Patent EA-002418-B1 (EA)
Title: Hetaroyl cyclohexanedione derivatives with herbicidal effect
Inventor: OTTEN MARTINA
IPC: C07D215/22
Filed: 1997-09-09
Abstract: 1. Hetaroyl derivatives of the formula I   where: R<1> and R<2> are each hydrogen, nitro, halogen, cyano, rhodano, hydroxyl, mercapto, C1-C6-alkyl, C1-C6-haloalkyl, C2-C6-alkenyl, C2-C6-alkynyl, C1-C6-alkoxy, C1-C6-haloalkoxy, C2-C6-alkenyloxy, C2-C6-alkynyloxy, C1-C6-alkylthio, C1-C6-haloalkylthio, C2-C6-alkenylthio, C2-C6-alkynylthio, C1-C6-alkylsulfinyl, C1-C6-haloalkylsulfinyl, C2-C6-alkenylsulfinyl, C2-C6-alkynylsulfinyl, C1-C6-alkylsulfonyl, C1-C6-haloalkylsulfonyl, C2-C6-alkenylsulfonyl, C2-C6-alkynylsulfonyl, C1-C6-alkoxysulfonyl, C1-C6-haloalkoxysulfonyl, C2-C6-alkenyloxysulfonyl, C2-C6-alkynyloxysulfonyl, phenyl, phenyloxy, phenylthio, phenylsulfinyl or phenylsulfonyl, where the last five substituents may be partially or fully halogenated and may carry one to three of the following groups: nitro, cyano, hydroxyl, C1-C4-alkyl, C1-C4-haloalkyl C1-C4-alkoxy, C1-C4-haloalkoxy; Z is a building block from the group consisting of Z<1> to Z<12>   where R<3>, R<5>, R<7> and R<9> are nitro, cyano, hydroxyl, mercapto, C2-C4-alkenyl, C2-C4-alkynyl, C2-C4-alkenyloxy, C2-C4-alkynyloxy, C2-C4-alkenylthio, C2-C4-alkynylthio, C1-C4-alkylsulfonyl, C1-C4-halogenalkylsulfinyl, C2-C4-alkenylsulfinyl, C2-C4-alkynylsulfinyl, C1-C4-alkylsulfonyl, C1-C4-halogenalkylsulfonyl, C2-C4-alkenylsulfonyl, C2-C4-alkynylsulfonyl, C1-C4-alkoxysulfonyl, C1-C4-halogenalkoxysulfonyl, C2-C4-alkenyloxysulfonyl, C2-C4-alkynyloxysulfonyl, -NR<12>R<13>, -CO2R<12>, -CONR<12>R<13>, phenyl, phenoxy, phenylthio, phenylsulfinyl or phenylsulfonyl, where the last five substituents may be partially or fully halogenated and may carry one to three of the following groups: nitro, cyano, hydroxyl, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy; or the radicals mentioned under R<4>; R<4>, R<6>, R<8> and R<10> are each hydrogen, halogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkylthio or C1-C4-haloalkylthio; or a -CR<3>R4 -CR<5> R<6>-, CR<7>R<8>- or CR<9>R<10>- unit may be replaced by C=O or C=NR<13>; R<11> is hydrogen, C1-C6-alkyl, C1-C6-haloalkyl, C3-C6-alkenyl, C3-C6-alkynyl, C1-C6-alkylcarbonyl, C1-C6-haloalkylcarbonyl, -CO2R<12>, -CONR<12>R<13> or SO2R<12>; R<12> is hydrogen, C1-C6-alkyl, C1-C6-haloalkyl, C3-C6-alkenyl, C3-C6-alkynyl or phenyl, where the last radical may be partially or fully halogenated and may carry one to three of the following radicals: nitro, cyano, hydroxyl, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy; R<13> is C1-C6-alkoxy, C1-C6-haloalkoxy, C3-C6-alkenyloxy, C3-C6-alkynyloxy or one of the radicals mentioned under R<12>; Q is a cyclohexane-1,3-dione ring, linked through position 2, of the formula II   where R<14>, R<15>, R<17> and R<19> are each hydrogen or C1-C4-alkyl; where R<16> is hydrogen, C1-C4-alkyl or C3-C4-cycloalkyl, where the last two groups may carry one to three of the following substituents: halogen, C1-C4-alkylthio or C1-C4-alkoxy; or is tetrahydropyran-3-yl, tetrahydropyran-4-yl, tetrahydrothiopyran-3-yl, l,3-dioxolan-2-yl, l,3-dioxan-2-yl, l,3-oxathiolan-2-yl, l,3-oxathian-2-yl, l,3-dithiolan-2-yl or l,3-dithian-2-yl, where the last 6 radicals may be substituted by one to three C1-C4-alkyl radicals; R<18> is hydrogen, C1-C4-alkyl or C1-C6-alkoxycarbonyl; or R<16> and R<19> together form a bond or a three- to six-membered carbocyclic ring; or the -CR<16>R<17>- unit may be replaced by C=O, and applicable in agriculture salts thereof. 2. Hetaroyl derivatives of the formula I as claimed in claim 1 or 2, where CR<9>R<10> is not C=O or C=NR<13> if Z is Z<9> and the "QCO-fragment" is para to the nitrogen of the building block Z. 3. Hetaroyl derivatives of the formula I as claimed in any of claims 1 to 2, where: R<1> and R<2> are each hydrogen, nitro, halogen, cyano, rhodano, hydroxyl, mercapto, C1-C6-alkyl, C1-C6-haloalkyl, C2-C6-alkenyl, C2-C6-alkynyl, C1-C6-alkoxy, C1-C6-haloalkoxy, C2-C6-alkenyloxy, C2-C6-alkynyloxy, C1-C6-alkylthio, C1-C6-haloalkylthio, C2-C6-alkenylthio, C2-C6-alkynylthio, C1-C6-alkylsulfinyl, C1-C6-haloalkylsulfinyl, C2-C6-alkenylsulfinyl, C2-C6-alkynylsulfinyl, C1-C6-alkylsulfonyl, C1-C6-haloalkylsulfonyl, C2-C6-alkenylsulfonyl, C2-C6-alkynylsulfonyl, C1-C6-alkoxysulfonyl, C1-C6-haloalkoxysulfonyl, C2-C6-alkenyloxysulfonyl, C2-C6-alkynyloxysulfonyl, phenyl, phenyloxy, phenylthio, phenylsulfinyl or phenylsulfonyl, where the last five substituents may be partially or fully halogenated and may carry one to three of the following groups: nitro, cyano, hydroxyl, C1-C4-alkyl, C1-C4-haloalkyl C1-C4-alkoxy, C1-C4-haloalkoxy; Z is a building block from the group consisting of Z<1> to Z<12>   where R<3>, R<5>, R<7> and R<9> are each hydrogen, halogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkylthio, C1-C4-haloalkylthio, nitro, cyano, hydroxyl, mercapto, C2-C4-alkenyl, C2-C4-alkynyl, C2-C4-alkenyloxy, C2-C4-alkynyloxy, C2-C4-alkenylthio, C2-C4-alkynylthio, C1-C4-alkylsulfonyl, C1-C4-halogenalkylsulfonyl, C2-C4-alkenylsulfonyl, C2-C4-alkynylsulfonyl, C1-C4-alkylsulfonyl, C1-C4-halogenalkylsulfonyl, C2-C4-alkenylsulfonyl, C2-C4-alkynylsulfonyl, C1-C4-alkoxysulfonyl, C1-C4-halogenalkoxysylfonyl, C2-C4-alkenylalkoxysulfonyl, C2-C4-alkynylalkoxysulfonyl, -NR<12>R<13>, -CO2R<12>, -CONR<12>R<13>, phenyl, phenoxy, phenylthio, phenylsulfinyl or phenylsulfonyl, where the last five substituents may be partially or fully halogenated and may carry one to three of the following groups: nitro, cyano, hydroxyl, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy; R<4>, R<6>, R8 and R<10> are each hydrogen; R<11> is hydrogen, C1-C6-alkyl, C1-C6-haloalkyl, C3-C6-alkenyl, C3-C6-alkynyl, C1-C6-alkylcarbonyl, C1-C6-haloalkylcarbonyl, -CO2R<L2>, -CONR<12>R<13> or SO2R<12>; R<12>  is hydrogen, C1-C6-alkyl, C1-C6-haloalkyl, C3-C6-alkenyl, C3-C6-alkynyl or phenyl, where the last radical may be partially or fully halogenated and may carry one to three of the following radicals: nitro, cyano, hydroxyl, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy; R<13> is C1-C6-alkoxy, C1-C6-haloalkoxy, C3-C6-alkenyloxy, C3-C6-alkynyloxy or one of the radicals mentioned under R<12>. 4. Hetaroyl derivatives of the formula I as claimed in any one of claims 1 to 3, where the variable Z is Z<1>, Z<2>, Z<11> or Z<12>. 5. Hetaroyl derivatives of the formula I as claimed in any one of claims 1 to 3, where the variable Z is Z<9> or Z<10>. 6. Hetaroyl derivatives of the formula I as claimed in any one of claims 1 to 5, wherein R<1> is nitro, halogen, cyano, rhodano, hydroxyl, mercapto, C1-C6-alkyl, C1-C6-haloalkyl, C2-C6-alkenyl, C2-C6-alkynyl, C1-C6-alkoxy, C1-C6-haloalkoxy, C2-C6-alkenyloxy, C2-C6-alkynyloxy, C1-C6-alkylthio, C1-C6-haloalkylthio, C2-C6-alkenylthio, C2-C6-alkynylthio, C1-C6-alkylsulfinyl, C1-C6-haloalkylsulfinyl, C2-C6-alkenylsulfinyl, C2-C6-alkynylsulfinyl, C1-C6-alkylsulfonyl, C1-C6-haloalkylsulfonyl, C2-C6-alkenylsulfonyl, C2-C6-alkynylsulfonyl, C1-C6-alkoxysulfonyl, C1-C6-haloalkoxysulfonyl, C2-C6-alkenyloxysulfonyl, C2-C6-alkynyloxysulfonyl, phenyl, phenyloxy, phenylthio, phenylsulfinyl or phenylsulfonyl, where the last five substituents may be partially or fully halogenated and may carry one to three of the following groups: nitro, cyano, hydroxyl, C1-C4-alkyl, C1-C4-haloalkyl C1-C4-alkoxy, C1-C4-haloalkoxy; and  R<2>  is hydrogen or one of the radicals mentioned under R<1>. 7. Hetaroyl derivatives of the formula Ia as claimed in any one of claims 1 to 4 and their N-oxides (formula Ia')   8. Hetaroyl derivatives of the formula Ib as claimed in any one of claims 1 to 4 and their N-oxides (formula Ib')   9. Hetaroyl derivatives of the formula Ic as claimed in any one of claims 1 to 4 and their N-oxides (formula Ic')   10. Hetaroyl derivatives of the formula Id as claimed in any one of claims 1 to 4 and their N-oxides (formula Id')   11. Hetaroyl derivatives of the formula le as claimed in any one of claims 1 to 4 and their N-oxides (formula Ie')   12. Hetaroyl derivatives of the formula If (where Z = Z<9>) or Ig (where Z = Z<10>) as claimed in any one of claims 1 to 3 or 5   13. A process for preparing compounds of the formula I as claimed in any one of claims 1 to 12, which comprises acylating the unsubstituted or substituted cyclohexane-1,3-dione with an activated carboxylic acid IIIa or with a carboxylic acid IIIb   where the variables R<1>, R<2> and Z are as defined in claim 1 and L is a nucleophilically replaceable leaving group and the acylation product is rearranged in the presence of a catalyst to give the compounds I. 14. A herbicidal composition comprising a herbicidally active amount of at least one hetaroyl derivative of the formula I or of an agriculturally useful salt of compound I as claimed in any one of claims 1 to 12 and at least one inert liquid and/or solid carrier and at least one surfactant. 15. Use of the hetaroyl derivatives of the formula I and their agriculturally useful salts as claimed in any one of claims 1 to 12 as herbicides.