The invention relates to 2-benzoylcyclohexane-1,3-diones of the formula I

The present invention relates to substituted 2-benzoyl-cyclohexane-1,3-diones of the formula I
where:
R1 and R2 are are each hydrogen, nitro, halogen, cyano, thiocyanato, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy-C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, xe2x80x94OR5, xe2x80x94OCOR6, xe2x80x94OSO2R6, xe2x80x94SH, xe2x80x94S(O)nR7, xe2x80x94SO2OR5, xe2x80x94SO2NR5R8, xe2x80x94NR8SO2R6 or xe2x80x94NR8COR6;
R3 is hydrogen, cyano, C1-C6-alkyl, C1-C6-haloalkyl, xe2x80x94OR7, xe2x80x94SR7 or xe2x80x94NR7R10;
R4 is hydrogen, C1-C6-alkyl, C3-C6-cycloalkyl, C3-C6-alkenyl, C4-C6-cycloalkenyl, C3-C6-alkynyl, xe2x80x94COR9, xe2x80x94CO2R9, xe2x80x94COSR9 or xe2x80x94CONR8R9, where the alkyl, cycloalkyl, alkenyl, cycloalkenyl and alkynyl radicals mentioned and R9 of the radicals xe2x80x94COR9, xe2x80x94CO2R9, xe2x80x94COSR9 and xe2x80x94CONR8R9 may be partially or fully halogenated and/or carry one to three of the following groups:
hydroxyl, mercapto, amino, cyano, R10, xe2x80x94OR10, xe2x80x94SR10, xe2x80x94NR8R10, xe2x95x90NOR10, xe2x80x94OCOR10, xe2x80x94SCOR10, xe2x80x94NR8COR10, xe2x80x94CO2R10, xe2x80x94COSR10, xe2x80x94CONR8R10, C1-C4-alkyliminooxy, C1-C4-alkoxyamino, C1-C4-alkylcarbonyl, C1-C4-alkoxy-C2-C6-alkoxycarbonyl, C1-C4-alkylsulfonyl, heterocyclyl, heterocyclyloxy, phenyl, benzyl, hetaryl, phenoxy, benzyloxy and hetaryloxy, where the last eight radicals mentioned may in turn be substituted;
X is oxygen or NR8:
n is 0, 1 or 2;
R5 is hydrogen, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy-C2-C6-alkyl, C3-C6-alkenyl or C3-C6-alkynyl;
R6 is C1-C6-alkyl or C1-C6-haloalkyl;
R7 is C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy-C2-C6-alkyl, C3-C6-alkenyl or C3-C6-alkynyl;
R8 is hydrogen or C1-C6-alkyl;
R9 is C1-C6-alkyl, C3-C6-alkenyl, C3-C6-alkynyl, phenyl or benzyl;
R10 is C1-C6-alkyl, C1-C6-haloalkyl, C3-C6-alkenyl or C3-C6-alkynyl;
Q is a cyclohexane-1,3-dione ring attached in position 2 with or without substitution;
and agriculturally useful salts thereof.
The invention additionally relates to processes and intermediates for preparing compounds of the formula I, to compositions comprising them, and to the use of the compounds of the formula I or of compositions comprising them for controlling harmful plants.
2-Benzoylcyclohexane-1,3-diones are known from the literature, for example from EP-A 278 742, EP-A 298 680, EP-A 320 864 and WO 96/14285.
However, the herbicidal properties of these prior art compounds and their compatibility with crop plants are not entirely satisfactory.
It is an object of the present invention to provide novel, in particular herbicidally active, compounds having improved properties.
We have found that this object is achieved by the 2-benzoyl-cyclohexane-1,3-diones of the formula I and their herbicidal action.
Furthermore, the invention provides herbicidal compositions comprising the compounds I and having a very good herbicidal activity. Additionally, the invention provides processes for preparing these compositions and methods for controlling undesirable vegetation using the compounds I.
The present invention also provides stereoisomers of the compounds of the formula I. Pure stereoisomers and also mixtures thereof are included.
The compounds of the formula I contain a carbon-nitrogen double bond and are therefore present as E isomers or Z isomers or as E/Z isomer mixtures. Furthermore, the compounds of the formula I may contain further carbon-carbon or carbon-nitrogen double bonds. The invention provides the pure geometric isomers and also mixtures thereof.
Depending on the substitution pattern, the compounds of the formula I may contain one or more chiral centers and, if this is the case, are present as mixtures of enantiomers or diastereomers. The invention provides the pure enantiomers or diastereomers and also mixtures thereof.
The compounds of the formula I may also be present in the form of their agriculturally useful salts, the kind of salt generally not being important. The salts of those cations or the acid additon salts of those acids whose cations or anions, respectively, do not adversely affect the herbicidal activity of the compounds I are generally suitable.
Suitable cations are in particular ions of the alkali metals, preferably lithium, sodium and potassium, of the alkaline earth metals, preferably calcium and magnesium, and of the transition metals, preferably manganese, copper, zinc and iron, and ammonium, where, if desired, one to four hydrogen atoms may be replaced by C1-C4-alkyl or hydroxyl-C1-C4-alkyl and/or one phenyl or benzyl, preferably diisopropylammonium, tetramethylammonium, tetrabutylammonium, trimethylbenzylammonium, furthermore phosphonium ions, sulfonium ions, preferably tri(C1-C4-alkyl)sulfonium and sulfoxonium ions, preferably tri(C1-C4-alkyl)sulfoxonium.
Anions of usable acid addition salts are primarily chloride, bromide, fluoride, hydrogen sulfate, sulfate, dihydrogen phosphate, hydrogen phosphate, nitrate, hydrogen carbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate and the anions of C1-C4-alkanoic acids, preferably formate, acetate, propionate and butyrate.
Emphasis is given to compounds of the formula I according to the invention where the variable Q is a cyclohexane-1,3-dione ring of the formula II linked in position 2
where II also represents the tautomeric formulae IIxe2x80x2 and IIxe2x80x3,
where
R11, R12, R14 and R16 are each hydrogen or C1-C4-alkyl;
R13 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-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, where the last 6 radicals mentioned may be substituted by one to three C1-C4-alkyl radicals;
R15 is hydrogen, C1-C4-alkyl or C1-C6-alkoxycarbonyl; or
R13 and R16 together form a xcfx80-bond or a three- to six-membered carbocylic ring; or
the CR13R14 unit is replaced by Cxe2x95x90O.
Emphasis is also given to compounds of the formula I according to the invention where
R4 is hydrogen, C1-C6-alkyl, C3-C6-cycloalkyl, C3-C6-alkenyl, C4-C6-cycloalkenyl, C3-C6-alkynyl, xe2x80x94COR9, xe2x80x94CO2R9, xe2x80x94COSR9 or xe2x80x94CONR8R9 where the alkyl, cycloalkyl, alkenyl-, cycloalkenyl and alkynyl radicals mentioned and R9 of the radicals xe2x80x94COR9, xe2x80x94CO2R9, xe2x80x94COSR9 and xe2x80x94CONR8R9 may be partially or fully halogenated and/or carry one to three of the following groups:
hydroxyl, mercapto, amino, cyano, R10, xe2x80x94OR10, xe2x80x94SR10, xe2x80x94NR8R10, xe2x95x90NOR10, xe2x80x94OCOR10, xe2x80x94SCOR10, xe2x80x94NR8COR10, xe2x80x94CO2R10, xe2x80x94COSR10, xe2x80x94CONR8R10, C1-C4-alkyliminooxy, C1-C4-alkoxyamino, C1-C4-alkylcarbonyl, C1-C4-alkoxy-C2-C6-alkoxycarbonyl, C1-C4-alkylsulfonyl, heterocyclyl, heterocyclyloxy, phenyl, benzyl, hetaryl, phenoxy, benzyloxy and hetaryloxy, where the last eight radicals mentioned may in turn be partially or fully halogenated and/or carry one to three radicals from the following group:
nitro, cyano, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkoxycarbonyl.
The organic moieties mentioned for the substituents R1-R16 or as radicals on phenyl, hetaryl and heterocylyl rings represent collective terms for lists of the individual group members. All hydrocarbon chains, ie. all alkyl, haloalkyl, cycloalkyl, alkoxyalkyl, alkoxy, haloalkoxy, alkyliminooxy, alkoxyamino, alkylthio, alkylsulfonyl, alkylcarbonyl, alkoxycarbonyl, alkoxyalkoxycarbonyl, alkenyl, cycloalkenyl and alkynyl moieties, may be straight-chain or branched. Unless stated otherwise, preference is given to halogenated substituents carrying one to five identical or different halogens. Halogen is in each case fluorine, chlorine, bromine or iodine.
Furthermore, the following moities represent, for example:
C2-C4-alkyl: ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl and 1,1-dimethylethyl;
C1-C4-alkyl and the alkyl moieties of C1-C4-alkylcarbonyl: C2-C4-alkyl as mentioned above, and methyl;
C2-C6-alkyl, and the alkyl moieties of C1-C6-alkoxy-C2-C6-alkyl: C2-C4-alkyl as mentioned above, and pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1-ethyl-1-methylpropyl and 1-ethyl-3-methylpropyl;
C1-C6-alkyl and the alkyl moieties of C1-C6-alkoxy-C1-C6-alkyl: C2-C6-alkyl as mentioned above, and methyl;
C1-C4-haloalkyl: a C1-C4-alkyl radical as mentioned above which is partially or fully substituted by fluorine, chlorine, bromine and/or iodine, ie. for example chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 2-fluoroethyl, 2-chloroethyl, 2-bromoethyl, 2-iodoethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, pentafluoroethyl, 2-fluoropropyl, 3-fluoropropyl, 2,2-difluoropropyl, 2,3-difluoropropyl, 2-chloropropyl, 3-chloropropyl, 2,3-dichloropropyl, 2-bromopropyl, 3-bromopropyl, 3,3,3-trifluoropropyl, 3,3,3-trichloropropyl, 2,2,3,3,3-pentafluoropropyl, heptafluoropropyl, 1-(fluoromethyl)-2-fluoroethyl 1-(chloromethyl)-2-chloroethyl, 1-(bromomethyl)-2-bromoethyl, 4-fluorobutyl, 4-chlorobutyl, 4-bromobutyl and nonafluorobutyl;
C1-C6-haloalkyl: C1-C4-haloalkyl as mentioned above, and 5-fluoropentyl, 5-chloropentyl, 5-bromopentyl, 5-iodopentyl, undecafluoropentyl, 6-fluorohexyl, 6-chlorohexyl, 6-bromohexyl, 6-iodohexyl and dodecafluorohexyl;
C1-C4-alkoxy and the alkoxy moieties of C1-C4-alkoxyamino, C1-C4-alkoxy-C2-C6-alkoxycarbonyl and C1-C4-alkoxycarbonyl: methoxy, ethoxy, propoxy, 1-methylethoxy, butoxy, 1-methylpropoxy, 2-methylpropoxy and 1,1-dimethylethoxy;
C1-C6-alkoxy and the alkoxy moieties of C1-C6-alkoxy-C1-C6-alkyl, C1-C4-alkoxy-C2-C6-alkoxycarbonyl and C1-C6-alkoxycarbonyl: C1-C4-alkoxy as mentioned above, and pentoxy, 1-methylbutoxy, 2-methylbutoxy, 3-methylbutoxy, 1,1-dimethylpropoxy, 1,2-dimethylpropoxy, 2,2-dimethylpropoxy, 1-ethylpropoxy, hexoxy, 1-methylpentoxy, 2-methylpentoxy, 3-methylpentoxy, 4-methylpentoxy, 1,1-dimethylbutoxy, 1,2-dimethylbutoxy, 1,3-dimethylbutoxy, 2,2-dimethylbutoxy, 2,3-dimethylbutoxy, 3,3-dimethylbutoxy, 1-ethylbutoxy, 2-ethylbutoxy, 1,1,2-trimethylpropoxy, 1,2,2-trimethylpropoxy, 1-ethyl-1-methylpropoxy and 1-ethyl-2-methylpropoxy;
C1-C4-haloalkoxy: a C1-C4-alkoxy radical as mentioned above which is partially or fully subsstituted by fluorine, chlorine, bromine and/or iodine, ie. for example fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorodifluoromethoxy, bromodifluoromethoxy, 2-fluoroethoxy, 2-chloroethoxy, 2-bromoethoxy, 2-iodoethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, 2-chlor-2-fluoroethoxy, 2-chloro-2,2-difluoroethoxy, 2,2-dichloro-2-fluoroethoxy, 2,2,2-trichloroethoxy, pentafluoroethoxy, 2-fluoropropoxy, 3-fluoropropoxy, 2-chloropropoxy, 3-chloropropoxy, 2-bromopropoxy, 3-bromopropoxy, 2,2-difluoropropoxy, 2,3-difluoropropoxy, 2,3-dichloropropoxy, 3,3,3-trifluoropropoxy, 3,3,3-trichloropropoxy, 2,2,3,3,3-pentafluoropropoxy, heptafluoropropoxy, 1-(fluoromethyl)-2-fluoroethoxy, 1-(chloromethyl)-2-chloroethoxy, 1-(bromomethyl)-2-bromoethoxy, 4-fluorobutoxy, 4-chlorobutoxy, 4-bromobutoxy and nonafluorobutoxy;
C1-C4-alkylthio: methylthio, ethylthio, propylthio, 1-methylethylthio, butylthio, 1-methylpropylthio, 2-methylpropylthio and 1,1-dimethylethylthio;
C1-C4-alkylsulfonyl (C1-C4-alkyl-S(xe2x95x90O)2xe2x80x94): methylsulfonyl, ethylsulfonyl, propylsulfonyl, 1-methylethylsulfonyl, butylsulfonyl, 1-methylpropylsulfonyl, 2-methylpropylsulfonyl and 1,1-dimethylethylsulfonyl;
C1-C4-alkyliminooxy: methyliminooxy, ethyliminooxy, 1-propyliminooxy, 2-propyliminooxy, 1-butyliminooxy and 2-butyliminooxy;
C3-C6-alkenyl: prop-1-en-1-yl, prop-2-en-1-yl, 1-methylethenyl, buten-1-yl, buten-2-yl, buten-3-yl, 1-methylprop-1-en-1-yl, 2-methylprop-1-en-1-yl, 1-methylprop-2-en-1-yl, 2-methylprop-2-en-1-yl, penten-1-yl, penten-2-yl, penten-3-yl, penten-4-yl, 1-methylbut-1-en-1-yl, 2-methylbut-1-en-1-yl, 3-methylbut-1-en-1-yl, 1-methylbut-2-en-1-yl, 2-methylbut-2-en-1-yl, 3-methylbut-2-en-1-yl, 1-methylbut-3-en-1-yl, 2-methylbut-3-en-1-yl, 3-methylbut-3-en-1-yl, 1,1-dimethylprop-2-en-1-yl, 1,2-dimethylprop-1-en-1-yl, 1,2-dimethylprop-2-en-1-yl, 1-ethylprop-1-en-2-yl, 1-ethylprop-2-en-1-yl, hex-1-en-1-yl, hex-2-en-1-yl, hex-3-en-1-yl, hex-4-en-1-yl, hex-5-en-1-yl, 1-methylpent-1-en-1-yl, 2-methylpent-1-en-1-yl, 3-methylpent-1-en-1-yl, 4-methylpent-1-en-1-yl, 1-methylpent-2-en-1-yl, 2-methylpent-2-en-1-yl, 3-methylpent-2-en-1-yl, 4-methylpent-2-en-1-yl, 1-methylpent-3-en-1-yl, 2-methylpent-3-en-1-yl, 3-methylpent-3-en-1-yl, 4-methylpent-3-en-1-yl, 1-methylpent-4-en-1-yl, 2-methylpent-4-en-1-yl, 3-methylpent-4-en-1-yl, 4-methylpent-4-en-1-yl, 1,1-dimethylbut-2-en-1-yl, 1,1-dimethylbut-3-en-1-yl, 1,2-dimethylbut-1-en-1-yl, 1,2-dimethylbut-2-en-1-yl, 1,2-dimethylbut-3-en-1-yl, 1,3-dimethylbut-1-en-1-yl, 1,3-dimethylbut-2-en-1-yl, 1,3-dimethylbut-3-en-1-yl, 2,2-dimethylbut-3-en-1-yl, 2,3-dimethylbut-1-en-1-yl, 2,3-dimethylbut-2-en-1-yl, 2,3-dimethylbut-3-en-1-yl, 3,3-dimethylbut-1-en-1-yl, 3,3-dimethylbut-2-en-1-yl, 1-ethylbut-1-en-1-yl, 1-ethylbut-2-en-1-yl, 1-ethylbut-3-en-1-yl, 2-ethylbut-1-en-1-yl, 2-ethylbut-2-en-1-yl, 2-ethylbut-3-en-1-yl, 1,1,2-trimethylprop-2-en-1-yl, 1-ethyl-1-methylprop-2-en-1-yl, 1-ethyl-2-methylprop-1-en-1-yl and 1-ethyl-2-methylprop-2-en-1-yl;
C2-C6-alkenyl: C3-C6-alkenyl as mentioned above, and ethenyl;
C3-C6-alkynyl: prop-1-yn-1-yl, prop-2-yn-1-yl, but-1-yn-1-yl, but-1-yn-3-yl, but-1-yn-4-yl but-2-yn-1-yl, pent-1-yn-1-yl, pent-1-yn-3-yl, pent-1-yn-4-yl, pent-1-yn-5-yl, pent-2-yn-1-yl, pent-2-yn-4-yl, pent-2-yn-5-yl, 3-methylbut-1-yn-3-yl, 3-methylbut-1-yn-4-yl, hex-1-yn-1-yl, hex-1-yn-3-yl, hex-1-yn-4-yl, hex-1-yn-5-yl, hex-1-yn-6-yl, hex-2-yn-1-yl, hex-2-yn-4-yl, hex-2-yn-5-yl, hex-2-yn-6-yl, hex-3-yn-1-yl, hex-3-yn-2-yl, 3-methylpent-1-yn-1-yl, 3-methylpent-1-yn-3-yl, 3-methylpent-1-yn-4-yl, 3-methylpent-1-yn-5-yl, 4-methylpent-1-yn-1-yl, 4-methylpent-2-yn-4-yl and 4-methylpent-2-yn-5-yl;
C2-C6-alkynyl: C3-C6-alkynyl as mentioned above, and ethynyl:
C3-C6-cycloalkyl: cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl;
C4-C6-cycloalkenyl: cyclobuten-1-yl, cyclobuten-3-yl, cyclopenten-1-yl, cyclopenten-3-yl, cyclopenten-4-yl, cyclohexen-1-yl, cyclohexen-3-yl and cyclohexen-4-yl;
heterocyclyl and the heteroclyl [sic] radicals in heterocyclyloxy: three- to seven-membered saturated or partially unsaturated mono- or polycyclic heterocycles containing one to three hetero atoms selected from a group consisting of oxygen, nitrogen and sulfur, such as oxiranyl, oxetan-3-yl, thietan-3-yl, 2-tetrahydrofuranyl, 3-tetrahydrofuranyl, 2-tetrahydrothienyl, 3-tetrahydrothienyl, 2-pyrrolidinyl, 3-pyrrolidinyl, 3-isoxazolidinyl, 4-isoxazolidinyl, 5-isoxazolidinyl, 3-isothiazolidinyl, 4-isothiazolidinyl, 5-isothiazolidinyl, 3-pyrazolidinyl, 4-pyrazolidinyl, 5-pyrazolidinyl, 2-oxazolidinyl, 4-oxazolidinyl, 5-oxazolidinyl, 2-thiazolidinyl, 4-thiazolidinyl, 5-thiazolidinyl, 2-imidazolidinyl, 4-imidazolidinyl, 1,2,4-oxadiazolidin-3-yl, 1,2,4-oxadiazolidin-5-yl, 1,2,4-thiadiazolidin-3-yl, 1,2,4-thiadiazolidin-5-yl, 1,2,4-triazolidin-3-yl, 1,3,4-oxadiazolidin-2-yl, 1,3,4-thiadiazolidin-2-yl, 1,3,4-triazolidin-2-yl, 2,3-dihydrofuran-2-yl, 2,3-dihydrofuran-3-yl, 2,3-dihydrofuran-4-yl, 2,3-dihydrofuran-5-yl, 2,5-dihydrofuran-2-yl, 2,5-dihydrofuran-3-yl, 2,3-dihydrothien-2-yl, 2,3-dihydrothien-3-yl, 2,3-dihydrothien-4-yl, 2,3-dihydrothien-5-yl, 2,5-dihydrothien-2-yl, 2,5-dihydrothien-3-yl, 2,3-dihydropyrrol-2-yl, 2,3-dihydropyrrol-3-yl, 2,3-dihydropyrrol-4-yl, 2,3-dihydropyrrol-5-yl, 2,5-dihydropyrrol-2-yl, 2,5-dihydropyrrol-3-yl, 2,3-dihydroisoxazol-3-yl, 2,3-dihydroisoxazol-4-yl, 2,3-dihydroisoxazol-5-yl, 4,5-dihydroisoxazol-3-yl, 4,5-dihydroisoxazol-4-yl, 4,5-dihydroisoxazol-5-yl, 2,5-dihydroisoxazol-3-yl, 2,5-dihydroisoxazol-4-yl, 2,5-dihydroxazol-5-yl, 2,3-dihydroisothiazol-3-yl, 2,3-dihydroisothiazol-4-yl, 2,3-dihydroisothiazol-5-yl, 4,5-dihydroisothiazol-3-yl, 4,5-dihydroisothiazol-4-yl, 4,5-dihydroisothiazol-5-yl, 2,5-dihydroisothiazol-3-yl, 2,5-dihydroisothiazol-4-yl, 2,5-dihydroisothiazol-5-yl, 2,3-dihydropyrazol-3-yl, 2,3-dihydropyrazol-4-yl, 2,3-dihydropyrazol-5-yl, 4,5-dihydropyrazol-3-yl, 4,5-dihydropyrazol-4-yl, 4,5-dihydropyrazol-5-yl, 2,5-dihydropyrazol-3-yl, 2,5-dihydropyrazol-4-yl, 2,5-dihydropyrazol-5-yl, 2,3-dihydrooxazol-2-yl, 2,3-dihydrooxazol-4-yl, 2,3-dihydrooxazol-5-yl, 4,5-dihydrooxazol-2-yl, 4,5-dihydrooxazol-4-yl, 4,5-dihydrooxazol-5-yl, 2,5-dihydrooxazol-2-yl, 2,5-dihydrooxazol-4-yl, 2,5-dihydrooxazol-5-yl, 2,3-dihydrothiazol-2-yl, 2,3-dihydrothiazol-4-yl, 2,3-dihydrothiazol-5-yl, 4,5-dihydrothiazol-2-yl, 4,5-dihydrothiazol-4-yl, 4,5-dihydrothiazol-5-yl, 2,5-dihydrothiazol-2-yl, 2,5-dihydrothiazol-4-yl, 2,5-dihydrothiazol-5-yl, 2,3-dihydroimidazol-2-yl, 2,3-dihydroimidazol-4-yl, 2,3-dihydroimidazol-5-yl, 4,5-dihydroimidazol-2-yl, 4,5-dihydroimidazol-4-yl, 4,5-dihydroimidazol-5-yl, 2,5-dihydroimidazol-2-yl, 2,5-dihydroimidazol-4-yl, 2,5-dihydroimidazol-5-yl, 2-morpholinyl, 3-morpholinyl, 2-piperidinyl, 3-piperidinyl, 4-piperidinyl, 3-tetrahydropyridazinyl, 4-tetrahydropyridazinyl, 2-tetrahydropyrimidinyl, 4-tetrahydropyrimidinyl, 5-tetrahydropyrimidinyl, 2-tetrahydropyrazinyl, 1,3,5-tetrahydrotriazin-2-yl, 1,2,4-tetrahydrotriazin-3-yl, 1,3-dihydrooxazin-2-yl, 1,3-dioxan-2-yl, 1,3-dithian-2-yl, 2-tetrahydropyranyl, 3-tetrahydropyranyl, 4-tetrahydropyranyl, 2-tetrahydrothiopyranyl, 3-tetrahydrothiopyranyl, 4-tetrahydrothiopyranyl, 1,3-dioxolan-2-yl, 1,3-dithiolan-2-yl, 3,4,5,6-tetrahydropyridin-2-yl, 4H-1,3-thiazin-2-yl, 4H-3,1-benzothiazin-2-yl, 1,1-dioxo-2,3,4,5-tetrahydrothien-2-yl, 2H-1,4-benzothiazin-3-yl, 2H-1,4-benzoxazin-3-yl, 1,3-dihydrooxazin-2-yl,
hetaryl and the hetaryl radicals in hetaryloxy:
aromatic mono- or polycyclic radicals which, in addition to carbon ring members, may contain one to four nitrogen atoms or one to three nitrogen atoms and one oxygen or one sulfur atom or one oxygen or one sulfur atom, for example 2-furyl, 3-furyl, 2-thienyl, 3-thienyl, 2-pyrrolyl, 3-pyrrolyl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 3-isothiazolyl, 4-isothiazolyl, 5-isothiazolyl, 3-pyrazolyl, 4-pyrazolyl, 5-pyrazolyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 2-imidazolyl, 4-imidazolyl, 1,2,4-oxadiazol-3-yl, 1,2,4-oxadiazol-5-yl, 1,2,4-thiadiazol-3-yl, 1,2,4-thiadiazol-5-yl, 1,2,4-triazol-3-yl, 1,3,4-oxadiazol-2-yl, 1,3,4-thiadiazol-2-yl, 1,3,4-triazol-2-yl, 2-pyridinyl, 3-pyridinyl, 4-pyridinyl, 3-pyridazinyl, 4-pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, 2-pyrazinyl, 1,3,5-triazin-2-yl, 1,2,4-triazin-3-yl, 1,2,4,5-tetrazin-3-yl, and the corresponding benzo-fused derivatives.
All phenyl and hetaryl rings are preferably unsubstituted or carry one to three halogens and/or one or two radicals from the following group: nitro, cyano, methyl, trifluoromethyl, methoxy, trifluoromethoxy or methoxycarbonyl.
Preferred with a view to the use of the compounds of the formula I according to the invention as herbicides are those compounds where the variables have the following meanings, in each case either on their own or in combination:
R1 is nitro, halogen, cyano, thiocyanato, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy-C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, xe2x80x94OR5 or xe2x80x94S(O)nR7;
particularly preferably nitro, halogen such as, for example, fluorine, chlorine or bromine, C1-C6-haloalkyl, xe2x80x94OR5 or xe2x80x94SO2R7 such as, for example, methylsulfonyl, ethylsulfonyl or difluoromethylsulfonyl; especially preferably nitro, fluorine, chlorine, bromine, trifluoromethyl, methoxy, ethoxy, methylsulfonyl, ethylsulfonyl or difluoromethylsulfonyl;
R2 is hydrogen, nitro, halogen, cyano, thiocyanato, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy-C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, xe2x80x94OR5 or xe2x80x94S(O)nR7;
particularly preferably hydrogen, nitro, halogen such as, for example, fluorine, chlorine or bromine, C1-C6-alkyl such as, for example, methyl or ethyl, C1-C6-haloalkyl, xe2x80x94OR5 or xe2x80x94SO2R7 such as, for example, methylsulfonyl, ethylsulfonyl or difluoromethylsulfonyl;
especially preferably nitro, fluorine, chlorine, bromine, methyl, ethyl, trifluoromethyl, methoxy, ethoxy, methylsulfonyl, ethylsulfonyl or difluoromethylsulfonyl;
R3 is hydrogen, cyano, C1-C6-alkyl, C1-C6-haloalkyl or xe2x80x94OR7;
R4 is hydrogen, C1-C6-alkyl, C3-C6-cycloalkyl, C3-C6-alkenyl or C3-C6-alkynyl, where the last 4 substituents mentioned may be partially or fully halogenated and/or carry one to three of the following groups: hydroxyl, mercapto, amino, cyano, xe2x80x94OR10, xe2x95x90NOR10, xe2x80x94OCOR10, xe2x80x94CO2R10, xe2x80x94COSR10, xe2x80x94CONR8R10, C1-C4-alkyliminooxy, C1-C4-alkylcarbonyl, C1-C4-alkoxy-C2-C6-alkoxycarbonyl, heterocyclyl, heterocyclyloxy, phenyl, benzyl, hetaryl, phenoxy, benzyloxy or hetaryloxy, where the last eight radicals mentioned may in turn be partially or fully halogenated and/or carry one to three radicals from the following group:
nitro, cyano, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkoxycarbonyl;
particularly preferably C1-C6-alkyl, C3-C6-cycloalkyl, C3-C6-alkenyl or C3-C6-alkynyl, where the last 4 substituents mentioned may be partially or fully halogenated and/or carry one to three of the following groups: hydroxyl, mercapto, amino, cyano, xe2x80x94OR10, xe2x95x90NOR10, xe2x80x94OCOR10, xe2x80x94CO2R10, xe2x80x94COSR10, xe2x80x94CONR8R10, C1-C4-alkyliminooxy, C1-C4-alkylcarbonyl, C1-C4-alkoxy-C2-C6-alkoxycarbonyl, heterocyclyl, heterocyclyloxy, phenyl, benzyl, hetaryl, phenoxy, benzyloxy or hetaryloxy, where the last eight radicals mentioned may in turn be partially or fully halogenated and/or carry one to three radicals from the following group:
nitro, cyano, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkoxycarbonyl;
X is oxygen or NH;
n is 0 or 2
R5 is hydrogen, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy-C2-C6-alkyl, C3-C6-alkenyl or C3-C6-alkynyl;
particularly preferably methyl, ethyl, trifluoromethyl, difluoromethyl, methoxyethyl, allyl or propargyl;
R7 is C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy-C2-C6-alkyl, C3-C6-alkenyl or C3-C6-alkynyl;
particularly preferably methyl, ethyl, trifluoromethyl, difluoromethyl, methoxyethyl, allyl or propargyl;
R8 is hydrogen or C1-C6-alkyl;
R10 is C1-C6-alkyl, C1-C6-haloalkyl, C3-C6-alkenyl or C3-C6-alkynyl;
R11, R12, R14 and R16 are each hydrogen or C1-C4-alkyl;
particularly preferably hydrogen, methyl or ethyl;
R13 is hydrogen, C1-C4-alkyl, C3-C4-cycloalkyl, where the last two groups may carry one to three of the following substituents: halogen, C1-C4-alkoxy or C1-C4-alkylthio; 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-dithian-2-yl or 1,3-dithiolan-2-yl, where the last six groups mentioned may in each case carry one to three C1-C4-alkyl radicals;
particularly preferably hydrogen, methyl, ethyl, cyclopropyl, di(methoxy)methyl, di(ethoxy)methyl, 2-ethylthiopropyl, 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, 5,5-dimethyl-1,3-dioxan-2-yl, 1,3-oxathiolan-2-yl, 1,3-oxathian-2-yl, 1,3-dithiolan-2-yl, 5,5-dimethyl-1,3-dithian-2-yl or 1-methylthiocyclopropyl;
R15 is hydrogen, C1-C4-alkyl or C1-C4-alkoxycarbonyl;
particularly preferably hydrogen, methyl or methoxycarbonyl.
It may also be advantageous for R13 and R16 to form a xcfx80-bond, thus forming a double bond system.
The CR13R14 unit may also be advantageously replaced by Cxe2x95x90O.
Particular preference is given to compounds of the formula Ia ( I where R1 is attached in position 4 of the phenyl ring and R2 is attached in position 2 of the phenyl ring).
Very particular preference is given to the compounds of the formula Ia in which R1 to R3, Q and X are as defined above and
R4 is hydrogen, C1-C6-alkyl, C3-C6-cycloalkyl, C3-C6-alkenyl or C3-C6-alkynyl, where the last 4 substituents may be partially or fully halogenated and/or carry one to three of the following groups: hydroxyl, mercapto, amino, cyano, xe2x80x94OR10, xe2x95x90NOR10, xe2x80x94OCOR10, xe2x80x94CO2R10, xe2x80x94COSR10, xe2x80x94CONR8R10, C1-C4-alkyliminooxy, C1-C4-alkylcarbonyl, C1-C4-alkoxy-C2-C6-alkoxycarbonyl, heterocyclyl, heterocyclyloxy, phenyl, benzyl, hetaryl, phenoxy, benzyloxy or hetaryloxy, where the last eight radicals mentioned may in turn be partially or fully halogenated and/or carry one to three radicals from the following group:
nitro, cyano, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkoxycarbonyl.
Most particular preference is given to the compounds Ia1 ( I where R1=Cl, R11, R12, R13, R14, R15, R16=H, R1 being attached in position 4 of the phenyl ring and R2 being attached in position 2 of the phenyl ring), in particular the compounds of Table 1.
Furthermore, most particular preference is given to the following 2-benzoylcyclohexane-1,3-diones of the formula I:
the compounds Ia2, in particular the compounds Ia2.001-Ia2.180, which differ from the corresponding compounds Ia1.001-Ia1.180 in that R13 is methyl:
xe2x80x83the compounds Ia3, in particular the compounds Ia3.001-Ia3.180, which differ from the corresponding compounds Ia1.001-Ia1.180 in that R13 and R14 are each methyl:
xe2x80x83the compounds Ia4, in particular the compounds Ia4.001-Ia4.180, which differ from the corresponding compounds Ia1.001-Ia1.180 in that R15 and R16 are each methyl:
xe2x80x83the compounds Ia5, in particular the compounds Ia5.001-Ia5.180, which differ from the corresponding compounds Ia1.001-Ia1.180 in that the CR13R14 unit is replaced by Cxe2x95x90O:
xe2x80x83the compounds Ia6, in particular the compounds Ia6.001-Ia6.180, which differ from the corresponding compounds Ia1.001-Ia1.180 in that R11, R15 and R16 are each methyl and the CR13R14 unit is replaced by Cxe2x95x90O:
xe2x80x83the compounds Ia7, in particular the compounds Ia7.001-Ia7.180, which differ from the corresponding compounds Ia1.001-Ia1.180 in that R11, R12, R15 and R16 are each methyl and the CR13R14 unit is replaced by Cxe2x95x90O:
xe2x80x83the compounds Ia8, in particular the compounds Ia8.001-Ia8.180, which differ from the corresponding compounds Ia1.001-Ia1.180 in that R1 is nitro:
xe2x80x83the compounds Ia9, in particular the compounds Ia9.001-Ia9.180, which differ from the corresponding compounds Ia1.001-Ia1.180 in that R1 is nitro and R13 is methyl:
xe2x80x83the compounds Ia10, in particular the compounds Ia10.001-Ia10.180, which differ from the corresponding compounds Ia1.001-Ia1.180 in that R1 is nitro and R13 and R14 are each methyl:
xe2x80x83the compounds Ia11, in particular the compounds Ia11.001-Ia11.180, which differ from the corresponding compounds Ia1.001-Ia1.180 in that R1 is nitro and R15 and R16 are each methyl:
xe2x80x83the compounds Ia12, in particular the compounds Ia12.001-Ia12.180, which differ from the corresponding compounds Ia1.001-Ia1.180 in that R1 is nitro and the CR13R14 unit is replaced by Cxe2x95x90O:
xe2x80x83the compounds Ia13, in particular the compounds Ia13.001-Ia13.180, which differ from the corresponding compounds Ia1.001-Ia1.180 in that R1 is nitro, R11, R15 and R16 are each methyl and the CR13R14 unit is replaced by Cxe2x95x90O:
xe2x80x83the compounds Ia14, in particular the compounds Ia14.001-Ia14.180, which differ from the corresponding compounds Ia1.001-Ia1.180 in that R1 is nitro, R11, R12, R15 and R16 are each methyl and the CR13R14 unit is replaced by Cxe2x95x90O:
xe2x80x83the compounds Ia15, in particular the compounds Ia15.001-Ia15.180, which differ from the corresponding compounds Ia1.001-Ia1.180 in that R1 is methylsulfonyl:
xe2x80x83the compounds Ia16, in particular the compounds Ia16.001-Ia16.180, which differ from the corresponding compounds Ia1.001-Ia1.180 in that R1 is methylsulfonyl and R13 is methyl:
xe2x80x83the compounds Ia17, in particular the compounds Ia17.001-Ia17.180, which differ from the corresponding compounds Ia1.001-Ia1.180 in that R1 is methylsulfonyl and R13 and R14 are each methyl:
xe2x80x83the compounds Ia18, in particular the compounds Ia18.001-Ia18.180, which differ from the corresponding compounds Ia1.001-Ia1.180 in that R1 is methylsulfonyl and R15 and R16 are each methyl:
xe2x80x83the compounds Ia19, in particular the compounds Ia19.001-Ia19.180, which differ from the corresponding compounds Ia1.001-Ia1.180 in that R1 is methylsulfonyl and the CR13R14 unit is replaced by Cxe2x95x90O:
xe2x80x83the compounds Ia20, in particular the compounds Ia20.001-Ia20.180, which differ from the corresponding compounds Ia1.001-Ia1.180 in that R1 is methylsulfonyl, R11, R15 and R16 are each methyl and the CR13R14 unit is replaced by Cxe2x95x90O:
xe2x80x83the compounds Ia21, in particular the compounds Ia21.001-Ia21.180, which differ from the corresponding compounds Ia1.001-Ia1.180 in that R1 is methylsulfonyl, R11 R12 R15 and R16 are each methyl and the CR13R14 unit is replaced by Cxe2x95x90O:
xe2x80x83the compounds Ia22, in particular the compounds Ia22.001-Ia22.180, which differ from the corresponding compounds Ia1.001-Ia1.180 in that R1 is trifluoromethyl:
xe2x80x83the compounds Ia23, in particular the compounds Ia23.001-Ia23.180, which differ from the corresponding compounds Ia1.001-Ia1.180 in that R1 is trifluoromethyl and R13 is methyl:
xe2x80x83the compounds Ia24, in particular the compounds Ia24.001-Ia24.180, which differ from the corresponding compounds Ia1.001-Ia1.180 in that R1 is trifluoromethyl and R13 and R14 are each methyl:
xe2x80x83the compounds Ia25, in particular the compounds Ia25.001-Ia25.180, which differ from the corresponding compounds Ia1.001-Ia1.180 in that R1 is trifluoromethyl and R15 and R16 are each methyl:
xe2x80x83the compounds Ia26, in particular the compounds Ia26.001-Ia26.180, which differ from the corresponding compounds Ia1.001-Ia1.180 in that R1 is trifluoromethyl and the CR13R14 unit is replaced by Cxe2x95x90O:
xe2x80x83the compounds Ia27, in particular the compounds Ia27.001-Ia27.180, which differ from the corresponding compounds Ia1.001-Ia1.180 in that R1 is trifluoromethyl, R11, R15 and R16 are each methyl and the CR13R14 unit is replaced by Cxe2x95x90O:
xe2x80x83the compounds Ia28, in particular the compounds Ia28.001-Ia28.180, which differ from the corresponding compounds Ia1.001-Ia1.180 in that R1 is trifluoromethyl, R11, R12, R15 and R16 are each methyl and the CR13R14 unit is replaced by Cxe2x95x90O:
Extraordinary preference is given to the compounds of the formula Iaxe2x80x2  I where R1 is attached in position 4 of the phenyl ring and R2 is attached in position 2 of the phenyl ring)
where
R1 is halogen or C1-C4-alkylsulfonyl;
R2 is halogen or C1-C4-alkyl, in particular halogen;
R3 is hydrogen, C1-C4-alkyl or C1-C4-alkoxy, in particular hydrogen or C1-C4-alkoxy;
R4 is C1-C6-alkyl, C3-C6-alkynyl, where these two substituents may be partially or fully halogenated and/or may carry one to three of the following groups: phenyl or hetaryl, where these groups may in turn be partially or fully halogenated;
X is oxygen;
R11, R121 R13, R14, R15, R16 are each hydrogen or C1-C4-alkyl.
The 2-benzoylcyclohexane-1,3-diones of the formula I can be obtained in a variety of ways, for example by the following process:
Reaction of cyclohexanediones of the formula II with an activated carboxylic acid IIIxcex1 or a carboxylic acid IIIxcex2 which is preferably activated in situ, to give the acylation product IV, and activated subsequent rearrangement.
L is a nucleophilically replaceable leaving group, such as halogen, for example bromine or chlorine, hetaryl, for example imidazolyl or pyridyl, carboxylate, for example acetate or trifluoroacetate, etc.
The activated carboxylic acid can be employed directly, as in the case of the acyl halides, or be generated in situ, for example by using dicyclohexylcarbodiimide, triphenylphosphine/azodicarboxylic acid esters, 2 pyridine disulfite [sic]/triphenylphosphine, carbonyldiimidazole, etc.
If appropriate, it may be advantageous to carry out the acylation reaction in the presence of a base. The reactants and the auxiliary base are advantageously employed in equimolar amounts. A slight excess of the auxiliary base, for example 1.2 to 1.5 molar equivalents based on II, may be advantageous in certain instances.
Suitable auxiliary bases are tertiary alkylamines, pyridine or alkali metal carbonates. Suitable solvents are, for example, chlorinated hydrocarbons, such as methylene chloride and 1,2-dichloroethane, aromatic hydrocarbons, such as toluene, xylene or chlorobenzene, ethers, such as diethyl ether, methyl tert-butyl ether, tetrahydrofuran and dioxane, polar aprotic solvents, such as acetonitrile, dimethylformamide and dimethyl sulfoxide, or esters such as ethyl acetate, or mixtures of these.
If acyl halides are used as activated carboxylic acid component, it may be advantageous to cool the reaction mixture to 0-10xc2x0 C. when adding this reaction partner. Subsequently, the mixture is stirred at 20-100xc2x0 C., preferably at 25-50xc2x0 C., until the reaction has ended. Work-up is carried out in a conventional manner, for example by pouring the reaction mixture into water and extracting the product of value. Suitable solvents for this purpose are in particular methylene chloride, diethyl ether and ethyl acetate. After drying off the organic phase and removal of the solvent, crude enol ester of the formula IV is preferably purified by chromatography. However, it is also possible to use the crude enol ester of the formula IV without further purification for the rearrangement.
The rearrangement of the enol esters of the formula IV to the compounds of the formula I is advantageously carried out at temperatures from 20 to 40xc2x0 C. in a solvent and in the presence of an auxiliary base and, if appropriate, with the aid of a cyano compound as catalyst.
Suitable solvents are, for example, acetonitrile, methylene chloride, 1,2-dichloroethane, ethyl acetate, toluene or mixtures of these. The preferred solvent is acetonitrile.
Suitable auxiliary bases are tertiary amines such as triethylamine or pyridine, or alkali metal carbonates, such as sodium carbonate and potassium carbonate, which are preferably employed in equimolar amounts or in up to four-fold excess, based on the enol ester. Preference is given to using triethylamine, preferably in twice the equimolar amount, based on the enol ester.
Suitable xe2x80x9crearrangement catalystsxe2x80x9d are inorganic cyanides, such as sodium cyanide and potassium cyanide, and organic cyano compounds, such as acetone cyanohydrin and trimethylsilyl cyanide. They are conventionally used in an amount of from 1 to 50 mol percent, based on the enol ester. Preference is given to using acetone cyanohydrin or trimethylsilyl cyanide, for example in an amount of from 5 to 15, preferably 10, mol percent, based on the enol ester.
Workup can be carried out in a manner known per se. For example, the reaction mixture is acidified with dilute mineral acid, such as, for example 5% strength hydrochloric acid or sulfuric acid, and extracted with an organic solvent, for example methylene chloride or ethyl acetate. The organic extract may be extracted with 5-10% strength alkali metal carbonate solution, for example sodium carbonate or potassium carbonate solution. The aqueous phase is acidified and the resulting precipitate is filtered off with suction and/or extracted with methylene chloride or ethyl acetate, dried and concentrated.
(Examples of the preparation of enol esters from cyclohexane-1,3-diones and of the cyanide-catalyzed rearrangement of the enol esters are given, for example, in EP-A 186 118, U.S. Pat. No. 4,780,127).
The cyclohexane-1,3-diones of the formula II used as starting materials are known or can be prepared by known processes (for example EP-A 71 707, EP-A 142 741, EP-A 243 313, U.S. Pat. No. 4,249,937; WO 92/13821).
The benzoic acid derivatives of the formula III are novel,
where:
R1, R2 are each hydrogen, nitro, halogen, cyano, thiocyanato, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy-C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, xe2x80x94OR5, xe2x80x94OCOR6, xe2x80x94OSO2R6, xe2x80x94SH, xe2x80x94S(O)nR7, xe2x80x94SO2OR5, xe2x80x94SO2NR5R8, xe2x80x94NR8SO2R6 or xe2x80x94NR8COR6;
R3 is hydrogen, cyano, C1-C6-alkyl, C1-C6-haloalkyl, xe2x80x94OR7, xe2x80x94SR7 or xe2x80x94NR7R10;
R4 is hydrogen, C1-C6-alkyl, C3-C6-cycloalkyl, C3-C6-alkenyl, C4-C6-cycloalkenyl, C3-C6-alkynyl, xe2x80x94COR9, xe2x80x94CO2R9, xe2x80x94COSR9 or xe2x80x94CONR8R9, where the alkyl, cycloalkyl, alkenyl, cycloalkenyl and alkynyl radicals mentioned and R9 of the radicals xe2x80x94COR9, xe2x80x94CO2R9, xe2x80x94COSR9 and xe2x80x94CONR8R9 may be partially or fully halogenated and/or carry one to three of the following groups:
hydroxyl, mercapto, amino, cyano, R10, xe2x80x94OR10, xe2x80x94SR10, xe2x80x94NR8R10,xe2x95x90NOR10, xe2x80x94OCOR10, xe2x80x94SCOR10, xe2x80x94NR8COR10, xe2x80x94CO2R10, xe2x80x94COSR10, xe2x80x94CONR8R10, C1-C4-alkyliminooxy, C1-C4-alkoxyamino, C1-C4-alkylcarbonyl, C1-C4-alkoxy-C2-C6-alkoxycarbonyl, C1-C4-alkylsulfonyl, heterocyclyl, heterocyclyloxy, phenyl, benzyl, hetaryl, phenoxy, benzyloxy and hetaryloxy, where the last eight radicals mentioned may in turn be substituted;
X is oxygen or NR8;
n is 0, 1 or 2;
R5 is hydrogen, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy-C2-C6-alkyl, C3-C6-alkenyl or C3-C6-alkynyl;
R6 is C1-C6-alkyl or C1-C6-haloalkyl;
R7 is C1-C6-alkyl, C1-C6-haloalkyl, C4-C6-alkoxy-C2-C6-alkyl, C3-C6-alkenyl or C3-C6-alkynyl;
R8 is hydrogen or C1-C6-alkyl;
R9 is C1-C6-alkyl, C3-C6-alkenyl, C3-C6-alkynyl, phenyl or benzyl;
R10 is C1-C6-alkyl, C1-C6-haloalkyl, C3-C6-alkenyl or C3-C6-alkynyl;
R17 is hydroxyl or a radical that can be removed by hydrolysis.
Examples of radicals that can be removed by hydrolysis are alkoxy, phenoxy, alkylthio and phenylthio radicals with or without substitution, halides, hetaryl radicals which are attached via nitrogen, amino and imino radicals with or without substitution, etc.
Preference is given to benzoyl halides IIIxcex1, where L=halogen  III where R17=halogen),
where the variables R1 to R4 and X are each as defined under formula III and
L is halogen, in particular chloride or bromide.
Preference is also given to the benzoic acids of the formula IIIxcex2  III where R17=hydroxyl),
where the variables R1 to R4 and X are each as defined under formula III.
Preference is also given to the benzoic acid esters of the formula IIIxcex3 ( III where M=C1-C6-alkoxy)
where the variables R1 to R4 and X are each as defined under formula III and
M is C1-C6-alkoxy.
With regard to the preferred compounds of the formula III, the remarks made under the compounds I apply to the radicals R1 to R4 and X.
The compounds of the formula IIIxcex1 (where L=halogen) can be prepared in a similar manner to literature methods (cf. L. G. Fieser, M. Fieser xe2x80x9cReagents for Organic Synthesisxe2x80x9d, Vol. I, p. 767-769 (1967)) by reacting benzoic acids of the formula IIIxcex2 with halogenating reagents such as thionyl chloride, thionyl bromide, phosgene, diphosgene, triphosgene, oxalyl chloride or oxalyl bromide.
The benzoic acids of the formula IIIxcex2 can be obtained in a similar manner to literature methods, inter alia by hydrolysis of the benzoic acid esters of the formula IIIxcex3 (where M=C1-C6-alkoxy).
The benzoic acid esters of the formula IIIxcex3 are obtainable in a variety of ways, for example by the following processes:
Isophthalic acid derivatives of the formula VI can be obtained by oxidation of aldehydes of the formula V in a manner known per se (J. March, xe2x80x9cAdvanced Organic Chemistryxe2x80x9d, 3rd Edition, p. 629 ff, Wiley-Interscience Publication, 1985).
In a similar manner to literature methods, the compounds of the formula VI can initially be converted into the corresponding activated carboxylic acids VII where L1 is a nucleophilically displaceable leaving group such as halogen, for example bromine or chlorine, hetaryl, for example imidazolyl or pyridyl, carboxylate, for example acetate or trifluoracetate etc., and then into the corresponding hydroxamic acid or carbohydrazide derivatives of the formula VIII (Australian J. Chem. 22, (1969), 1731-1735; ibid 22 (1969), 161-173; J. Org. Chem. 27 (1974), 1341-1349).
Alkylation of compounds of the formula VIII leads to compounds of the formula IIIxcex3 (where R3=OR7) in a manner known per se (EP-A 463 989; Synthesis (1983), 220-222; U.S. Pat. No. 4,931,088; J. Org. Chem. 31 (1971), 284-294; J. Chem. Soc. Perk. II (1977), 1080-1084).
Compounds of the formula IIIxcex3 are obtained in a manner known per se by reacting aldehydes/ketones of the formula IX with xe2x80x9calkoxamines or alkylhydrazinesxe2x80x9d. In a similar manner to processes known from the literature, it is possible to react aldehydes/ketones of the formula IX with hydroxylamine or hydrazine and to alkylate them subsequently (J. March, xe2x80x9cAdvanced Organic Chemistryxe2x80x9d, 3rd Edition, p. 359, p. 805-806, Wiley-Interscience Publication, 1985).
It is possible to convert nitriles of the formula X in a manner known per se by alcoholysis (R7OH) into imino esters which can be reacted in a further step with hydroxylamines or hydrazines to give compounds of the formula IIIxcex3 (J. March, xe2x80x9cAdvanced Organic Chemistryxe2x80x9d, 3rd Edition, p. 792-793, Wiley-Interscience Publication, 1985; U.S. Pat. No. 4,965,390).
In a similar manner to processes known from the literature, nitriles of the formula X can be prepared from the corresponding aldehydes V (J. March, xe2x80x9cAdvanced Organic Chemistryxe2x80x9d, 3rd Edition, p. 806-807, Wiley-Interscience Publication, 1985). It is also possible to obtain nitrites of the formula X from anilines of the formula XI by employing the Sandmeyer reaction or from aryl halides of the formula XII by the Rosemund/von Braun reaction using metal cyanides, in particular CuCN (J. March, xe2x80x9cAdvanced Organic Chemistryxe2x80x9d, 3rd Edition, p. 594, p. 648, Wiley-Interscience Publication, 1985).
In a similar manner to processes known from the literature, the aldehydes of the formula V can be prepared from the corresponding toluenes of the formula XIII by conversion into the xcfx89-halotoluene XIV and subsequent oxidation (cf. Synth. Commun. 22 (1992) 1967-1971).

Substituted 2-benzoyl-cyclohexan-1,3-diones with herbicidal effect

Abstract: where

Abstract: R1, R2 are each hydrogen, nitro, halogen, cyano, thiocyanato, alkyl, haloalkyl, alkoxyalkyl, alkenyl, alkynyl, xe2x80x94OR5, xe2x80x94OCOR6, xe2x80x94OSO2R6, xe2x80x94SH, xe2x80x94S(O)nR7, xe2x80x94SO2OR5, xe2x80x94SO2NR5R8, xe2x80x94NR8SO2R6 or xe2x80x94NR8COR6;

Abstract: R3 is hydrogen, cyano, alkyl, haloalkyl, xe2x80x94OR7, xe2x80x94SR7 or xe2x80x94NR7R10;

Abstract: R4 is hydrogen, substituted or unsubstituted alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, xe2x80x94COR9, xe2x80x94CO2R9, xe2x80x94COSR9 or xe2x80x94CONR8R9;

Abstract: X is oxygen or NR8;

Abstract: n is 0, 1 or 2;

Abstract: R5 is hydrogen, alkyl, haloalkyl, alkoxyalkyl, alkenyl or alkynyl;

Abstract: R6 is alkyl or haloalkyl;

Abstract: R7 is alkyl, haloalkyl, alkoxyalkyl, alkenyl or alkynyl;

Abstract: R8 is hydrogen or alkyl;

Abstract: R9 is alkyl, alkenyl, alkynyl, phenyl or benzyl;

Abstract: R10 is alkyl, haloalkyl, alkenyl or alkynyl;

Abstract: Q is a cyclohexane-1,3-dione ring with or without substitution attached in position 2;

Abstract: and agriculturally useful salts thereof;

Abstract: to processes and intermediates for preparing the compounds of the formula I; to compositions comprising them; and to the use of these derivatives or compositions comprising them for controlling undesirable plants.


An overload management system is provided, including a method and an apparatus, for controlling the operation of electrical equipment in a short-term overload region above the equipment's continuous capability operation curve, without suffering significant loss of equipment life. This overload management system is particularly beneficial for use with equipment having load management capability, such as a modular thyristor controlled series capacitor (TCSC) system using phase controlled firing based on monitored capacitor voltage and line current. For vernier operation, the system predicts an upcoming firing angle for switching a switching device to govern the current received by the electrical device, such as to bypass line current around a series capacitor of the TCSC system. The overload management system may serve as one of several higher-level controllers providing input to a vernier controller for accommodating competing objectives of various system demands.

The present invention relates generally to an overload management system, including a method and an apparatus, for controlling the operation of electrical equipment in a short-term overload region above the equipment's continuous capability operation curve, without suffering significant loss of equipment life. This overload management system is particularly beneficial for use with equipment having load management capability, including thyristor-controlled power equipment, such as high voltage direct current (HVDC) equipment, motor drives, static volt-ampere-reactive (VAR) compensators (SVC), and thyristor-controlled series compensation (TCSC) systems.
The present invention may be used in combination with a modular order distribution logic firing control system, which accommodates the competing objectives of various system demands in an alternating current (AC) power distribution system. These system demands may include minimizing losses in scheduling control, stabilizing transients, damping subsynchronous resonance (SSR) oscillations, damping direct current (DC) offset, and damping power-swings, as well as more efficiently using the overload capability of electrical equipment in accordance with the present invention.
Power equipment is typically rated in terms of continuous capability limits and short-term overload capability limits. The cost of a particular installation may be minimized by designing the equipment for normal operating conditions, and then using an operational philosophy which intentionally uses this inherent overload capability of the equipment. For example, a TCSC system may be designed for normal line current, even though the line current may exceed the steady-state rating for short durations for a limited number of times over the life span of the TCSC equipment.
One common overload index used by designers specifying equipment is the thirty minute rating. The equipment may be operated during a rare overload event in the thirty minute rating region, for instance, while system operators redispatch power flows over the power system. Another commonly used index is the transient rating region, for instance, on the order of a ten second overload rating. The equipment may be operated in the transient rating region after a major contingency, such as a fault, to delay bypassing operations until the system stabilizes.
For instance, typical TCSC systems are designed with the intent that occasionally the inherent short-term overload capability of the capacitor will be used. However, the recently realized ability of a TCSC system to amplify the current through the capacitor using vernier conduction adds significantly to the complexity of the TCSC system, in comparison with a conventional series capacitor system. Such vernier operation of a TCSC system is shown in the related U.S. Pat. No. 5,202,538, to Larsen et al., referenced in the first paragraph above. Thus, any attempt to operate such a vernier controlled TCSC system must also address this current amplification characteristic.
Other controlled series compensation systems have been proposed, but without including any type of an overload management function. For example, such earlier systems are proposed by N. Christl, et al. in the paper entitled "Advanced Series Compensation (ASC) With Thyristor-Controlled Impedance," CIGRE Paper No. 14/37/38-05 (Paris, 1992); and by A. J. F. Keri, et al., in the article entitled "Improving Transmission System Performance Using Controlled Series Capacitors," CIGRE Paper No. 14/37/38-07 (Paris, 1992).
In the past, other overload management systems have been proposed. For example, one primitive overload management system has been used with HVDC equipment. During serious power system disturbances, this earlier management system operates the HVDC system above its continuous rating for a specified length of time. After this overload operation, the HVDC system may return to a normal rate of operation or, in some cases shutdown is required for a specified recovery period. Unfortunately, during this recovery shutdown period, power must be rerouted around the HVDC equipment. Also, this earlier management system is implemented as a discrete function, with step-wise control. Thus, this earlier system is not capable of tailoring its response to match levels of overload operation required to accurately respond to fluctuating system disturbances.
Indeed, earlier strategies for handling equipment overloads in general have allowed cyclic operation between normal and overload conditions with discrete, step-wise transitions between conditions, and with durations for specific time periods. For example, overload operation at 137% may be allowed for two hours during a 24-hour cycle. This daily cycle is referred to in industry standards as an "assumed load cycle," with equipment designed to withstand certain temperature rises during such normal and overload conditions. These conventional operating strategies are illustrated in various equipment standards, such as those for power transformers.
Thus, a need exists for an improved overload management system for efficiently operating electrical devices in their short term overload regions, which is directed toward overcoming, and not susceptible to, the above limitations and disadvantages.


The present invention provides new antiviral compounds and pharmacological compositions comprising these new compounds and their use in the prophylaxis, prevention and treatment of viral infections, particularly adenovirus and herpes virus infections.

Adenovirus infections are widespread in society and are occasionally associated with severe, but rarely with life-threatening, disease in otherwise healthy individuals. In contrast, adenovirus infections present a real threat to immunocompromised individuals and can result in disseminated and fatal disease. The number of patients undergoing immunosuppressive therapy for solid organ or hematopoietic stem cell transplantation is steadily increasing, as is the number of AIDS patients, and this makes the problem of adenovirus infections even more urgent to solve. There is no formally approved treatment of adenovirus infections today, and existing antiviral agents evaluated for their anti-adenoviral effect give inconsistent results.
Human adenoviruses are very common pathogens and comprise at least 51 different serotypes; together, these form six different species, A-F. Adenoviruses (Ads) are associated with a wide variety of clinical symptoms in humans, such as upper respiratory illness, acute respiratory disease, gastroenteritis, hemorrhagic cystitis, and even keratoconjunctivitis (Wadell, G. 1984. Molecular epidemiology of human adenoviruses. Current topics in microbiology and immunology 110:191-220. Wadell et al. 1999. Adenoviruses, p. 970-982. In. Murray et al. (eds.), Manual of Clinical Microbiology, 7th ed. ASM Press.).
These infections can result in severe disease, although an Ad infection is most commonly self-limited in otherwise healthy individuals. The problem is much more pronounced in immunocompromised individuals. This group is steadily growing as a result of increasing numbers of AIDS patients and patients undergoing immunosuppressive therapy for solid organ or hematopoietic stem cell transplantation, and also because of increased survival times of these patients. Immunocompromised individuals are at high risk of developing disseminated disease and multiple organ failure, and an Ad infection can become a serious life-threatening disease (Janney et al. 1990. Fatal adenovirus infection in a child with acquired immunodeficiency syndrome. Pediatr. Infect. Dis. J. 9:434-436). In immunocompromised children, Ads are an important cause of disease and case fatality rates of above 50% have been reported (Hierholzer 1992. Adenoviruses in the immunocompromised host. Clinical Microbiology Reviews 5:262-274). In pediatric bone marrow transplant (BMT) recipients the incidence of Ad infection is substantially higher than in adult BMT recipients (Baldwin et al. 2000. Outcome and clinical course of 100 patients with adenovirus infection following bone marrow transplantation. Bone Marrow Transplantation 26:1333-1338).
A number of different Ads have been isolated from immunocompromised patients, most frequently from species A, B, or C (Kojaoghlanian et al. 2003. The impact of adenovirus infection on the immunocompromised host. Rev Med Virol 13:155-71). Species B serotypes are predominantly associated with renal syndromes and species C serotypes are usually associated with hepatitis. In recent years, infections with Ad serotype 31 (species A) have been increasingly reported and they often occur in patients with infections involving multiple Ad serotypes, occasionally with lethal outcome (Leruez-Ville et al. 2006. Description of an adenovirus A31 outbreak in a paediatric haematology unit. Bone Marrow Transplant 38:23-28.).
There are no approved specific antiviral compounds for treatment of Ad infections available today. Established antiviral drugs including cidofovir, ribavirin, and ganciclovir have been tested for anti-adenoviral activity both in in vitro experiments and in the clinical setting. The clinical efficacy is inconclusive, since varying results have been reported for the drugs. Of the approved drugs, Cidofovir appears to be most effective against Ads (Morfin et al. 2005. In vitro susceptibility of adenovirus to antiviral drugs is species-dependent. Antiviral Therapy 10:225-229). However, cidofovir is associated with nephrotoxicity and acute renal failure (Izzedine et al. 2005. Antiviral Drug-Induced Nephrotoxicity. American Journal of Kidney Diseases 45:804-817). The need for new anti-adenoviral substances is clearly increasing due to the large number of immuno-compromised patients undergoing transplantations, and also patients suffering from AIDS or with genetic immunodeficiencies.
Herpes viruses are divided into alpha, beta and gamma herpes viruses. All studied herpes viruses enter a latent state after the primary infection. This means that they later in life can be activated and cause morbidity and in immunocompromized persons even mortality. Herpes simplex virus (HSV)1 & 2 and varicellae virus are the members of alpha herpes viruses. The U-L 23 gene of HSV encodes a nucleoside kinase also called thymidine kinase. This gene product is targeted by acyclovir and its derivatives. This is an effective therapeutic drug against HSV 1 & 2 and it has also been used against varicella-zoster (VZ) infections in adults and immunocompromized children and adults. There is however a need for new alternative antiviral drugs that can be used on acyclovir resistant strains and viruses that do not express a thymidine kinase.
Screening of large compound collections with purified protein or whole cell-based assays, i.e. high-throughput screening (HTS), is a common method to identify biologically active compounds. Cell-based approaches are commonly more labor-intensive but have the benefit of a wider screening without the limitation of having a preconceived idea of the mechanism of action. We have developed a unique whole-cell reporter gene assay based on a GFP-expressing replication-competent Ad vector (Sandberg et al. 2009. Replication-Competent Ad11p Vector (RCAd11p) Efficiently Transduces and Replicates in Hormone-Refractory Metastatic Prostate Cancer Cells. Human Gene Therapy 20:361-373). The assay can identify compounds that directly or indirectly affect adenoviral protein expression. This assay was used to screen approximately 9,800 compounds, resulting in a number of compounds that have an inhibitory effect on Ads without killing the host cells. The inhibitory effect was ascertained at four different stages of the viral replication cycle. Here, we describe the screening method and report on a novel inhibitors of Ad replication that is effective on Ad types representing the six species of human adenoviruses as well as on Herpes simplex virus 1 (HSV-1).
US 2006/0035245 describes a method for identifying anti-HIV agents comprising
i) determining the effect of the agent on the activity of Tn5 transponase, and
ii) determining if the agent can inhibit HIV integrase. The compound 2-[[2-(Benzoylamino)benzoyl]amino]-benzoic acid (herein referred to as compound A02) was found to inhibit Tn5 transponase, but failed to inhibit HIV integrase.


Muck and very wet material is removed from the surface of a moving conveyor belt by means of three scraper assemblies adjacent the head pulley of a conveyor belt installation. Each scraper assembly has a resilient, normally flat scraper blade with a tapered side, the opposite side being supported on an angle secured at each end to an operating lever which may be rotated by an air cylinder to engage the tapered side of the scraper blade with, and to flex the scraper blade against, the moving conveyor belt. The pressures in the air cylinders are adjusted so that the first scraper blade receives the greatest flexing force, and the second scraper blade a lesser flexing force, and the third scraper blade the least flexing force. This is done by supplying the air cylinders through progressively differently set pressure reducing valves connected to a common compressed air main.

1. Field of the Invention
This invention relates broadly to an improved scraper system for cleaning conveyor belts. More specifically, this invention relates to an improved scraper system embodying resilient tapered blades held and flexed by air cylinders against a moving conveyor belt as it passes around a head pulley of a conveyor belt installation to remove muck and very wet material from the conveyor belt.
2. Description of the Prior Art
Conveyor belt cleaning systems have long been known and used.
Thus, U.S. Pat. No. 3,047,133 (1962) to Searles shows a plurality of pairs of resilient discs held together by backing discs of smaller diameter, which resilient discs are mounted for rotation on a shaft and which are so urged towards engagement with the conveyor belt that the said resilient discs spread apart from each other beyond the diameters of their respective backing discs, thus presenting rotating circular segments to the face of the conveyor belt and thereby effecting the desired cleaning action. This design, while good for cleaning granulated gritty substances from the conveyor belt, has not proven to be totally satisfactory for removing muck and very wet materials from the conveyor belt.
Scrapers are also commonly used to clean conveyor belts, but are blunt and not tapered where they engage the belts. When in operation against a moving conveyor belt from which material is to be removed, the material has a tendency to chew out or erode the leading edges of the scrapers forming pockets between the scrapers and the conveyor belt, and to remain in the pockets, causing a smear action and carry-back, thus reducing cleaning efficiency.
Various mechanical means, such as ratchet mechanisms, threaded mountings, springs and counterweights have been employed to hold the above mentioned scrapers against the moving conveyor belt, but none provides for constant adjustment of scraper position at a substantially fixed degree of flexing across the entire width of the moving conveyor belt whereby the entire surface of the belt is scraped clean despite wear on the scrapers and unevenness or other on-uniformity of the belt or of the head pulley under the belt.


This disclosure is directed to an antenna coil and its support which comprises a terminal board made of heat resisting plastic material. The terminal board is provided with mountings, each of which has an opening extending in the vertical direction. Also provided are antenna supporting members, each having an antenna supporting portion at the upper part thereof and an insert or connector portion at the lower part thereof, the insert being adapted to be inserted in the opening of a respective mounting. Further, in accordance with another aspect of the invention, an antenna coil with a terminal board is disclosed, wherein at least one of the antenna supporting members is provided with a coil bobbin, the coil bobbin being molded integral with the respective antenna supporting member.

The present invention relates to an antenna coil and its support means, and more particularly to an antenna coil with a terminal board (a so called ferrite antenna) widely used for radio, tape recorders associated with radio or the like. It substantially comprises antenna supporting members, mountings for fastening to a base board and/or antenna support means.
It has been recognized that the hitherto known antenna coil or antenna support means has a number of drawback which are caused by physical, chemical or thermal conditions or other economical conditions inherrent to the structure of the hitherto known antenna coil.
Prior to considering the description of the antenna coil and its support means in accordance with the present invention, the conventional antenna coil support will be briefly described below in order to facilitate understanding of the present invention.

Antenna coil and its support structure mounting


The present invention discloses a bumper-cart light assembly of a golf cart. The bumper-cart light assembly includes a bumper body, a lower support, an integral cart light assembly and two upper supports. The two upper supports are symmetrically arranged at the upper end of the bumper body respectively. The lower support is arranged at the lower end of the bumper. The periphery of the bumper body extends rearwards to form a recess. The upper end of the bumper body forms a connecting tab. The upper end of the bumper protrudes upwards to form a protrusion provided with a receiving groove. The two upper supports are located at the two sides of the protrusion respectively. The middle of the bumper body is provided with an air inlet. The lower end of the bumper body is provided with an upward recess. The bumper-cart light assembly can carry a driving light assembly.

With development of the automobile industry and wide application of engineering plastics in that industry, the safety performance of automobile bumpers, which act as safety devices for absorbing and buffering external impact and for protecting pedestrians and both front and rear portions of automobile bodies, is receiving increasing attention. However, usually a bumper can only absorb energy and cannot carry a vehicle light assembly. At present, vehicle light assemblies are provided on the automobile body housings.


A passive seatbelt system which includes a runner piece which anchors the upper end of a passenger restraining belt which is guided by a guide rail fastened to a vehicle body and which is moved so that the belt is automatically fastened or removed from a passenger. The guide rail includes a base part which is fastened to the vehicle body and a pair of guide arms which hold the runner piece in a space between the guide arms and the base part whereby the runner piece is securely held during a vehicular emergency.

1. Field of Invention
This invention relates to passive seatbelt systems and more particularly to passive seatbelt systems which automatically fasten and unfasten the restraining belt from a passenger.
2. Prior Art
Seatbelt systems restrain passengers and prevent them from colliding with dangerous objects during vehicular emergencies. As a result, such systems make it possible to achieve a conspicuous improvement in passenger safety. In spite of this fact, however, the percentage of passengers who wear seatbelts is extremely low because of the difficulty in donning seatbelts, etc. As a result, various types of passive seatbelt systems have been proposed which make it possible to automatically fasten the belt around the passenger after the passenger has seated himself in the vehicle.
Among these systems, passive seatbelt systems which automatically fasten the belt around the passenger and remove the belt from around the passenger by the use of the driving force of a motor, etc., to move a runner piece which anchors the outer end of the belt have been highly rated because of their reliable operation. In such passive seatbelt systems, the tension on the belt is transmitted to the vehicle body via the runner piece. It is therefore necessary that the guide rail which serves as a guide part for the runner piece be of sufficient strength. However, in cases where a large, strong guide rail is used, the projection of parts of the passive seatbelt system into the passenger compartment decreases the passenger space in the vehicle and is dangerous in that it increases the possibility of a passenger colliding with the projecting portions during a vehicular emergency.


An image forming apparatus includes a main body in which a cassette unit to accommodate a plurality of sheets of paper, a toner cartridge unit to contain toner, an imaging unit to flow into the toner contained in the toner cartridge unit, a transfer unit which transfers an image formed by the imaging unit onto the paper, and a waste toner collection unit to collect waste toner discharged from the imaging unit and the transfer unit, and a control panel unit to receive user commands, wherein at least four of the cassette unit, the toner cartridge unit, the imaging unit, the transfer unit, the waste toner collection unit, and the control panel unit are disposed so as to be accessed by a user in the same direction.

1. Field of the Invention
The present general inventive concept relates to an image forming apparatus. More particularly, the present general inventive concept relates to a cover structure which enables users to easily replace expendables or components which are mounted in an image forming apparatus.
2. Description of the Related Art
High-speed and high-end devices generally have many optional components, so the number of components which must be replaced, attached or detached by users or service engineers is relatively large.
For example, such optional components may include a developing unit which develops images, a toner cartridge which supplies toner to the developing unit, an intermediate transfer belt unit which forms an image by overlapping four color toners, a waste toner collection unit which collects waste toner generated in the intermediate transfer belt or a photoconductive body, a paper feeding cassette which supplies paper, and a finisher which performs post-processing (stapling, folding, rotating, offsetting, pasting or punching) of printed paper. These optional components are frequently used in the business-to-business (B2B) market or corporate printers, and the use frequency thereof is likely to increase.
When designing an image forming apparatus in order to mount these option components, the paper feeding cassette and the developing unit may be attached or detached on the front of the image forming apparatus so that access by users is easy, and the intermediate transfer unit may be attached or detached to a side of the image forming apparatus, and other components such as the waste toner collection unit may be attached or detached in different diverse directions.
The reason that optional components are disposed to be accessible by the user in different directions is that the user cannot easily access important components or careful components and only service engineers having expertise can install or replace such components.
There is a recent trend that large devices which require replacement of diverse components are designed to be replaced directly by the user rather than be maintained and repaired by service engineers. Accordingly, each replaceable component is modularized and the structure of the image forming apparatus is improved in order for users to have easy access.
However, even if replaceable component are modularized, if attachment and detachment of each replaceable component are made in different directions, users having no expertise may not know in which direction each component is attached or detached, and the user must take the time to learn this for each component.
In addition, since one side of the image forming apparatus is generally disposed adjacent to a wall or other object, when optional components are attached or detached in the direction to the wall or other object, the image forming apparatus must be moved in order to attach or detach the optional components.
In addition, if option components are designed to be attached or detached in diverse directions, covers which are opened and closed to attach or detach in diverse directions have to be installed so that there is a space for installation and for an increased numbers of components to be considered as well as design restrictions.
In addition, if covers are designed to be opened and closed in diverse directions, a space and components for each cover, a space and components for opening or closing each cover, and a space and components for fixing each cover are required, with the result that the size of the image forming apparatus becomes larger and the structure becomes more complicated.
Furthermore, in order to open and close the covers in diverse directions, a space over a certain size must be secured so that the space for using the image forming apparatus is significantly wider than the space for installing the image forming apparatus, so space usage is inefficient.


A method and apparatus for ground bounce and power supply bounce detection in devices have been disclosed. In one case one input to a differential amplifier is coupled to a reference voltage and another input to the differential amplifier is coupled to a measurement point and the output of the differential amplifier is coupled to a flip flop. The flip flop has an output indicating when a bounce threshold is exceeded.

As electronic devices bus widths and bus speeds increase, the components that drive those busses must accommodate the accompanying current surges through the power (VDD) and ground (VSS) connections of the components. The current surge flowing through the impedance in component power connections, results in a voltage oscillation between the component power or ground reference level and the "system" power or ground voltage reference level. Some common names for this voltage oscillation include "Ground Bounce", "VDD Bounce", and "Simultaneous Switching Noise" (SSI). These bounces may upset the circuitry and/or cause it to not operate properly. This may present a problem.
Measuring ground bounce or simultaneous switching noise on a component is done in a controlled lab bench environment. The test may be performed several ways, however it usually involves forcing one un-terminated output to a logic low state and attaching an oscilloscope between this output and the ground reference level in the system. The output should provide a low impedance path to the internal ground level (e.g. die ground in an IC (integrated circuit)), and the setup will allow an observation of any fluctuation in the voltage of the die ground relative to the system ground. While in this setup, as many other outputs as practical are forced to simultaneously switch from a logic high state to a low logic state. The fluctuation in the die voltage or "bounce" is observed on the oscilloscope. The bench environment may not represent the actual system usage of a component, resulting in false or incomplete results. This may present a problem.
Measuring VDD bounce is performed in a similar way, except the un-terminated output is forced to a logic high, and the remaining outputs are forced to switch from a logic low to a logic high. The bench environment may not represent the actual system usage of a component, resulting in false or incomplete results. This may present a problem.

This patent is subject to a terminal disclaimer.

Method and apparatus for ground bounce and power supply bounce detection


A tape feed and dispensing mechanism for feeding a tape containing a carrier strip carrying articles to be dispensed and a protective covering for covering the carrier strip and retaining the articles upon it. A stripping device strips the covering strip from the carrier strip to access the carried parts. A disposal mechanism is provided that returns the stripped covering strip to a disposal area beneath the tape being fed and this includes an arrangement for turning the tape through 90.degree. as it passes by the strip of tape being fed. In one embodiment, the carrier strip is also returned to the same disposal area so that both strips can be disposed of at the same time.

This invention relates to a waste tape disposing means of a tape feeder and more particularly to an improved arrangement for disposing of waste tape from a tape feeding mechanism.
One commonly employed form of assembling mechanism employs small parts that are fed on a tape and which are protected within a protective cover. This protective cover is stripped back from the tape during the feeding operation so as to access the parts carried on the tape. Generally, the tape containing the parts is wound onto a feed roll and is fed to the assembly apparatus. A stripping mechanism is positioned forwardly of the feed roll and the protective cover is stripped back and then rolled onto a take-up roll for disposal. Generally, these take-up rolls are disposed immediately above the feed tape and hence have limited capability for holding the stripped protective cover.
This arrangement may be best understood by reference to FIG. 1 which is a figure showing a prior art type of feed and waste tape take-up mechanism. As may be seen in this Figure, a feed tape roll, indicated generally by the reference numeral 11 is provided on which a tape, indicated generally by the reference numeral 12 is wound. The feed roll 11 is supported for rotation in a feed direction about an axis, with the direction of feed being indicated by the arrow A.
The tape 12 includes a backing or carrier portion 13 which is formed with individual recesses, which will be discussed and described later in the specification, in which parts to be assembled are contained. A protective cover film 14 is provided over the carrier tape 13 and is intended to hold these small parts in position.
The parts carried on the carrier tape 13 are normally, as noted, small parts and may include components that will be employed and added onto a printed circuit board to provide a functional circuit. The parts to be assembled may, for example, be integrated chips or the like.
A stripper mechanism, indicated generally by the reference numeral 15 is positioned in the line of feed of the tape from the feed roll 11 and is positioned adjacent a back-up roller, indicated generally by the reference numeral 16, which may also drive the tape 12 in a feed direction and which has driving teeth 17 for this purpose.
The stripping mechanism 15 is provided with a slot 18 through which the protective cover 14 is fed and then is returned back onto a take-up roll, indicated generally by the reference numeral 19 and which is supported for rotation about an axis 21. The take-up roll 19 may be driven in an appropriate manner.
As may be readily apparent from the illustrated prior art construction, the positioning of the take-up roller 19 next to the feed roller 11 dictates a small diameter for the take-up roller. Therefore, the apparatus must be stopped quite frequently in order to permit new take-up rollers to be inserted and the older take-up roller being disposed. Said another way, this type of prior art construction does not permit continuous operation because of the necessity of periodically stopping the equipment to remove the filled up take-up roller.
It is, therefore, a principal object of this invention to provide an improved waste tape disposing means for a tape feeder.
It is a further object of this invention to provide a waste tape disposing means for a tape feeder that will permit continuous operation.
It is a further object of this invention to provide a waste tape disposing means for a tape feeder wherein the waste tape may be transported to a remote area and easily disposed of without encumbering the equipment.
In addition to the necessity of removing and disposing of the protective cover, the carrier tape also must be transported to a disposal area once the individual pieces have been removed from it. Normally this has been done by removing the back-up or carrier tape to a different area and possibly winding it on a further take-up roller. Hence, the protective cover and carrier tape are transported to different locations and must be disposed of separately. This obviously complicates the mechanism and does not permit a compact assembly.
It is, therefore, a still further object of this invention to provide a waste tape disposing structure wherein both a protective tape and a carrier tape may be removed to the same location and disposed of simultaneously.
It is a further object of this invention to provide a waste tape disposing means wherein both waste carrier and protective tapes can be reassembled and disposed of together.

Waste tape disposing means of tape feeder


A hockey stick shaft is a hollow, thin-walled tube formed of titanium or a titanium alloy. The tube wall has a thickness which may be uniform, tapered or stepped. The titanium or titanium alloy is of an alpha, a near-alpha, an alpha-beta or a highly-aged beta type. The titanium or titanium alloy has an elastic modulus greater than 13 million pounds per square inch (psi), a yield strength above 50,000 psi and a wall thickness ranging from 0.020 to 0.045 inches. An alternate hockey stick shaft has a titanium or titanium alloy core and exterior formed of a composite material. The titanium or titanium alloy core is of an alpha, a near-alpha, an alpha-beta or a beta type and has a yield strength above roughly 40,000 psi and a wall thickness ranging from 0.010 to 0.040 inches.

1. Technical Field
The invention relates generally to hockey sticks. More particularly, the invention relates to a hockey stick having a light-weight shaft which is highly durable, impact-damage-resistant and dynamically responsive. Specifically, the invention relates to a thin-walled hockey stick shaft made of titanium or a titanium alloy.
2. Background Information
Wood has been the traditional material of construction for ice and street hockey sticks. As such, the hard wood, Northern white-ash, is typically used in solid form for stick shafting (shafts) and blades. This hard wood has been attractive for hockey sticks based on high availability, flexibility, strength, hardness, ease of manufacturability into sticks, and, especially, low relative cost.
Produced from a natural product, however, wood sticks inherently exhibit strong property directionality (i.e. texture), a relatively low elastic modulus, weak areas from defects and/or grain and composition inconsistencies, significant variability in durability and stiffness, and property and dimensional changes and/or warpage over time (instability). Furthermore, wood is highly susceptible to mechanical damage (cracking, splitting, chipping, denting) when impacted, especially when damage is imposed parallel to the grain direction. Wood sticks can become brittle at either temperature extreme, and/or over time as the natural moisture content of the wood diminishes (i.e., dries out). Flexure characteristics can change over time with use. Wood also possesses inherent energy dampening qualities, which act to reduce elastic energy transfer (snap) from the stick to the puck being shot.
Some of these limitations with wood hockey sticks have been alleviated over the years through the application of fiberglass and/or carbon fiber reinforced plastic layers and laminates applied around the wood core. Not only does the fiberglass outer layer retard moisture egress from the wood core to extend stick shelf-life, it offers improved impact damage and cracking resistance to the wood. Furthermore, the glass and/or carbon fiber type and lay pattern can be used to enhance and control wood shaft and/or blade stiffness and dynamic response. Unfortunately, this fiberglass laminated and reinforced wood design results in fairly stiff and heavy hockey sticks (e.g., ˜660 grams for a one-piece stick).
In the pursuit to improve hockey stick durability, consistency, and achieve lower net weight, extruded hollow aluminum alloy shafts (thin-wall seamless rectangular tubulars) were introduced around the mid to late 1980's. With this design, a replaceable laminated wood blade is inserted (with hot glue) into the hosel end of the aluminum shaft. Aluminum alloys, such as the 7005 alloy typically used in tennis rackets and baseball bats, offered tempered yield strengths on the order of 45,000–50,000 pounds per square inch (psi), in combination with good flexibility (elastic modulus ˜10.1 million psi) and a low density of 0.10 lb/in3. In order to achieve the shaft stiffness and damage/impact tolerance required, these aluminum shafts were typically designed with 0.045–0.060″ thick constant or tapered walls. As a result, modest shaft weight reductions on the order of 10–15% were achieved over wood. This metal shaft also featured performance consistency, long-term stability, and damage tolerance/life extension, compared to wood sticks. The integration of composite materials with aluminum to create "hybrid" shafts in the early 1990's provided further means to trim shaft weight, enhance shaft dynamic response/energy transfer, and adjust/control stiffness. Here again, glass- and/or carbon-reinforced plastic laminates and/or Kevlar (aramid) wraps were applied over aluminum tubular core reinforcements to control stiffness and create flex points along the shaft length.
Despite these shaft material/design advances, commercial production of aluminum alloy hockey stick shafts has recently been discontinued. Fundamentally, this occurred due to the commercial availability of even lighter, more dynamically responsive, and often lower priced single-piece or two-piece all-composite sticks. Aluminum's inherent combination of lower strength and modulus properties limited the ability to design lighter weight sticks with the durability to withstand the rigors of hockey play. These aluminum shafts were known to suffer out-of-plane permanent set (yielding from bending), denting, and cracking in hosel corners.
With their market entry in the mid-1990's, all-composite shafts and one-piece sticks today represent approximately two-thirds of the hockey stick market in North America. Despite prices which can range from 3–6 times that of wood stocks, the current market predominance of all-composite hockey sticks/shafts primarily stems from three basic performance features:                1. Lower weight: Composite shafts typically weigh 280–340 grams, or roughly 460–500 grams for a one-piece hockey stick. This represents a net weight reduction in the range of 25–37% over wood. Lighter weight translates into a faster and/or harder shot.        2. A wider range of stiffness: Typically, offense players prefer less-stiff (more flexible) shaft response for puck control and wrist-shots with quick snap. Stiffer sticks are generally favored by defensemen for slap-shots. Shaft stiffness is often commercially rated on the unofficial scale of 70–120 lb/in, related to the load to achieve a shaft mid-span deflection of one inch.        3. Improved, consistent energy transfer: Composite shafts/sticks exhibit enhanced elastic energy storage and transfer to the puck compared to wood shafts. This stems from reduced matrix dampening and the nature of glass- and/or carbon-fiber lay. Unlike wood, these flex and energy characteristics are highly controlled and consistent from stick to stick.
Despite these attractive performance features, inadequate durability and impact damage tolerance of these fiber-reinforced plastic composites represent their greatest limitations. Composites are well known for their minimal resistance to impact damage which can produce undetectable, internal mechanical damage to the composite (e.g., fiber-matrix separation). This internal damage is very sensitive to the degree and direction of impact, and the shape-hardness of the impacting body. Although composite shafts may utilize Kevlar outer sheet wraps to mitigate impact damage to the composite substrate, brittle, cracking failure of composite shafts is still life limiting. This lack of durability is very serious since each all-composite shaft currently typically retails for $70–100, and the one-piece composite stick is typically priced in the range of $170–200. This poor stick life cycle cost scenario has recently financially impacted professional hockey teams, where replacement composite stick budgets have skyrocketed. Less critical durability issues with composites include effects at extreme temperature limits. Repeated overheating of the shaft hosel area incurred during blade replacement procedure using hot glue can produce composite blistering and weakening, whereas very cold outdoor winter temperatures can make sticks more prone to brittle fracture.
U.S. Pat. No. 5,863,268 granted to Birch discloses a metal goalkeeper's hockey stick, which has a blade and shaft which are preferably formed of an aluminum alloy, but which may also be formed of a titanium alloy. However, the Birch hockey stick is specifically one used by a goalie or goaltender, which is completely different than that of a "player" hockey stick, that is, one used by the players (forward and defense men) other than the goalie. Goalie sticks and player sticks are not interchangeable with one another and indeed each would be completely inadequate if used in the stead of the other.
The goalie hockey stick is configured for a completely different purpose than the player hockey stick. The goalie stick is configured primarily for blocking shots or deflecting shots away and thus utilizes a substantially enlarged blade for that purpose, along with a substantially shortened shaft. By contrast, the player sticks are alternately used for maneuvering and/or passing the puck quickly while sometimes skating at high speeds; making wrist-shots with quick snap; and making slap-shots which launch the puck at high speed. Thus, sticks with various stiffness and flex characteristics are important in player sticks. Typically, forward or offensive players prefer less-stiff (more flexible) shaft response for puck control and wrist-shots with quick snap. Stiffer sticks are generally favored by defense men for slap-shots.
In keeping with the difference in purposes of the sticks, the blade of the goalie stick, as shown by Birch, has a horizontal portion and an upstanding portion which is substantially longer than (nearly twice as long as) the horizontal portion. In addition, the upstanding portion of the blade is roughly the same width as the horizontal portion. By contrast, the blade of the player stick has a relatively short upwardly extending portion, mainly for the purpose of providing a transition for connecting to the shaft. This upwardly extending portion is also substantially narrower than the horizontal portion of the player blade.
While the Birch shaft is a hollow tube, it is substantially shorter at approximately 32 inches than the shaft of the typical player hockey stick, which is roughly 50 inches, although this varies. Due in part to the relatively long upstanding portion of the goalie blade, a longer shaft is not suitable for use with the goalie stick. The substantially longer shaft of the player stick alone creates a completely different dynamic aspect from that of a goalie stick shaft. As a result of the distinct purpose and the correspondingly different size, the player stick shaft must incorporate various parameters quite distinct from those of the goalie stick shaft.


In at least one embodiment, a battery is provided comprising an anode and cathode, a separator between the anode and cathode, and a shutdown layer between the separator and the anode or cathode. The shutdown layer may include low melting point material and a conductive material within the low melting point material forming a conductive network within the shutdown layer. At a melting point temperature of the low melting point material, the conductive network is reduced such that at least a portion of the shutdown layer is substantially electrically non-conductive. The shutdown layer may be a free-standing layer or may be coated one or both of the electrodes.

The term "electric vehicle" as used herein, includes vehicles having an electric motor for vehicle propulsion, such as battery electric vehicles (BEV), hybrid electric vehicles (HEV), and plug-in hybrid electric vehicles (PHEV). A BEV includes an electric motor, wherein the energy source for the motor is a battery that is re-chargeable from an external electric grid. A HEV includes an internal combustion engine and an electric motor, wherein the energy source for the engine is fuel and the energy source for the motor is a battery. A PHEV is like a HEV, but the PHEV has a larger capacity battery that is rechargeable from the external electric grid. Lithium-ion (Li-ion) batteries are used in BEV, HEV, and PHEV. Due to the nature of vehicle application, these Li-ion batteries are exposed to potential electrical and mechanical abuse during their lifetime. Such abuse may induce a short-circuit internal to the battery cell.

Rechargeable battery with shutdown layer comprising a low melting point material and an electrically conductive material


Provided is a low density parity check decoder, which includes a bit node calculating unit configured to calculate a bit node, a check node calculating unit configured to calculate a check node, a control unit configured to control calculation of the bit node and the check node, and a storage unit configured to store calculation values of the bit node or the check node, wherein the control unit calculates the bit node or the check node so that the node calculations are overlapped, by using an address offset value of the storage unit, thereby reducing a decoding time.

A communication system uses an error correcting code in order to ensure reliable communication through a channel. A low density parity check (LDPC) code exhibiting performance close to the Shannon limit is a representative error correcting code. The LDPC code has higher performance in comparison to a turbo code as a message size is greater, and does not show an error floor at relatively high SNR (Signal to Noise Ratio). The LDPC code may be expressed using a Tanner graph which shows a connection state according to edges between a bit node and a check node. A LDPC decoder operates by operating and updating information transferred along the edges between nodes on the Tanner graph.
Generally, the LDPC code has very great coding complexity, and thus leads to excessive use of a system storage and becomes a main restraint factor when implementing LDPC codes. In addition, when implementing LDPC codes, access conflict among memories storing bit nodes, check nodes, and their input/output values may cause serious problems. Therefore, an efficient decoder structure capable of solving these problems is needed.

DVB-S2 LDPC decoder using overlapped decoding scheme

KOREA UNIVERSITY RESEARCH AND BUSINESS FOUNDATION


A semiconductor device includes an n+ type semiconductor substrate 1 and a super junction region that has, on the top of the substrate 1, an n and p type pillar regions 2 and 3 provided alternately. The device also includes, in the top surface of the super junction region, a p type base region 4 and an n type source layer 5. The device also includes a gate electrode 7 on the region 4 and layer 5 via a gate-insulating film 6, a drain electrode 9 on the bottom of the substrate 1, and a source electrode 8 on the top of the substrate 1. In the top surface of the super junction region in the terminal region, a RESURF region 10 is formed. The RESURF region has a comb-like planar shape with repeatedly-formed teeth having tips facing the end portion of the terminal region.

1. Field of the Invention
The present invention relates to a semiconductor device, and more particularly, to a semiconductor device including a super junction region.
2. Description of the Related Art
Vertical power metal oxide semiconductor field effect transistors (MOSFET) each have an ON-resistance that largely depends on the electrical resistance of the conductive layer (drift layer). The drift layer's electrical resistance depends on the impurity concentration thereof. A higher impurity concentration causes a lower ON-resistance. The higher impurity concentration, however, provides a lower breakdown voltage of the pn junction between the drift layer and the base layer. The impurity concentration thus cannot be higher than a limit level based on a breakdown voltage. There is a trade-off between the device breakdown voltage and the ON-resistance. It is important to improve the trade-off to provide a low power consumption semiconductor device. The trade-off has a limit level based on the device material. Providing a trade-off beyond the limit level is the way to achieve the low ON-resistance semiconductor device.
A known example of the MOSFET to solve the problems has a super junction region in the drift layer. The super junction region has vertical strip p and n type pillar regions. The two type pillar regions are alternately embedded in a lateral direction. The super junction region has the same charge amount (impurity amount) in the p and n type pillar regions to form a pseudo non-doped layer. The non-doped layer may hold the high breakdown voltage. The super junction region also has a highly doped n type pillar region through which a current passes through. The low ON-resistance beyond the material limit is thus provided.
In the semiconductor device having the super junction region, in order for the device region to hold the high breakdown voltage, the impurity amount should be accurately controlled in the n and p type pillar regions. Like the device region, the terminal region in the semiconductor device may be provided with a high concentration n type pillar region and also a high concentration p type pillar region to provide the high breakdown voltage. In the terminal region, the depletion layer may be extended both in the longitudinal direction of the alternately embedded pillar regions and in the direction perpendicular thereto. The electric field concentration may thus be reduced at the end portion of the p type base layer extending to the terminal region. The high breakdown voltage may thus be provided. In order to extend the depletion layer in the direction perpendicular to the longitudinal direction of the alternately embedded pillar regions, a known configuration includes a RESURF region and a field plate electrode in the surface of the terminal region (see, for example, JP 2003-273355).
Variation of the impurity amount of the p and n type pillar regions in the super junction region in the semiconductor device will decrease the breakdown voltage of the device region and the terminal region. Variation of the impurity amount of the p and n type pillar regions in the super junction region in the terminal region will change the electric field distribution in the terminal region. The electric field distribution change in the terminal region may generate a local electric field concentration. The electric field concentration may contribute to the reliability reduction, including the leak current variation, and the device breakdown due to the breakdown voltage reduction in the terminal region.

Semiconductor device including a resurf region with forward tapered teeth