal action. The compounds of formula I generally exhibit strong herbicidal action in this test.

Table B1 :

Ex. No. g/ha Panicum Echinochloa Amaranthus Chenopodiυm Sinapis Stellaria 1.002 250 9 9 9 nt 9 9 1.013 250 10 7 7 7 7 6 1.057 250 10 10 9 10 10 10 Ex. No. g/ha Panicum Echinochloa Amaranϊhus Chenopodium Sinapis Stellaria 1.073 250 10 9 9 __£__ 8 10

Example B2: Herbicidal action after emergence of the plants (post-emergence herbicidal action) Monocotyledonous and dicotyledonous test plants are sown in standard soil in seed trays. At the 2- to 3-leaf stage, 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 emulsif iable 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. After a test duration of 2 to 3 weeks, the test is evaluated in accordance with a scale of ten ratings (10 = total damage, 0 = no action). Ratings of from 10 to 6 (especially from 10 to 7) indicate good to very good herbicidal action. The compounds of formula I generally exhibit a strong herbicidal action in this test.

Table B2:

Ex. No. g/ha Echinochloa Xanthium lpomea Chenopodium Kochia Sinapis Stellaria 1.002 250 7 8 9 10 9 9 9 1.013 250 7 7 7 8 9 7 8 1.020 250 8 8 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 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

Example B3: Comparison test with respect to the prior art (post-emergence herbicidal action) Monocotyledonous and dicotyledonous test plants are sown in standard soil in seed trays. At the 2- to 3-leaf stage, 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 15 g/ha. The test plants are then grown on in a greenhouse under optimum conditions. After a test duration of 2 to 3 weeks, the test is evaluated in accordance with a scale of ten ratings (10 = total damage, 0 = no action). Ratings of from 10 to 6 (especially from 10 to 7) indicate good to very good herbicidal action.

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.

In a biological comparison, compounds of formula I exhibit action superior to that of the prior art against specific weeds and grasses. In the following Example, compound 1.002 from Table 1 of this patent application is compared with a compound from the prior art having a corresponding structure, which compound is disclosed in column 12, Table A, Example 8 of US 5,801 ,120; the rate of application in these tests is 15 g/ha.

Compound from the prior art (US 5,801 ,120):

Compound according to the present invention (Table 1 , Example: 1.002):

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).

Table B3:

Ex. No. g/ha Panicum Digitaria Amaranthus Kochia Sinapis Stellaria 1.002 15 7 7 8 9 8 8 A 15 5 2 6 4 6 5