Patent EA-002923-B1 (EA)
Title: Substituted 2-(3-alkenyl-benzoyl)-cyclohexane-1,3-diones
Inventor: BUMANN ERNST
IPC: C07C45/54
Filed: 1998-04-24
Abstract: 1. A 2-(3-alkenylbenzoyl)cyclohexane-1,3-dione of the formula I   an agriculturally useful salts thereof wherein the substitutes have the following meanings in the formula I: R<1>, R<2> are hydrogen, nitro, halogen, cyano, thiocyanato, C1-C6 -alkyl, C1-C6 -haloalkyl, C1-C6 -alkoxy-C1-C6 -alkyl, C2-C6 -alkenyl, C2-C6 -alkynyl, -OR<6>, -OCOR<7>, -OSO2 R<7>, -SH, -S(O)n R<8>, -SO2OR<6>, -SO2NR<6> R<9>, -NR<9>SO2 R<7> or -NR<9>COR<7>; R<3> is hydrogen, halogen, C1-C6 -alkyl, C1-C6 -haloalkyl, C1-C6 -alkoxy, C2-C6 -alkenyl, C2-C6 -alkynyl; R<4>, R<5> are hydrogen, nitro, halogen, cyano, thiocyanato, C1-C6 -alkyl, C1-C6 -haloalkyl, C3-C6 -cycloalkyl, C2-C6 -alkenyl, C4-C6 -cycloalkenyl, C2-C6 -alkynyl, C1 -C6-alkoxy, C1-C6 -alkylthio, C1-C6 -haloalkoxy, -COR<10>, -CO2 R<10>, -COSR<10>, -CONR<10> R<11>, -C(R<12>)=NR<13>, -PO(OR<10>)(OR<11>), C1-C4 -alkyl which has attached to it a radical from the following group: hydroxyl, -COR<10>, -CO2 R<10>, -COSR<10>, -CONR<10>R<11> or -C(R<12>)=NR<13>; heterocyclyl, heterocyclyl-C1-C4 -alkyl, phenyl, phenyl-C1-C4 -alkyl, hetaryl, hetaryl-C1-C4 -alkyl, it being possible for the six last-mentioned radicals can be substituted or R4 and R<5> together form a C2-C6 -alkanediyl chain which can be optionally mono- to tetrasubstituted by C1-C4 -alkyl and/or can be optionally interrupted by oxygen or sulfur or by a nitrogen which is unsubstituted or substituted by C1-C4 -alkyl; n is 0, 1 or 2; R<6> is hydrogen, C1-C6 -alkyl, C1-C6 -haloalkyl, C1-C6 -alkoxy-C2-C6 -alkyl, C3-C6 -alkenyl or C3-C6 -alkynyl; R<7> is C1-C6 -alkyl or C1-C6 -haloalkyl; R<8> is C1-C6 -alkyl, C1-C6 -haloalkyl, C1-C6 -alkoxy-C2-C6 -alkyl, C3-C6 -alkenyl or C3-C6 -alkynyl; R<9> is hydrogen or C1-C6 -alkyl; R<10> is hydrogen, C1-C6 -alkyl, C3-C6 -cycloalkyl, C1-C6 -haloalkyl, C3-C6 -alkenyl, C3-C6 -alkynyl, phenyl or benzyl, it being possible for the two last-mentioned radicals to be partially or fully halogenated and/or to have attached to them one to three radicals from amongst the following group: nitro, cyano, C1-C4 -alkyl, C1-C4 -haloalkyl, C1-C4 -alkoxy, C1-C4 -haloalkoxy, C1-C4 -alkylcarbonyl or C1-C4 -alkoxycarbonyl; R<11> is hydrogen, C1-C6 -alkyl, C3-C6 -alkenyl or C3-C6 -alkynyl; or R<10> and R<11> together form a C2-C6 -alkanediyl chain which optionally can be mono- to tetrasubstituted by C1-C4 -alkyl and/or optionally can be interrupted by oxygen or sulfur or by a nitrogen which is unsubstituted or substituted by C1-C4 -alkyl; R<12> is hydrogen, C1-C6 -alkyl, C1-C6 -haloalkyl, C1-C6 -alkoxy, C1-C6 -alkoxycarbonyl, C3-C6 -cycloalkyl, C2-C6 -alkenyl, C2-C6 -alkynyl, phenyl or benzyl, it being possible for the two last-mentioned radicals optionally to be partially or fully halogenated and/or to have attached to them one to three radicals from amongst the following group: nitro, cyano, C1-C4 -alkyl, C1-C4 -haloalkyl, C1-C4 -alkoxy, C1-C4 -haloalkoxy, C1-C4 -alkylcarbonyl or C1-C4 -alkoxycarbonyl; R<13> is C1C6 -alkyl, C1-C6 -haloalkyl, C3-C6 -cycloalkyl, C3-C6 -alkenyl, C3-C6 -alkynyl, C1-C6 -alkoxy, C1-C6 -haloalkoxy, C3-C6 -cycloalkyloxy, C3-C6 -alkenyloxy, C3-C6 -alkynyloxy, phenyl, benzyl or phenyl-C1-C4 -alkoxy, it being possible for the three last-mentioned radicals optionally to be partially or fully halogenated and/or to have attached to them one to three radicals from amongst the following group: nitro, cyano, C1-C4 -alkyl, C1-C4 -haloalkyl, C1-C4 -alkoxy, C1-C4 -haloalkoxy, C1-C4 -alkylcarbonyl or C1-C4 -alkoxycarbonyl; Q is an unsubstituted or substituted cyclohexane-1,3-dione ring which is linked in the 2-position; 2. A 2-(3-alkenylbenzoyl)cyclohexane-1,3-dione of the formula I as claimed in Claim 1 where Q is is linked in the 2-position cyclohexane-1,3-dione ring of the formula II   wherein R<14>, R<15>, R<17> and R<19> are hydrogen or C1-C4 -alkyl; R<16> is hydrogen, C1-C4 -alkyl, C1-C4 -haloalkyl or C3-C4 -cycloalkyl, it being possible for the three last-mentioned groups to have attached to them one to three of the following substituents: C1-C4 -alkylthio or C1-C4 -alkoxy; or is tetrahydropyran-2-yl, tetrahydropyran-3-yl, tetrahydropyran-4-yl, tetrahydrothiopyran-2-yl, tetrahydrothiopyran-3-yl, tetrahydrothiopyran-4-yl, 1,3-dioxolan-2-yl, 1,3-dioxan-2-yl, 1,3-oxathiolan-2-yl, 1,3-oxathian-2-yl, 1,3-dithiolan-2-yl or 1,3-dithian-2-yl, it being possible for the 6 last-mentioned radicals to 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 π bond or a three- to six-membered carbocyclic ring; or the CR<16>R<17> unit may be replaced by C=O. 3. A 2-(3-alkenylbenzoyl)cyclohexane-1,3-dione of the formula I as claimed in Claim 1 or 2, where R<4>, R<5> are hydrogen, nitro, halogen, cyano, thiocyanato, C1-C6 -alkyl, C1-C6 -haloalkyl, C3-C6 -cycloalkyl, C2-C6 -alkenyl, C4-C6 -cycloalkenyl, C2-C6 -alkynyl, C1-C6 -alkoxy, C1-C6 -alkylthio, C1-C6 -haloalkoxy, -COR<10>, -CO2R<10>, -COSR<10>, -CONR<10>R<11>, -C(R<12>)=NR<13>, -PO(OR<10>)(OR<11>), C1-C4 -alkyl which has attached to it a radical from amongst the following group: -COR<10>, -CO2 R<10>, -COSR<10>, -CONR<10>R<11> or -C(R<12>)=NR<13> ; heterocyclyl, heterocyclyl-C1-C4 -alkyl, phenyl, phenyl-C1-C4 -alkyl, hetaryl, hetaryl-C1-C4 -alkyl, it being possible for the six last-mentioned radicals to be substituted;  or R<4> and R<5> together form a C2-C6 -alkanediyl chain which optionally can be mono- to tetrasubstituted by C1-C4 -alkyl and/or interrupted by oxygen or sulfur or by a nitrogen which is unsubstituted or substituted by C1-C4 -alkyl; and R<13> is C1-C6 -alkyl, C1-C6 -haloalkyl, C3-C6 -cycloalkyl, C3-C6 -alkenyl, C3-C6 -alkynyl, C1-C6 -alkoxy, C1-C6 -haloalkoxy, C3-C6 -cycloalkoxy, C3-C6 -alkenyloxy, C3-C6 -alkynyloxy, phenyl, benzyl or benzyloxy, the three last-mentioned radicals optionally to be partially or fully halogenated and/or to have attached to them one to three radicals from amongst the following group: nitro, cyano, C1-C4 -alkyl, C1-C4 -haloalkyl, C1-C4 -alkoxy, C1-C4 -haloalkoxy, C1-C4 -alkylcarbonyl or C1-C4 -alkoxycarbonyl. 4. A 2-(3-alkenylbenzoyl)cyclohexane-1,3-dione of the formula I as claimed in Claims 1 to 3, where R<1> is nitro, halogen, cyano, thiocyanato, C1-C6 -alkyl, C1-C6 -haloalkyl, C1-C6 -alkoxy-C1-C6 -alkyl, C2-C6 -alkenyl, C2-C6 -alkynyl, -OR<6> or -S(O)nR<8> ; R<2> is hydrogen or a radical as mentioned above under R<1>. 5. A 2-(3-alkenylbenzoyl)cyclohexane-1,3-dione of the formula I as claimed in Claims 1 3, where R<4> is hydrogen, nitro, halogen, cyano, thiocyanato, C1-C6 -alkyl, C1-C6 -haloalkyl, C3-C6 -cycloalkyl, C2-C6 -alkenyl, C4-C6 -cycloalkenyl, C2-C6 -alkynyl, C1-C6 -alkoxy, C1-C6 -alkylthio, C1-C6 -haloalkoxy, -COR<10>, -CO2R<10>, -COSR<10>, -CONR<10>R<11>, -C(R<12>)=NR<13>, -PO(OR<10>)(OR<11>), C1-C4 -alkyl which has attached to it a radical from amongst the following group: -COR<10>, -CO2R<10>, -COSR<10>, -CONR<10>R<11> or -C(R<12>)=NR<13> ; heterocyclyl, heterocyclyl-C1-C4 -alkyl, phenyl, phenyl-C1-C4 -alkyl, hetaryl, hetaryl-C1-C4 -alkyl, it being possible for the six last-mentioned radicals to be substituted; R<5> is hydrogen, halogen, cyano, thiocyanato, C1-C6 -alkyl, C1-C6 -haloalkyl, -COR<10>, -CO2 R<10>, -COSR<10>, -CONR<10>R<11> or -PO(OR<10>)(OR<11>); or R<4> and R<5> together are a C2-C6 -alkanediyl chain which can be mono- to tetrasubstituted by C1-C4 -alkyl and/or can be interrupted by oxygen or sulfur or by a nitrogen which is unsubstituted or substituted by C1-C4 -alkyl. 6. A 2-(3-alkenylbenzoyl)cyclohexane-1,3-dione of the formula Ia   where the substituents R<1> to R<5> and Q have the meanings mentioned in Claims 1 to 5. 7. A process for the preparation of a 2-(3-alkenylbenzoyl)cyclohexane-1,3-dione of the formula I as claimed in any of Claims 1 to 6, which comprises acylating an unsubstituted or substituted cyclohexane-1,3-dione Q with an activated carboxylic acid IIIα or with a carboxylic acid IIIβ,    where the substituents R<1> to R<5> have the meanings mentioned in Claim 1 and L is a nucleophilically displaceable leaving group, and, if desired, subjecting the acylation product to a rearrangement reaction in the presence of a catalyst to give the compounds I. 8. A composition comprising a herbicidally active amount of at least one compound of the formula I or of an agriculturally useful salt of I as claimed in Claims 1 to 6 and auxiliaries conventionally used for the formulation of crop protection products. 9. A process for the preparation of a herbicidally active composition as claimed in Claim 8, which comprises mixing a herbicidally active amount of at least one compound of the formula I or of an agriculturally useful salt of I as claimed in Claims 1 to 6 and auxiliaries conventionally used for the formulation of crop protection products. 10. A method of controlling undesired vegetation, which comprises allowing a herbicidally active amount of at least one compound of the formula I or of an agriculturally useful salt of I as claimed in Claims 1 to 6 to act on plants, their environment and/or on seeds. 11. The use of the compounds of the formula I and agriculturally useful salts thereof I as claimed in Claims 1 to 6 as herbicides.