WO2005047281A1 - Novel herbicides - Google Patents

Novel herbicides Download PDF

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WO2005047281A1
WO2005047281A1 PCT/EP2004/012878 EP2004012878W WO2005047281A1 WO 2005047281 A1 WO2005047281 A1 WO 2005047281A1 EP 2004012878 W EP2004012878 W EP 2004012878W WO 2005047281 A1 WO2005047281 A1 WO 2005047281A1
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crc
halo
amino
formyl
cyano
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PCT/EP2004/012878
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French (fr)
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Ottmar Franz Hueter
Hans-Georg Brunner
Michel Muehlebach
Anthony O'sullivan
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Syngenta Participations Ag
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Publication of WO2005047281A1 publication Critical patent/WO2005047281A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/54—1,3-Diazines; Hydrogenated 1,3-diazines

Definitions

  • the present invention relates to novel, herbicidally active pyrimidino-imidazoles, to processes for their preparation, to compositions comprising those compounds, and to their use in controlling weeds, especially in crops of useful plants, or in inhibiting plant growth.
  • Pyrimidino-imidazoles are described, for example, as intermediates for the synthesis of angiotensin II antagonists in WO 95/22543 and also as antibacterials in WO 03/004509 and WO 02/083111.
  • the present invention accordingly relates to compounds of formula I
  • Ri is hydrogen, halogen, cyano, amino, hydroxy, nitro, formyl, -COOH, -CONH 2> -CSNH 2 , C ⁇ -C 6 alkyl, halo-C C 6 alkyl, C C 6 alkoxy, halo-C C 6 alkoxy, d-Cealkylamino, halo-C- ⁇ -C 6 - alkylamino, CrC 6 dialkylamino wherein the alkyl groups are the same or different or together with the nitrogen atom to which they are bonded form a 4- to 7-membered ring which may contain a further hetero atom selected from N, O and S, halo-C C 6 dialkylamino wherein the alkyl groups are the same or different, (C ⁇ -C 6 alkyl)S(O) m , (halo-CrC 6 alkyl)S(O) m , (CrC 6 alkylamino)S(O) m , where
  • R 2 is hydrogen, cyano, hydroxy, amino, formyl, -CONH 2 , -CSNH 2 , d-C 6 alkyl; C C 6 alkyl substituted by halogen, amino, d-C 6 alkylamino, d-C 6 dialkylamino, hydroxy, cyano, d-C - alkoxy or by formyl; d-C 6 alkoxy; d-C 6 alkoxy substituted by halogen, amino, d-C 6 alkyl- amino, C ⁇ -C 6 dialkylamino, hydroxy, cyano, C C 4 alkoxy or by formyl; d-C 6 alkylamino, halo- CrC 6 alkylamino, CrC 6 dialkylamino wherein the alkyl groups are the same or different, halo- C ⁇ -C 6 dialkylamino wherein the alkyl groups are the same or different, (C ⁇ -C 6 alkyl)S(O)
  • R 3 is hydrogen, halogen, cyano, amino, hydroxy, nitro, formyl, -COOH, -CONH 2 , -CSNH 2 , d-Cealkyl, halo-CrC 6 alkyl, CrC 6 alkoxy, halo-CrC 6 alkoxy, CrC 6 alkylamino, halo-CrC 6 - alkylamino, Crddialkylamino wherein the alkyl groups are the same or different or together with the nitrogen atom to which they are bonded form a 4- to 7-membered ring which may be interrupted by N, O or S, halo-d-C 6 dialkylamino wherein the alkyl groups are the same or different, (d-C 6 alkyl)S(O) m , (halo-d-C 6 alkyl)S(O) m , (d-C 6 alkyIamino)S(O) m , (d-C 6 dialky
  • R 4 is hydrogen, halogen, cyano, amino, nitro, formyl, -COOH, -CONH 2 , -CSNH 2 , d-C 6 alkyI, halo-CrC 6 alkyl, d-C 6 alkoxy, halo-CrC 6 alkoxy, CrC 6 alkylamino, CrC 6 dialkylamino wherein the alkyl groups are the same or different or together with the nitrogen atom to which they are bonded form a 4- to 7-membered ring, halo-CrC 6 dialkylamino wherein the alkyl groups are the same or different, (CrC 6 alkyl)S(O) m , (halo-C 1 -C 6 alkyl)S(O) ITl , d-Cealkoxy-d-Cealkyl, halo-CrC 6 alkoxy-CrC 6 alkyl, d-C 6 alkylcarbonyl; CrC
  • A is d-C alkylene; CrC 4 alkylene substituted by halogen, amino, d-C 6 alkylamino, CrCedialkylamino, hydroxy, cyano, d-C alkoxy or by formyl; d-C oxyalkylene; CrC 4 oxyalkylene substituted by halogen, amino, d-C 6 alkylamino, CrCedialkylamino, hydroxy, cyano, d-C 4 alkoxy or by formyl; CrC 4 alkyleneoxy; CrC 4 alkyleneoxy substituted by halogen, amino, d-Cealkylamino, d-C 6 dialkylamino, hydroxy, cyano, d-C alkoxy or by formyl; C C 4 oxy- alkyleneoxy; d-C oxyalkyIeneoxy substituted by halogen, amino, d-Cealkylamino, CrCedialkylamino, hydroxy,
  • Q is aryl, aryl substituted one or more times by halogen, cyano, hydroxy, amino, nitro, formyl, -COOH, -CONH ⁇ , -CSNH 2 , d-Cealkyl, halo-d-C 6 alkyl, CrC 6 alkoxy, halo-C C 6 aIkoxy, CrC 6 alkylamino, halo-CrC 6 alkylamino, d-Cedialkylamino wherein the alkyl groups are the same or different or together with the nitrogen atom to which they are bonded form a 4- to 7- membered ring, halo-CrC 6 dialkylamino wherein the alkyl groups are the same or different, (CrC 6 alkyl)S(O) m> (haIo-C C 6 alkyl)S(O) m , (CrC 6 alkylamino)S(O) m , (CrC 6
  • alkyl as a group perse or as a structural element in other substituents, for example in alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, alkylcarbonyl, alkoxycarbonyl, alkylamino, aikoxyiminomethyl, alkylaminocarbonyl and alkylaminothio- carbonyl, is either straight-chain alkyl, that is to say, for example, methyl, ethyl, propyl, butyl, pentyl or hexyl, or branched alkyl, for example isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl or isohexyl.
  • the alkyl radicals may be substituted by one or more substituents such as halogen, amino, d-C 6 alkylamino, d-Cedialkylamino, hydroxy, cyano, formyl or C r C 4 alkoxy.
  • substituents such as halogen, amino, d-C 6 alkylamino, d-Cedialkylamino, hydroxy, cyano, formyl or C r C 4 alkoxy.
  • radicals such as dialkyl-, dialkenyl- or dialkynyl-amino, both the alkyl groups may have the number of carbon atoms specified in the definition.
  • Alkenyl as a group perse or as a structural element in other substituents, for example in alkenyloxy, is either straight-chained, for example vinyl, 1-methylvinyl, allyl, 1 -butenyl or 2- hexenyl, or branched, for example isopropenyl.
  • the alkenyl radicals may be substituted by one or more substituents such as halogen, amino, CrC 6 alkylamino, d-Cedialkylamino, hydroxy, cyano, formyl or d-C 4 alkoxy.
  • Alkynyl as a group perse or as a structural element in other substituents, for example in alkynyloxy, is either straight-chained, for example propargyl, 2-butynyl or 5-hexynyl, or branched, for example 2-ethynylpropyl or 2-propargylisopropyl.
  • the alkynyl radicals may be substituted by one or more substituents such as halogen, amino, CrC 6 alkylamino, CrC 6 dialkylamino, hydroxy, cyano, tri(CrC 6 alkyl)silyl, formyl or d-C 4 alkoxy.
  • Cycloalkyl is cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.
  • the cycloalkyl radicals may be substituted by one or more radicals such as halogen, amino, CrC 6 alkylamino, d-Cedialkylamino, hydroxy, cyano, formyl or d-C 4 alkoxy.
  • Alkylene as a group perse or as a structural element in other groups, for example in haloalkylene, is either straight-chained, for example -CH 2 CH 2 -, -CH 2 CH 2 CH 2 - or -CH 2 CH 2 CH 2 CH 2 -, or branched, for example -CH(CH 3 )-, -CH(C 2 H 5 )-, -C(CH 3 ) 2 -, -CH(CH 3 )CH 2 - or -CH(CH 3 )CH(CH 3 )-.
  • the alkylene radicals may be substituted by one or more radicals such as halogen, amino, d-Cealkylamino, d-C 6 dialkylamino, hydroxy, cyano, formyl or d-C 4 alkoxy.
  • Aryl is preferably phenyl or naphthyl, especially phenyl.
  • the aryl radicals may be substituted by one or more radicals such as halogen, cyano, hydroxy, amino, nitro, formyl, -COOH, -CONHg, -CSNH 2 , d-Cealkyl, halo-CrC 6 alkyl, CrC 6 alkoxy, halo-C C 6 alkoxy, d-Cealkylamino, halo-CrC 6 alkylamino, CrC 6 dialkylamino wherein the alkyl groups are the same or different or together with the nitrogen atom to which they are bonded form a 4- to 7- membered ring, halo-CrC 6 dialkylamino wherein the alkyl groups are the same or different, (CrC 6 alkyl)S(O) m , (halo-CrCealkyl)S(O) m , (
  • heterocycles in the definitions of Q preference is given to 5- or 6-membered aromatic rings containing one to three hetero atoms especially selected from the group consisting of N, O and S.
  • Preferred heterocycles are pyrazinyl, pyridyl(3'), pyridyl(2'), pyridyl(4'), pyrimidinyl(2'), pyrimidinyl(4'), pyrimidinyl(5'), pyridazinyl(3'), pyridazinyl(4'), thiazolyl(2'), thiazolyl(4'), thiazolyl(5'), pyrrolyl(2'), pyrrolyl(3'), pyrazolyl(3'), pyrazolyl(4'), pyrazolyl(5'), oxazoly
  • the heterocycles may be substituted by one or more radicals such as halogen, cyano, hydroxy, amino, nitro, formyl, -COOH, -CONH 2 , -CSNH 2 , Crdalkyl, halo-d-C 6 alkyl, CrC 6 alkoxy, halo-CrC 6 alkoxy, CrC 6 alkylamino, halo- CrC 6 alkylamino, CrCedialkylamino wherein the alkyl groups are the same or different or together with the nitrogen atom to which they are bonded form a 4- to 7-membered ring, halo-CrC 6 dialkylamino wherein the alkyl groups are the same or different, (CrC 6 alkyl)S(O) m , (halo-CrC 6 alkyl)S(O) m , (CrC 6 alkylamino)S(O) m , (CrC 6 dialkylamino)S
  • the non-aromatic heterocycles may, in addition, contain one or more carbonyl groups, for example 2-pyrrolidonyl(1'), succinimidyl(l'), gamma-butyrolactonyl(3'), ethylene- carbonatyl(4'), tetrahydrothiophen-3-onyl(2'), tetrahydro-2H-pyran-2-onyl(3'), tetrahydro-4H- pyran-4-onyl(3'), 2-piperidonyl(1 '), epsilon-caprolactamyl(l ').
  • 2-pyrrolidonyl(1') succinimidyl(l'), gamma-butyrolactonyl(3'), ethylene- carbonatyl(4'), tetrahydrothiophen-3-onyl(2'), tetrahydro-2H-pyran-2-onyl(3'), tetrahydro-4
  • Halogen as a group perse or as a structural element in other substituents, for example in haloalkyl, haloalkenyl and haloalkynyl, is fluorine, chlorine, bromine or iodine, especially fluorine, chlorine or bromine, more especially fluorine or chlorine, very especially fluorine.
  • Halo-substituted substituents such as haloalkyl, haloalkenyl and haloalkynyl, may be partially halogenated or perhalogenated, it being possible in the case of polyhalogenation for the halogen substituents to be the same or different.
  • haloalkyl as a group per se or as a structural element in other substituents such as haloalkenyl, are methyl substituted from one to three times by fluorine, chlorine and/or bromine, such as CHF 2 or CF 3 ; ethyl substituted from one to five times by fluorine, chlorine and/or bromine, such as CH 2 CF 3 , CF 2 CF 3 , CF 2 CCI 3 , CF 2 CHCI 2 , CF 2 CHF 2) CF 2 CFCI 2l CF 2 CHBr 2 , CF 2 CHCIF, CF 2 CHBrF or CCIFCHCIF; propyl or isopropyl substituted from one to seven times by fluorine, chlorine and/or bromine, such as CH 2 CHBrCH 2 Br, CF 2 CHFCF 3 , CH 2 CF 2 CF 3 , CF(CF 3 ) 2 or CH(CF 3 ) 2 ; and butyl or one of its is
  • Compounds of formula I having at least one basic centre are capable of forming acid addition salts.
  • Those acid addition salts are formed, for example, with strong inorganic acids, such as mineral acids, e.g. perchloric acid, sulfuric acid, nitric acid, nitrous acid, a phosphoric acid or a hydrohalic acid, with strong organic carboxylic acids, such as substituted, e.g. halo-substituted, C r C 4 alkanecarboxylic acids, e.g. acetic acid, saturated or unsaturated dicarboxylic acids, e.g.
  • strong inorganic acids such as mineral acids, e.g. perchloric acid, sulfuric acid, nitric acid, nitrous acid, a phosphoric acid or a hydrohalic acid
  • strong organic carboxylic acids such as substituted, e.g. halo-substituted, C r C 4 alkanecarboxylic acids, e.g
  • oxalic, malonic, succinic, maleic, fumaric and phthalic acid hydroxycarboxylic acids, e.g. ascorbic, lactic, malic, tartaric and citric acid, or benzoic acid, or with organic sulfonic acids, such as unsubstituted or substituted, e.g. halo- substituted, d-C alkane- or aryl-sulfonic acids, e.g. methane- or p-toluene-sulfonic acid.
  • compounds of formula I having at least one acid group are capable of forming salts with bases.
  • Suitable salts with bases are, for example, metal salts, such as alkali metal and alkaline earth metal salts, e.g. sodium, potassium and magnesium salts, and salts with ammonia or an organic amine, such as morpholine, piperidine, pyrrolidine, a mono-, di- or tri- lower alkylamine, e.g. ethyl-, diethyl-, triethyl- or dimethyl-propyl-amine, or a mono-, di- or tri- hydroxy-lower alkylamine, e.g. mono-, di- or tri-ethanolamine.
  • corresponding internal salts may optionally be formed.
  • Preferred compounds of formula I are those wherein the substituent R 4 is hydrogen.
  • a further group of preferred compounds of formula I comprises those wherein R is hydrogen and R 3 is halogen or methyl.
  • R 4 is hydrogen and R- ⁇ is halogen, ha!o-d-C 6 alkyl or (CrC 6 alkyl)S(O) m , wherein m is 0, 1 or 2.
  • R 4 is hydrogen
  • R 3 is bromine, chlorine or methyl
  • Ri is halogen, halo-CrC 6 alkyl or (CrC 6 alkyl)S(O) m , wherein m is 0, 1 or 2.
  • the compounds of formula I can be prepared by means of processes, known per se and described, for example, in WO 95/22543, wherein pyrimidines functionalised in the 5-position and imidazoles functionalised in the 4-position are linked catalytically or 5-(2-haloalkyl- carbonyl)-pyrimidines are cyclised with amidines, by, for example, reacting a suitable trialkyltin-imidazole with a suitable 5-bromo-pyrimidine under palladium catalysis.
  • other imidazole compounds e.g. imidazole-boronic acids, imidazole zinc compounds or imidazole magnesium compounds, can also be reacted with 5-halo- or 5- triflate-pyrimidines under transition metal catalysis, preferably palladium or nickel catalysis.
  • X leaving group, e.g. Br, Cl, OSO 2 CF 3
  • the trialkyltin-imidazoles, imidazole-boronic acids, imidazole zinc compounds and imidazole magnesium compounds can be prepared using methods known per se from the imidazole unsubstituted in the 4-position by deprotonation using an organolithium compound, e.g. n- butyllithium, and subsequent transmetallation.
  • the trialkyltin-imidazoles, imidazole-boronic acids, imidazole zinc compounds and imidazole magnesium compounds can be prepared by halogen-metal exchange starting from a 4-halo-imidazole and using an organolithium compound, e.g. n-butyllithium, or using magnesium or an organomagnesium compound and subsequent transmetallation.
  • the 5-trialkyltin-pyrimidines, pyrimidine-5-boronic acids, pyrimidine-5-zinc compounds and pyrimidine-5-magnesium compounds can be prepared using methods known perse from the pyrimidine unsubstituted in the 5-position by deprotonation using an organolithium compound, e.g. n-butyllithium, and subsequent transmetallation.
  • an organolithium compound e.g. n-butyllithium
  • the 5-trialkyltin- pyrimidines, pyrimidine-5-boronic acids, pyrimidine-5-zinc compounds and pyrimidine-5- magnesium compounds can be prepared by halogen-metal exchange starting from a 5-haIo- pyrimidine and using an organolithium compound, e.g. n-butyllithium, or using magnesium or an organomagnesium compound and subsequent transmetallation.
  • the compounds of formula I can also be obtained by cyclisation of 5-(2-haloalkylcarbonyl)- pyrimidines, especially 5-(2-bromoalkylcarbonyl)-pyrimidines with amidines.
  • the NH group of the imidazole can subsequently be derivatised with an electrophile. 15
  • 5-(2-Haloalkylcarbonyl)-pyrimidines are obtained, for example, by halogenation of 5- (alkylcarbonyl)-pyrimidines or 5-(2-hydroxyalkylcarbonyl)-pyrimidines using a halogenating agent.
  • Y H
  • OH halogenating agent e.g. HBr
  • Br 2 X I, Br, Cl
  • a further method for the preparation of 5-(alkylcarbonyl)-pyrimidines starts from 5-halo- pyrimidines, preferably 5-bromo-pyrimidines, which, under transition metal catalysis, preferably palladium or nickel catalysis, in the presence of carbon monoxide and an alcohol, are converted into the 5-alkyloxycarbonyl compounds.
  • the 5-alkyloxycarbonyl compounds can be converted into the 5-(alkylcarbonyl)-pyrimidines by methods known perse, e.g. by reaction with malonic acid derivatives and subsequent hydrolysis.
  • alkyl-alcohol, CO solvent
  • aprotic, inert, organic solvents are hydrocarbons, e.g. benzene, toluene, xylene or cyclohexane, chlorinated hydrocarbons, e.g. dichloromethane, trichloromethane, tetrachloro- methane or chlorobenzene, ethers, e.g. diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran or dioxane, nitriles, e.g. acetonitrile or propionitrile, and amides, e.g.
  • hydrocarbons e.g. benzene, toluene, xylene or cyclohexane
  • chlorinated hydrocarbons e.g. dichloromethane, trichloromethane, tetrachloro- methane or chlorobenzene
  • ethers
  • reaction temperatures are preferably from -78°C to +120°C.
  • the reactions are generally slightly exothermic and may usually be carried out at room temperature. In order to shorten the reaction time or else to initiate the reaction, brief heating up to the boiling point of the reaction mixture may be carried out, where appropriate.
  • the reaction times may also be reduced by adding a few drops of base as reaction catalyst.
  • bases are tertiary amines, e.g.
  • inorganic bases such as hydrides, e.g. sodium or calcium hydride, hydroxides, e.g. sodium or potassium hydroxide, carbonates, e.g. sodium or potassium carbonate, or hydrogen carbonates, e.g. potassium or sodium hydrogen carbonate, to be used as bases.
  • hydrides e.g. sodium or calcium hydride
  • hydroxides e.g. sodium or potassium hydroxide
  • carbonates e.g. sodium or potassium carbonate
  • hydrogen carbonates e.g. potassium or sodium hydrogen carbonate
  • the compounds of formula I may be isolated in conventional manner by concentration and/or evaporation of the solvent and purified by recrystallisation or trituration of the solid residue in solvents in which they are not readily soluble, such as ethers, aromatic hydrocarbons or chlorinated hydrocarbons.
  • the present invention relates also to herbicidal compositions which, in addition to comprising customary inert formulation adjuvants, comprise as active ingredient a compound of formula I
  • R 1 is hydrogen, halogen, cyano, amino, hydroxy, nitro, formyl, -COOH, -CONH 2 , -CSNH 2 , Crdalkyl, halo-d-C 6 alkyl, d-C 6 alkoxy, halo-C C 6 alkoxy, CrC 6 alkylamino, halo-d-dr alkylamino, CrCedialkylamino wherein the alkyl groups are the same or different or together with the nitrogen atom to which they are bonded form a 4- to 7-rr ⁇ embered ring which may be interrupted by a further N, O or S, halo-d-C 6 dialkyIamino wherein the alkyl groups are the same or different, (d-C 6 alkyl)S(O) m , (halo-C r C 6 alkyl)S(O) m , (d-Cealkylamino ⁇ O)TM (d- C 6 dialkyI
  • R 2 is hydrogen, cyano, hydroxy, amino, formyl, -CONH 2 , -CSNH 2 , CrC 6 alkyl; CrC 6 alkyl substituted by halogen, amino, d-Cealkylamino, d-Cedialkylamino, hydroxy, cyano, Crdalkoxy or by formyl; d-C 6 alkoxy; Crdalkoxy substituted by halogen, amino, CrCealkylamino, CrC 6 dialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; CrC 6 alkyIamino, halo- CrC 6 alkylamino, CrCedialkylamino wherein the alkyl groups are the same or different, halo- d-Cedialkylamino wherein the alkyl groups are the same or different, (CrCealkyl)S(O) m , (halo-CrC 6 alkyl
  • R 3 is hydrogen, halogen, cyano, amino, hydroxy, nitro, formyl, -COOH, -CONH 2 , -CSNH 2 , Crdalkyl, halo-d-C 6 alkyl, CrC 6 alkoxy, halo-CrC 6 alkoxy, d-C 6 alkylamino, halo-C C 6 - alkylamino, CrC 6 dialkylamino wherein the alkyl groups are the same or different or together with the nitrogen atom to which they are bonded form a 4- to 7-membered ring which may be interrupted by a hetero atom such as N, O or S, halo-d-C 6 dialkylamino wherein the alkyl groups are the same or different, (CrC 6 alkyl)S(O) m , (halo-CrC 6 alkyl)S(O) m , (CrC 6 alkyl- amino)S(O) m , (C
  • R 4 is hydrogen, halogen, cyano, amino, nitro, formyl, -COOH, -CONH 2 , -CSNH 2 , d-C 6 alkyl, halo-d-C 6 alkyl, Crdalkoxy, halo-d-dalkoxy, d-Cealkylamino, CrCedialkylamino wherein the alkyl groups are the same or different or together with the nitrogen atom to which they are bonded form a 4- to 7-membered ring, halo-Crddialkylamino wherein the alkyl groups are the same or different, (CrC ⁇ alkyl)S(O) m> (halo-d-C 6 alkyl)S(O)m, Crdalkoxy-CrCealkyl, halo-CrC 6 alkoxy-CrC 6 alkyl, C C 6 alkylcarbonyl; d-dalkylcarbonyl substituted by
  • A is d-dalkylene; d-C 4 alkylene substituted by halogen, amino, d-Cealkylamino, d-Cedialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; d-C 4 oxyalkylene; C C 4 oxyalkylene substituted by halogen, amino, d-dalkylamino, Crddialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; d-dalkyleneoxy; d-dalkyleneoxy substituted by halogen, amino, CrC 6 alkylamino, CrC 6 dialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; d-C 4 oxy- alkyleneoxy; CrC oxyalkyleneoxy substituted by halogen, amino, d-Cealkylamino, C n -C 6 di- alkylamino
  • Q is aryl, aryl substituted one or more times by halogen, cyano, hydroxy, amino, nitro, formyl, -COOH, -CONH 2 , -CSNH 2 , d-dalkyl, halo-d-dalkyl, C C 6 alkoxy, haIo-C ⁇ -C 6 alkoxy, CrC 6 alkylamino, halo-CrC 6 alkylamino, CrC 6 dialkylamino wherein the alkyl groups are the same or different or together with the nitrogen atom to which they are bonded form a 4- to 7- membered ring, halo-d-C 6 dialkylamino wherein the alkyl groups are the same or different, (d-C 6 alkyl)S(O) m , (halo-CrC 6 alkyl)S(O) m , (CrC 6 alkylamino)S(O) m , (C r C 6 dialkyl
  • the compounds of formula I may be used as herbicides in their unmodified form, that is to say as obtained in the synthesis, but they are preferably formulated in customary manner together with the adjuvants conventionally employed in formulation technology, for example into emulsifiable concentrates, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granules or microcapsules.
  • Such formulations are described, for example, on pages 9 to 13 of WO 97/34485.
  • the methods of application such as spraying, atomising, dusting, wetting, scattering or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances.
  • compositions, preparations or mixtures comprising the compound (active ingredient) of formula I, or at least one compound of formula I, and, usually, one or more solid or liquid formulation adjuvants, are prepared in known manner, e.g. by homogeneously mixing and/or grinding the active ingredient(s) with the formulation adjuvants, for example solvents or solid carriers.
  • formulation adjuvants for example solvents or solid carriers.
  • Surface-active compounds surfactants
  • solvents and solid carriers are given, for example, on page 6 of WO 9 7 /34485.
  • suitable surface- active compounds are non-ionic, cationic and/or anionic surfactants and surfactant mixtures having good emulsifying, dispersing and wetting properties.
  • Suitable anionic, non-ionic and cationic surfactants are listed, for example, on pages 7 and 8 of WO 97/34485.
  • the surfactants conventionally employed in formulation technology which are described, inter alia, in "McCutcheon's Detergents and Emulsifiers Annual” MC Publishing Corp., Ridgewood New Jersey, 1981 , Stache, H., "Tensid-Taschenbuch", Carl Hanser Verlag, Kunststoff/Vienna, 1981 , and M. and J. Ash, "Encyclopedia of Surfactants", Vol. I-III, Chemical Publishing Co., New York, 1980-81 , are also suitable for the preparation of the herbicidal compositions according to the invention.
  • the herbicidal formulations generally contain from 0.1 to 99 % by weight, especially from 0.1 to 95 % by weight, of herbicide, from 1 to 99.9 % by weight, especially from 5 to 99.8 % by weight, of a solid or liquid formulation adjuvant, and from 0 to 25 % by weight, especially from 0.1 to 25 % by weight, of a surfactant.
  • a surfactant especially from 0.1 to 25 % by weight
  • compositions may also comprise further ingredients, such as stabilisers, for example vegetable oils or epoxidised vegetable oils (epoxidised coconut oil, rapeseed oil or soybean oil), anti-foams, for example silicone oil, preservatives, viscosity regulators, binders, tackifiers, and also fertilisers or other active ingredients.
  • stabilisers for example vegetable oils or epoxidised vegetable oils (epoxidised coconut oil, rapeseed oil or soybean oil), anti-foams, for example silicone oil, preservatives, viscosity regulators, binders, tackifiers, and also fertilisers or other active ingredients.
  • the compounds of formula I are generally applied to the plant or the locus thereof at rates of application of from 0.001 to 4 kg/ha, especially from 0.005 to 2 kg/ha.
  • concentration required to achieve the desired effect can be determined by experiment. It is dependent on the nature of the action, the stage of development of the cultivated plant and of the weed and on the application (place, time, method) and may vary within wide limits as a function of those parameters.
  • the compounds of formula I are distinguished by herbicidal and growth-inhibiting properties, allowing them to be used in crops of useful plants, especially cereals, cotton, soybeans, sugar beet, sugar cane, plantation crops, rape, maize and rice, and also for non-selective weed control.
  • crops of useful plants especially cereals, cotton, soybeans, sugar beet, sugar cane, plantation crops, rape, maize and rice, and also for non-selective weed control.
  • crops is to be understood as including also crops that have been made tolerant to herbicides or classes of herbicides as a result of conventional methods of breeding or genetic engineering techniques.
  • the weeds to be controlled may be either monocotyledonous or dicotyledonous weeds, such as, for example, Stellaria, Nasturtium, Agrostis, Digitaria, Avena, Setaria, Sinapis, Lolium, Solanum, Echinochloa, Scirpus, Monochoria, Sagittaria, Bromus, Alopecurus, Sorghum halepense, Rottboellia, Cyperus, Abutilon, Sida, Xanthium, Amaranthus, Chenopodium, Ipomoea, Chrysanthemum, Galium, Viola and Veronica.
  • Stellaria Nasturtium, Agrostis, Digitaria, Avena, Setaria, Sinapis, Lolium, Solanum, Echinochloa, Scirpus, Monochoria, Sagittaria, Bromus, Alopecurus, Sorghum halepense, Rottboellia, Cyperus, Abutilon,
  • Example P-2 Preparation of 2-amino-5-(5-chloro-1 -methyI-2-trifluoromethyl-1 H-imidazol-4- yl)-pyrimidine
  • the intermediate is dissolved in 100 ml of methylene chloride and, after adding 10.26 g (1.2 eq.) of pyridinium dichromate, is stirred for 20 hours at room temperature.
  • the reaction mixture is filtered over Hyflo.
  • the organic phase is washed with H 2 O/brine, dried and concentrated.
  • 0.95 g of the title product is obtained in the form of a colourless oil.
  • Example P-5 D Preparation of 5-(1 ,5-dimethyl-2-trifluoromethyl-1 H-imidazol-4-yl)-pyrimidine
  • Example B1 Herbicidal action prior to emergence of the plants (pre-emerqence action) Monocotyledonous and dicotyledonous test plants are sown in standard soil in pots. Immediately after sowing, the test compounds, in the form of an aqueous suspension (prepared from a wettable powder (Example F3, b) according to WO 97/34485) or in the form of an emulsion (prepared from an emulsifiable concentrate (Example F1 , c) according to WO 97/34485), are applied by spraying, in an optimum concentration (500 litres of water per ha). The test plants are then grown in a greenhouse under optimum conditions.
  • an aqueous suspension prepared from a wettable powder (Example F3, b) according to WO 97/34485)
  • an emulsion prepared from an emulsifiable concentrate (Example F1 , c) according to WO 97/34485
  • the test is evaluated after a test duration of 4 weeks.
  • the compounds according to Tables 1 and 2 exhibit good to very good herbicidal action.
  • the same results are obtained when the compounds of formula I are formulated in accordance with the other Examples according to WO 97/34485.
  • test plants Monocotyledonous and dicotyledonous test plants are sown in standard soil in pots.
  • the test compounds in the form of an aqueous suspension (prepared from a wettable powder (Example F3, b) according to WO 97/34485) or in the form of an emulsion (prepared from an emulsifiable concentrate (Example F1 , c) according to WO 97/34485), are applied by spraying, in an optimum concentration (500 litres of water per ha).
  • the test plants are then grown on in a greenhouse under optimum conditions.
  • the test is evaluated after a test duration of 2 to 3 weeks.
  • Tables 1 and 2 exhibit good to very good herbicidal action.
  • the compounds tested exhibit good to very good control of Digitaria sanguinalis and Setaria italica.

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Abstract

Compounds of formula (I), wherein the substituents are as defined in claim 1, are suitable for use as herbicides.

Description

Novel herbicides
The present invention relates to novel, herbicidally active pyrimidino-imidazoles, to processes for their preparation, to compositions comprising those compounds, and to their use in controlling weeds, especially in crops of useful plants, or in inhibiting plant growth.
Pyrimidino-imidazoles are described, for example, as intermediates for the synthesis of angiotensin II antagonists in WO 95/22543 and also as antibacterials in WO 03/004509 and WO 02/083111.
Novel pyrimidino-imidazoles that have herbicidal and growth-inhibiting properties have now been found.
The present invention accordingly relates to compounds of formula I
Figure imgf000002_0001
wherein
Ri is hydrogen, halogen, cyano, amino, hydroxy, nitro, formyl, -COOH, -CONH2> -CSNH2, Cι-C6alkyl, halo-C C6alkyl, C C6alkoxy, halo-C C6alkoxy, d-Cealkylamino, halo-C-ι-C6- alkylamino, CrC6dialkylamino wherein the alkyl groups are the same or different or together with the nitrogen atom to which they are bonded form a 4- to 7-membered ring which may contain a further hetero atom selected from N, O and S, halo-C C6dialkylamino wherein the alkyl groups are the same or different, (Cι-C6alkyl)S(O)m, (halo-CrC6alkyl)S(O)m, (CrC6alkylamino)S(O)m,
Figure imgf000002_0002
wherein the alkyl groups are the same or different, (halo-CrC6dialkylamino)S(O)m wherein the alkyl groups are the same or different, CrC6alkylsulfonyloxy, halo-C C6alkylsulfonyloxy, CrC6alkylS(O)mamino; C C6alkyl- S(O)mamino substituted by halogen, amino, CrC6alkylamino, Cι-C6dialkylamino, hydroxy, cyano, d-C4alkoxy or by formyl; Cι-C6alkoxy-Cι-C6alkyl, halo-d-Cealkoxy-d-C-ealkyl, Cι-C6alkoxy-Cι-C6alkyloxy, halo-d-Cealkoxy-d-Cβalkyloxy, d-C6alkoxy-d-C6alkylamino, halo-CrCealkoxy-d-Cealkylamino, C1-C6alkylS(O)m-C1-C6alkyl, halo-d-C6alkylS(O)m- Cι-C6alkyl, C1-C6alkylS(O)m-C1-C6alkyloxy, halo-C1-C6alkylS(O)m-C1-C6alkyloxy, C1-C6alkylS(O)m-C1-C6alkylamino, halo-C -C6alkylS(O)m-C1-C6alkylamino, C C6alkylcarbonyl; Cι-C6alkylcarbonyl substituted by halogen, amino, d-C6alkylamino, CrC6dialkyIamino, hydroxy, cyano, C C4alkoxy or by formyl; d-C6alkoxycarbonyI; d-C6alkoxycarbonyl substituted by halogen, amino, Cι-C6alkylamino, d-C6dialkylamino, hydroxy, cyano, d-C4alkoxy or by formyl; d-C6alkylcarbonyloxy; d-C6alkylcarbonyloxy substituted by halogen, amino, d-C-ealkylamino, CrC6dialkylamino, hydroxy, cyano, Cι-C4alkoxy or by formyl; formylamino, d-C6alkylcarbonylamino; C C6alkylcarbonylamino substituted by halogen, amino, d-C6alkylamino, d-C6dialkylamino, hydroxy, cyano, d-C4alkoxy or by formyl; C-t-C6alkylaminocarbonyl; d-C6alkylaminocarbonyl substituted by halogen, amino, d-C6alkylamino, d-C6dialkylamino, hydroxy, cyano, C C4alkoxy or by formyl; d-C6dialkyl- aminocarbonyl wherein the alkyl groups are the same or different; d-C6dialkylaminocarbonyl substituted by halogen, amino, Cι-C6alkylamino, d-C6dialkylamino, hydroxy, cyano, d-C4alkoxy or by formyl, wherein the alkyl groups are the same or different; C2-C6alkenyl, halo-C2-C6alkenyl, C3-C6alkenyloxy, halo-C3-C6alkenyloxy, (C2-C6alkenyl)S(O)m, (halo- C2-C6alkenyl)S(O)m, C3-C6alkenylamino, halo-C3-C6alkenylamino, C3-C6dialkenylamino wherein the alkenyl radicals are the same or different, halo-C3-C6dialkenylamino wherein the alkenyl radicals are the same or different, C3-C6cycloalkyl; C3-C6cycloalkyl substituted by halogen, amino, C-|-C6alkylaιnino, d-C6dialkylamino, hydroxy, cyano, C C4alkoxy or by formyl; tri(C1-C6alkyl)silyl; tri(d-Cealkyl)silyI substituted by halogen, amino, d-C-ealkylamino, d-C6dialkylamino, hydroxy, cyano, d-C alkoxy or by formyl; pentafluorothio, C2-C6alkynyl; C2-C6alkynyl substituted by halogen, amino, Cι-C6alkylamino, d-C6dialkylamino, hydroxy, cyano, C-ι-C4alkoxy, tri(d -C6alkyl)silyl or by formyl; C3-C6alkynyloxy, halo-C3-C6alkynyloxy, (C3-C6all<ynyl)S(O)m, (halo-C3-C6alkynyl)S(O)m, C3-C6alkynylamino, halo-C3-C6alkynylamino, C3-C6diall<ynylamino wherein the alkynyl radicals are the same or different, halo- C3-C6dialkynylamino wherein the alkynyl radicals are the same or different, -Q or -A-Q;
R2 is hydrogen, cyano, hydroxy, amino, formyl, -CONH2, -CSNH2, d-C6alkyl; C C6alkyl substituted by halogen, amino, d-C6alkylamino, d-C6dialkylamino, hydroxy, cyano, d-C - alkoxy or by formyl; d-C6alkoxy; d-C6alkoxy substituted by halogen, amino, d-C6alkyl- amino, Cι-C6dialkylamino, hydroxy, cyano, C C4alkoxy or by formyl; d-C6alkylamino, halo- CrC6alkylamino, CrC6dialkylamino wherein the alkyl groups are the same or different, halo- Cι-C6dialkylamino wherein the alkyl groups are the same or different, (Cι-C6alkyl)S(O)m, (halo-Cι-C6alkyl)S(O)m, (d-C6aikylamino)S(O)m, (d-C6dialkylamino)S(O)m wherein the alkyl groups are the same or different, (halo-d-C6dialkylamino)S(O)m wherein the alkyl groups are the same or different, halo-d-C6alkoxy-d-C6alkyl, d-C6alkylS(O)m-CrC6alkyl, halo- d-C-6alkylS(O)m-Cι-C6alkyl, d-C6alkylcarbonyl; d-C6alkylcarbonyl substituted by halogen, amino, d-C6alkylamino, d-C6dialkylamino, hydroxy, cyano, Cι-C alkoxy or by formyl; CrC6alkoxycarbonyl; C-ι-C6alkoxycarbonyl substituted by halogen, amino, Cι-C6alkylamino, Cι-C6dialkylamino, hydroxy, cyano, Cι-C4alkoxy or by formyl; d-C6alkylcarbonyloxy; Cι-C6alkylcarbonyloxy substituted by halogen, amino, d-dalkylamino, d-C6dialkylamino, hydroxy, cyano, CrC4alkoxy or by formyl; formylamino, Cι-C6alkylcarbonylamino; d-C6alkyl- carbonylamino substituted by halogen, amino, C-ι-C6alkylamino, CrCedialkylamino, hydroxy, cyano, d-C4alkoxy or by formyl; d-C6alkylaminocarbonyl; d-C6alkylaminocarbonyl substituted by halogen, amino, d-C6alkylamino, d-C6dialkylamino, hydroxy, cyano, Cι-C alkoxy or by formyl; d-Cedialkylaminocarbonyl wherein the alkyl groups are the same or different; d-Cedialkylaminocarbonyl substituted by halogen, amino, d-C6alkylamino, CrCedialkylamino, hydroxy, cyano, C C alkoxy or by formyl, wherein the alkyl groups are the same or different; C2-C6alkenyl, halo-C2-C6alkenyl, C2-C6alkenyloxy, halo-C2-C6- alkenyloxy, (C2-C6alkenyl)S(O)m, (halo-C2-C6alkenyl)S(O)m, C3-C6cycloalkyl; C3-C6cycloalkyl substituted by halogen, amino, CrC6alkylamino, CrC6dialkylamino, hydroxy, cyano, d-C4alkoxy or by formyl; tri(CrC6alkyl)silyl; tri(CrC6alkyl)silyl substituted by halogen, amino, d-Cealkylamino, d-C6dialkylamino, hydroxy, cyano, C C4alkoxy or by formyl; C2-C6alkynyl; C2-C6alkynyl substituted by halogen, amino, d-C6alkylamino, CrC6dialkylamino, hydroxy, cyano, d-C4alkoxy or by formyl, -Q or -A-Q;
R3 is hydrogen, halogen, cyano, amino, hydroxy, nitro, formyl, -COOH, -CONH2, -CSNH2, d-Cealkyl, halo-CrC6alkyl, CrC6alkoxy, halo-CrC6alkoxy, CrC6alkylamino, halo-CrC6- alkylamino, Crddialkylamino wherein the alkyl groups are the same or different or together with the nitrogen atom to which they are bonded form a 4- to 7-membered ring which may be interrupted by N, O or S, halo-d-C6dialkylamino wherein the alkyl groups are the same or different, (d-C6alkyl)S(O)m, (halo-d-C6alkyl)S(O)m, (d-C6alkyIamino)S(O)m, (d-C6dialkyl- amino)S(O)m wherein the alkyl groups are the same or different, (halo-CrC6dialkylamino)- S(O)m wherein the alkyl groups are the same or different, CrC6alkylsulfonyloxy, halo-d-C6- alkylsulfonyloxy, CrCealkylS(O)mamino; CrC6alkylS(O)mamino substituted by halogen, amino, CrC6alkylamino, CrCedialkylamino, hydroxy, cyano, C C alkoxy or by formyl; d-Cealkoxy-d-Cealkyl, halo-d-Cealkoxy-CrCealkyl, CrC6alkoxy-CrC6alkyloxy, halo- d-Cealkoxy-d-Cealkyloxy, Ci-Cealkoxy-CrCealkylamino, halo-CrC6alkoxy-CrC6alkylamino, CrC6alkylS(O)m-CrC6alkyl, halo-CrC6alkylS(O)m-CrC6alkyl, CrC6alkylS(O)m-CrC6alkyloxy, halo-CrC6alkylS(O)m-CrC6alkyloxy, CrC6alkylS(O)m-CrC6alkylamino, halo-CrC6alkylS(O)m- CrC6alkylamino, CrC6alkyIcarbonyl; CrC6alkylcarbonyl substituted by halogen, amino, d-Cealkylamino, CrC6dialkylamino, hydroxy, cyano, d-C4alkoxy or by formyl; d-C6alkoxy- carbonyl; CrC6alkoxycarbonyl substituted by halogen, amino, CrC6alkylamino, CrCedialkylamino, hydroxy, cyano, d-C4alkoxy or by formyl; d-C6alkylcarbonyloxy; CrC6alkylcarbonyI- oxy substituted by halogen, amino, C C6alkylamino, CrC6dialkylamino, hydroxy, cyano, d-C alkoxy or by formyl; formylamino, d-C6alkylcarbonyIamino; Cι-C6alkylcarbonyIamino substituted by halogen, amino, CrC6alkylamino, CrC6dialkylamino, hydroxy, cyano, d-C4alkoxy or by formyl; d-C6alkylaminocarbonyl; CrC6alkylaminocarbonyl substituted by halogen, amino, CrC6alkylamino, CrC6dialkylamino, hydroxy, cyano, d-C alkoxy or by formyl; d-C6dialkylaminocarbonyl wherein the alkyl groups are the same or different; d-C6dialkylaminocarbonyl substituted by halogen, amino, CrC6alkylamino, CrCedialkylamino, hydroxy, cyano, d-C alkoxy or by formyl, wherein the alkyl groups are the same or different; C2-C6alkenyl, halo-C2-C6alkenyl, C3-C6alkenyIoxy, halo-C3-C6alkenyloxy, (C2-C6alkenyl)S(O)m, (halo-C2-C6alkenyl)S(O)m, C3-C6alkenylamino, halo-C3-C6alkenylamino, C3-C6dialkenylamino wherein the alkenyl radicals are the same or different, halo- C3-C6dialkenylamino wherein the alkenyl radicals are the same or different, C3-C6cycloalkyl; C3-C6cycloalkyl substituted by halogen, amino, d-Cealkylamino, CrCedialkylamino, hydroxy, cyano, C C4alkoxy or by formyl; tri(CrC6alkyl)silyl; tri(d-C6alkyl)silyl substituted by halogen, amino, CrC6alkylamino, CrC6dialkylamino, hydroxy, cyano, C C alkoxy or by formyl; pentafluorothio, C2-C6alkynyl; C2-C6alkynyl substituted by halogen, amino, d-Cealkylamino, CrCedialkylamino, hydroxy, cyano, C C4alkoxy, tri(d-C6alkyl)silyI or by formyl; C3-C6alkynyloxy, halo-C3-C6alkynyloxy, (C3-C6alkynyl)S(O)m, (halo-C3-C6alkynyl)S(O)m, C3-C6alkynylamino, halo-C3-C6alkynylamino, C3-C6dialkynylamino wherein the alkynyl radicals are the same or different, or halo-C3-C6dialkynylamino wherein the alkynyl radicals are the same or different;
R4 is hydrogen, halogen, cyano, amino, nitro, formyl, -COOH, -CONH2, -CSNH2, d-C6alkyI, halo-CrC6alkyl, d-C6alkoxy, halo-CrC6alkoxy, CrC6alkylamino, CrC6dialkylamino wherein the alkyl groups are the same or different or together with the nitrogen atom to which they are bonded form a 4- to 7-membered ring, halo-CrC6dialkylamino wherein the alkyl groups are the same or different, (CrC6alkyl)S(O)m, (halo-C1-C6alkyl)S(O)ITl, d-Cealkoxy-d-Cealkyl, halo-CrC6alkoxy-CrC6alkyl, d-C6alkylcarbonyl; CrC6alkylcarbonyl substituted by halogen, amino, CrC6alkylamino, CrCedialkylamino, hydroxy, cyano, d-C4alkoxy or by formyl; d-C6aIkoxycarbonyl; CrC6alkoxycarbonyl substituted by halogen, amino, d-C6alkylamino, CrC6dialkylamino, hydroxy, cyano, d-C alkoxy or by formyl; d-C6alkylcarbonylamino; CrCealkylcarbonylamino substituted by halogen, amino, CrC6alkylamino, CrC6dialkylamino, hydroxy, cyano, CrC4alkoxy or by formyl; CrC6alkylaminocarbonyI; CrC6alkylaminocarbonyl substituted by halogen, amino, d-C6alkylamino, CrC6dialkylamino, hydroxy, cyano, d-C4- alkoxy or by formyl; Ci-C6dialkylaminocarbonyl wherein the alkyl groups are the same or different; CrC6dialkylaminocarbonyl substituted by halogen, amino, d-C6alkylamino, CrCedialkylamino, hydroxy, cyano, d-C4alkoxy or by formyl, wherein the alkyl groups are the same or different; C2-C6alkenyl, halo-C2-C6alkenyl, C3-C6cycIoalkyl; C3-C6cycloalkyl substituted by halogen, amino, CrC6alkylamino, d-Cedialkylamino, hydroxy, cyano, C C4- alkoxy or by formyl; tri(Cι-C6alkyl)silyl, C2-C6alkynyl; or C2-C6alkynyl substituted by halogen, amino, CrC6alkylamino, d-Cedialkylamino, hydroxy, cyano, d-C alkoxy, tri(C1-C6alkyl)silyl or by formyl;
A is d-C alkylene; CrC4alkylene substituted by halogen, amino, d-C6alkylamino, CrCedialkylamino, hydroxy, cyano, d-C alkoxy or by formyl; d-C oxyalkylene; CrC4oxyalkylene substituted by halogen, amino, d-C6alkylamino, CrCedialkylamino, hydroxy, cyano, d-C4alkoxy or by formyl; CrC4alkyleneoxy; CrC4alkyleneoxy substituted by halogen, amino, d-Cealkylamino, d-C6dialkylamino, hydroxy, cyano, d-C alkoxy or by formyl; C C4oxy- alkyleneoxy; d-C oxyalkyIeneoxy substituted by halogen, amino, d-Cealkylamino, CrCedialkylamino, hydroxy, cyano, d-C alkoxy or by formyl; d-C aminoalkylene; Crdamino- alkylene substituted by halogen, amino, CrC6alkylamino, d-C6dialkylamino, hydroxy, cyano, d-C alkoxy or by formyl; CrC4alkyleneamino; d.-C4alkyleneamino substituted by halogen, amino, CrC6alkyIamino, CrC6dialkylamino, hydroxy, cyano, d-C alkoxy or by formyl; d-C4- aminoalkyleneamino; Cι-C4aminoalkyleneamino substituted by halogen, amino, d-C6alkyl- amino, d-Cedialkylamino, hydroxy, cyano, d-C4alkoxy or by formyl; d-C4thioalkylene; Cι-C4thioaIkylene substituted by halogen, amino, CrC6alkylamino, CrC6dialkylamino, hydroxy, cyano, C C alkoxy or by formyl; C3-C6cycloalkylene; C3-C6cycloalkylene substituted by halogen, amino, Cι-C6alkylamino, CrCedialkylamino, hydroxy, cyano, d-C alkoxy or by formyl; C2-C4alkenylene; C2-C4alkenylene substituted by halogen, amino, CrC6aIkylamino, d-Cedialkylamino, hydroxy, cyano, d-C4alkoxy or by formyl; C2-C4alkynylene; C2-C4alkynyl- ene substituted by halogen, amino, CrC6alkylamino, CrCedialkylamino, hydroxy, cyano, d-C4alkoxy or by formyl; O, S, NH, formylamino, d-C alkylamino, S(O)m, oxysulfonyl, sulfonyloxy, aminosulfonyl, sulfonylamino, carbonyl, oxycarbonyl, carbonyloxy, oxycarbonyloxy, carbonylamino, aminocarbonyl, aminocarbonyloxy, oxycarbonylamino or aminocarbonylamino;
Q is aryl, aryl substituted one or more times by halogen, cyano, hydroxy, amino, nitro, formyl, -COOH, -CONH≥, -CSNH2, d-Cealkyl, halo-d-C6alkyl, CrC6alkoxy, halo-C C6aIkoxy, CrC6alkylamino, halo-CrC6alkylamino, d-Cedialkylamino wherein the alkyl groups are the same or different or together with the nitrogen atom to which they are bonded form a 4- to 7- membered ring, halo-CrC6dialkylamino wherein the alkyl groups are the same or different, (CrC6alkyl)S(O)m> (haIo-C C6alkyl)S(O)m, (CrC6alkylamino)S(O)m, (CrC6dialkyl- amino)S(O)m wherein the alkyl groups are the same or different, (halo-CrC6dialkylamino)- S(O)m wherein the alkyl groups are the same or different, CrC6alkylsulfonyloxy, halo-d-C6- alkylsulfonyloxy, CrC6alkylS(O)mamino; d-C6alkylS(O)mamino substituted by halogen, amino, CrC6alkylamino, CrCedialkylamino, hydroxy, cyano, d-C4alkoxy or by formyl; CrC6alkoxy-CrC6alkyl, halo-CrC6alkoxy-CrCealkyl, Ci-Cealkoxy-CrCealkyloxy, halo- CrCealkoxy-d-Cealkyloxy, CrC6alkoxy-CrCealkylamino, halo-CrC6alkoxy-CrC6alkylamino, Cι-CealkylS(O)m-CrC6alkyl, halo-CrC6alkylS(O)m-CrC6alkyl, CrC6alkylS(O)m-CrC6alkyloxy, halo-CrC6alkylS(O)m-CrC6alkyloxy, CrC6alkylS(O)m-CrC6alkylamino, halo-CrCealkylS(O)m- CrC6alkylamino, CrC6alkylcarbonyl; CrC6alkylcarbonyl substituted by halogen, amino, CrC6alkylamino, d-C6dialkylamino, hydroxy, cyano, Cι-C alkoxy or by formyl; d-C6alkoxy- carbonyl; C-i -C6aIkoxycarbonyl substituted by halogen, amino, CrC6alkylamino, CrCedialkylamino, hydroxy, cyano, d-C alkoxy or by formyl; d-C6alkylcarbonyloxy; d-C6alkyl- carbonyloxy substituted by halogen, amino, C C6alkylamino, CrCedialkylamino, hydroxy, cyano, d-C4alkoxy or by formyl; formylamino, CrC6alkyIcarbonylamino; CrCealkylcarbonylamino substituted by halogen, amino, CrC6alkylamino, CrC6dialkylamino, hydroxy, cyano, d-C alkoxy or by formyl; CrC6alkylaminocarbonyl; d-C6alkylaminocarbonyl substituted by halogen, amino, CrC6alkylamino, CrC6dialkylamino, hydroxy, cyano, d-C4alkoxy or by formyl; CrC6dialkyIaminocarbonyl wherein the alkyl groups are the same or different; d-Cedialkylaminocarbonyl substituted by halogen, amino, CrC6alkylamino, d-Cedialkylamino, hydroxy, cyano, d-C4alkoxy or by formyl, wherein the alkyl groups are the same or different; C2-C6alkenyl, halo-C2-C6alkenyl, C3-C6alkenyloxy, halo-C3-C6alkenyloxy, (C2-C6- alkenyl)S(O)m, (haIo-C2-C6alkenyI)S(O)m, C3-C6alkenylamino, halo-C3-C6alkenylamino, C3-C6- dialkenylamino wherein the alkenyl radicals are the same or different, halo-C3-C6dialkenyl- amino wherein the alkenyl radicals are the same or different, C3-C6cycloalkyl; C3-C6cycloalkyl substituted by halogen, amino, d-Cealkylamino, d-Cedialkylamino, hydroxy, cyano, d-C4- alkoxy or by formyl; tri(C1-C6alkyl)silyl; tri(CrC6alkyl)silyl substituted by halogen, amino, CrC6alkylamino, d-Cedialkylamino, hydroxy, cyano, d-C alkoxy or by formyl; pentafluoro- thio; C2-C6alkynyl, or C2-C6alkynyl substituted by halogen, amino, d-Cealkylamino, CrCedialkylamino, hydroxy, cyano, d-C4alkoxy, tri(C1-C6alkyl)silyl or by formyl; C3-C6alkynyloxy, haIo-C3-C6alkynyloxy, (C3-C6alkynyl)S(O)m, (halo-C3-C6alkynyl)S(O)m, C3-C6alkynyIamino, halo-C3-C6alkynylamino, C3-C6dialkynylamino wherein the alkynyl radicals are the same or different, halo-C3-C6dialkynylamino wherein the alkynyl radicals are the same or different, or Q is a monocyclic heterocycle, or a monocyclic heterocycle substituted one or more times by halogen, cyano, hydroxy, amino, nitro, formyl, -COOH, -CONH2, -CSNH2, d-C6alkyl, halo-C C6alkyl, d-C6alkoxy, hald-CrC6alkoxy, CrC6alkylamino, halo-CrC6alkylamino, CrC6dialkylamino wherein the alkyl groups are the same or different or together with the nitrogen atom to which they are bonded form a 4- to 7-membered ring, halo-CrC6dialkyl- amino wherein the alkyl groups are the same or different, (CrC6alkyl)S(O)m, (halo-d-C6- alkyl)S(O)m, (CrCealkylamino)S(O)m, (CrC6dialkyIamino)S(O)m wherein the alkyl groups are the same or different, (halo-CrC6dialkylamino)S(O)m wherein the alkyl groups are the same or different, CrC6alkylsulfonyloxy, halo-d-C6alkylsulfonyloxy, CrC6alkylS(O)mamino; CrC6alkylS(O)mamino substituted by halogen, amino, CrC6alkylamino, CrCedialkylamino, hydroxy, cyano, Cι-C alkoxy or by formyl; CrC6alkoxy-CrC6alkyI, halo-CrC6alkoxy-CrC6- alkyl, CrCealkoxy-d-Cβalkyloxy, halo-CrC6alkoxy-CrC6alkyloxy, CrCealkoxy-CrC6alkyl- amino, halo-CrCealkoxy-d-Cealkylamino, Cι-C6alkylS(O)m-CrC6alkyl, halo-C C6alkylS(O)m- d-C6alkyl, CrC6alkylS(O)m-CrC6alkyloxy, halo-CrC6alkylS(O)m-CrC6alkyloxy, d-C6alkyl- S(O)m-d-C6alkylamino, halo-CrC6alkylS(O)m-CrC6alkylamino, CrC6alkylcarbonyl; CrC6alkylcarbonyl substituted by halogen, amino, CrC6alkylamino, d-C6dialkylamino, hydroxy, cyano, d-C4alkoxy or by formyl; CrC6alkoxycarbonyl; CrC6alkoxycarbonyI substituted by halogen, amino, CrC6alkylamino, CrCedialkylamino, hydroxy, cyano, d-C4alkoxy or by formyl; CrC6alkylcarbonyloxy; CrC6alkylcarbonyloxy substituted by halogen, amino, CrC6alkylamino, CrC6dialkylamino, hydroxy, cyano, d-C alkoxy or by formyl; formylamino, CrC6alkylcarbonylamino; CrC6alkylcarbonylamino substituted by halogen, amino, CrC6alkylamino, CrC6dialkylamino, hydroxy, cyano, d-C4alkoxy or by formyl; CrCealkylaminocarbonyl; CrCealkylaminocarbonyl substituted by halogen, amino, CrC6alkylamino, CrC6dialkylamino, hydroxy, cyano, C C alkoxy or by formyl; d-C6- dialkylaminocarbonyl wherein the alkyl groups are the same or different; CrC6dialkylamino- carbonyl substituted by halogen, amino, CrC6alkylamino, d-Cedialkylamino, hydroxy, cyano, d-dalkoxy or by formyl, wherein the alkyl groups are the same or different; C2-C6alkenyl, halo-C2-C6alkenyl, C3-C6alkenyloxy, halo-C3-C6alkenyIoxy, (C2-C6alkenyl)- S(O)m, (haIo-C2-C6alkenyl)S(O)m, C3-C6alkenylamino, halo-C3-C6alkenylamino, C3-C6dialkenylarnino wherein the alkenyl radicals are the same or different, halo- C3-C6dialkenylamino wherein the alkenyl radicals are the same or different, C3-C6cycloalkyl; C3-C6cycloalkyl substituted by halogen, amino, CrC6alkylamino, d-C6dialkylamino, hydroxy, cyano, C C4alkoxy or by formyl; tri(d-C6alkyl)silyl; tri(d-C6alkyl)silyl substituted by halogen, amino, CrC6alkylamino, CrC6dialkylamino, hydroxy, cyano, d-C4alkoxy or by formyl; pentafluorothio; C2-C6alkynyl, or C2-C6alkynyl substituted by halogen, amino, d-C6alkylamino, CrC6dialkylamino, hydroxy, cyano, C C4alkoxy, tri(CrC6alkyl)silyl or by formyl; C3-C6alkynyloxy, halo-C3-C6alkynyloxy, (C3-C6alkynyl)S(O)m, (halo-C3-C6alkynyI)- S(O)m, C3-C6alkynylamino, halo-C3-C6a!kynylamino, C3-C6dialkynylamino wherein the alkynyl radicals are the same or different, haio-C3-C6dialkynylamino wherein the alkynyl radicals are the same or different, and m is 0, 1 or 2, and also to enantiomers, mixtures of enantiomers, tautomers, mixtures of tautomers, agrochemically acceptable salts of compounds of formula I, N-oxides of those compounds and enantiomers, mixtures of enantiomers, tautomers, mixtures of tautomers and agrochemically acceptable salts thereof, with the exclusion of 5-(2-butyl-3H-imidazol-4-yl)-pyrimidine, 5-(5-ethyl-2-(4- f luorophenyl)-1 H-imidazol-4-yl)-pyrimidine hydrochlohde, N-{5-[2-(4-f luorophenyl)-5-propyl- 1 H-imidazol-4-yl]-pyrimidin-2-yl}-acetamide dihydrochloride, 5-(1 H-imidazol-4-yl)-pyrimidine dihydrochloride and 4-(4-pyrimidin-5-yl-imidazol-1 -yl)-butylamine.
In the compounds of formula I, alkyl, as a group perse or as a structural element in other substituents, for example in alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, alkylcarbonyl, alkoxycarbonyl, alkylamino, aikoxyiminomethyl, alkylaminocarbonyl and alkylaminothio- carbonyl, is either straight-chain alkyl, that is to say, for example, methyl, ethyl, propyl, butyl, pentyl or hexyl, or branched alkyl, for example isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl or isohexyl. The alkyl radicals may be substituted by one or more substituents such as halogen, amino, d-C6alkylamino, d-Cedialkylamino, hydroxy, cyano, formyl or CrC4alkoxy. In radicals such as dialkyl-, dialkenyl- or dialkynyl-amino, both the alkyl groups may have the number of carbon atoms specified in the definition.
Alkenyl, as a group perse or as a structural element in other substituents, for example in alkenyloxy, is either straight-chained, for example vinyl, 1-methylvinyl, allyl, 1 -butenyl or 2- hexenyl, or branched, for example isopropenyl. The alkenyl radicals may be substituted by one or more substituents such as halogen, amino, CrC6alkylamino, d-Cedialkylamino, hydroxy, cyano, formyl or d-C4alkoxy.
Alkynyl, as a group perse or as a structural element in other substituents, for example in alkynyloxy, is either straight-chained, for example propargyl, 2-butynyl or 5-hexynyl, or branched, for example 2-ethynylpropyl or 2-propargylisopropyl. The alkynyl radicals may be substituted by one or more substituents such as halogen, amino, CrC6alkylamino, CrC6dialkylamino, hydroxy, cyano, tri(CrC6alkyl)silyl, formyl or d-C4alkoxy.
C3-C6Cycloalkyl is cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl. The cycloalkyl radicals may be substituted by one or more radicals such as halogen, amino, CrC6alkylamino, d-Cedialkylamino, hydroxy, cyano, formyl or d-C4alkoxy. Alkylene, as a group perse or as a structural element in other groups, for example in haloalkylene, is either straight-chained, for example -CH2CH2-, -CH2CH2CH2- or -CH2CH2CH2CH2-, or branched, for example -CH(CH3)-, -CH(C2H5)-, -C(CH3)2-, -CH(CH3)CH2- or -CH(CH3)CH(CH3)-. The alkylene radicals may be substituted by one or more radicals such as halogen, amino, d-Cealkylamino, d-C6dialkylamino, hydroxy, cyano, formyl or d-C4alkoxy.
Aryl is preferably phenyl or naphthyl, especially phenyl. The aryl radicals may be substituted by one or more radicals such as halogen, cyano, hydroxy, amino, nitro, formyl, -COOH, -CONHg, -CSNH2, d-Cealkyl, halo-CrC6alkyl, CrC6alkoxy, halo-C C6alkoxy, d-Cealkylamino, halo-CrC6alkylamino, CrC6dialkylamino wherein the alkyl groups are the same or different or together with the nitrogen atom to which they are bonded form a 4- to 7- membered ring, halo-CrC6dialkylamino wherein the alkyl groups are the same or different, (CrC6alkyl)S(O)m, (halo-CrCealkyl)S(O)m, (d-C6alkylamino)vS(O)m, (d-C6dialkylamino)- S(O)m wherein the alkyl groups are the same or different, (halo-CrC6dialkylamino)S(O)m wherein the alkyl groups are the same or different, d-C6alkylsulfonyloxy, halo-d-C6alkyl- sulfonyloxy, CrC6alkylS(O)mamino; d-C6alkylS(O)mamino substituted by halogen, amino, CrC6alkylamino, d-Cedialkylamino, hydroxy, cyano, C C4alkoxy or by formyl; d-C6alkoxy- CrC6alkyl, halo-CrC6alkoxy-CrC6alkyl, Ci-Cealkoxy-CrCealkyloxy, halo-d-C6alkoxy- d-C6alkyloxy, CrC6alkoxy-CrC6alkylamino, halo-CrCealkoxy-d-Cealkylamino, d-C6alkyl- S(O)m-d-C6alkyl, halo-d-C6alkylS(O)m-CrC6alkyl, CrC6aikylS(O)m-CrC6aIkyloxy, halo- CrC6alkylS(O)m-CrC6alkyloxy, CrC6alkylS(O)m-CrC6alkylamino, halo-Cι-C6alkylS(O)m- CrC6alkylamino, CrC6alkylcarbonyl; CrC6alkylcarbonyl substituted by halogen, amino, d-Cealkylamino, CrCedialkylamino, hydroxy, cyano, d-C4alkoxy or by formyl; Crdalkoxy- carbonyl; CrC6alkoxycarbonyl substituted by halogen, amino, CrC6alkylamino, d-Cedialkylamino, hydroxy, cyano, d-C4alkoxy or by formyl; CrC6alkylcarbonyloxy; CrC6alkylcarbonyl- oxy substituted by halogen, amino, CrC6alkyIamino, d-Cedialkylamino, hydroxy, cyano, Crdalkoxy or by formyl; formylamino, CrC6alkylcarbonylamino; CrC6alkylcarbonylamino substituted by halogen, amino, CrC6aIkylamino, CrC6diaIkylamino, hydroxy, cyano, d-C4- alkoxy or by formyl; CrCealkylaminocarbonyl; CrC6aIkylaminocarbonyl substituted by halogen, amino, Crdalkylamino, d-C6dialkylamino, hydroxy, cyano, d-C4alkoxy or by formyl; CrC6dialkylaminocarbonyl wherein the alkyl groups are the same or different; CrC6dialkylaminocarbonyI substituted by halogen, amino, CrC6alkylamino, CrCedialkylamino, hydroxy, cyano, C-ι-C4alkoxy or by formyl, wherein the alkyl groups are the same or different; C2-C6alkenyl, halo-C2-C6alkenyl, C3-C6alkenyloxy, haIo-C3-C6aIkenyloxy, (C2-C6- alkenyl)S(O)m, (halo-C2-C6alkenyI)S(O)m, C3-C6alkenylamino, halo-C3-C6alkenylamino, C3-C6- dialkenylamino wherein the alkenyl radicals are the same or different, halo-C3-C6dialkenyl- amino wherein the alkenyl radicals are the same or different, C3-C6cycloalkyl; C3-C6cycloalkyl substituted by halogen, amino, CrC6alkylamino, d-Cedialkylamino, hydroxy, cyano, d-C alkoxy or by formyl; tri(CrC6alkyl)silyl; tri(CrC6alkyl)silyl substituted by halogen, amino, d-C6alkylamino, d-Cedialkylamino, hydroxy, cyano, d-C alkoxy or by formyl; pentafluorothio; C2-C6alkynyl, or C2-C6alkynyl substituted by halogen, amino, CrGealkylamino, d-Cedialkylamino, hydroxy, cyano, C C4alkoxy, tri(CrC6alkyl)silyl or by formyl; C3-C6alkynyloxy, halo-C3-C6alkynyloxy, (C3-C6alkynyl)S(O)mι (halo-C3-Cealkynyl)S(O)mι C3-C6alkynylamino, halo-C3-C6alkynylamino, C3-C6dialkynylamino wherein the alkynyl radicals are the same or different, halo-C3-C6dialkynylamino wherein the alkynyl radicals are the same or different.
Among the heterocycles in the definitions of Q preference is given to 5- or 6-membered aromatic rings containing one to three hetero atoms especially selected from the group consisting of N, O and S. Preferred heterocycles are pyrazinyl, pyridyl(3'), pyridyl(2'), pyridyl(4'), pyrimidinyl(2'), pyrimidinyl(4'), pyrimidinyl(5'), pyridazinyl(3'), pyridazinyl(4'), thiazolyl(2'), thiazolyl(4'), thiazolyl(5'), pyrrolyl(2'), pyrrolyl(3'), pyrazolyl(3'), pyrazolyl(4'), pyrazolyl(5'), oxazoly|(2'), oxazolyl(4'), oxazolyl(5'), furyl(2'), furyl(3'), thienyl(2'), thienyl(3'), isothiazolyl(3'), isothiazolyl(4'), isothiazolyl(5'), isothiazolyl(3'), isothiazolyl(4'), isothiazolyl(5'), triazolyl(3'), triazolyl(4'), triazolyl(5'), and also 3- to 7-membered non-aromatic heterocycles such as, especially, oxiranyl(2'), thiranyl(2'), aziridinyl(2'), oxetanyI(2'), oxetanyl(3'), thietanyl(2'), thietanyl(3'), azetidinyl(l '), azetidinyl(2'), azetidinyl(3'), tetrahydrofuranyl(2'), tetrahydrofuranyI(3'), 1 ,3-dioxolanyl(2'), 1 ,3-dioxolanyl(4'), tetrahydrothiophenyl(2'), tetrahydrothiophenyl(3'), tetramethylenesulfoxidyl(2'), tetramethylenesulfonyl(2'), 1 ,3- dithiolanyl(2'), pyrrolidinyl(l '), pyrrolidinyl(2'), pyrrolidinyl(3'), tetrahydropyranyl(2'), tetrahydropyranyl(3'), tetrahydropyranyl(4'), 1 ,3-dioxanyl(2'), 1 ,3-dioxanyl(4'), 1 ,3- dioxanyl(4'), pentamethylenesulfidyl(2'), pentamethylenesulfidyl(3'), pentamethylene- sulfidyl(4'), pentamethylenesulfoxidyl(2'), pentamethylenesulfonyl(2'), 1 ,3-dithianyl(2'), pipe dyl(l '), piperidyl(2'), piperidyl(3'), piperidyl(4'), morpholinyl(4'), thiomorpholinyl(4'), oxepanyl(2') and hexamethyleneimino(l '). The heterocycles may be substituted by one or more radicals such as halogen, cyano, hydroxy, amino, nitro, formyl, -COOH, -CONH2, -CSNH2, Crdalkyl, halo-d-C6alkyl, CrC6alkoxy, halo-CrC6alkoxy, CrC6alkylamino, halo- CrC6alkylamino, CrCedialkylamino wherein the alkyl groups are the same or different or together with the nitrogen atom to which they are bonded form a 4- to 7-membered ring, halo-CrC6dialkylamino wherein the alkyl groups are the same or different, (CrC6alkyl)S(O)m, (halo-CrC6alkyl)S(O)m, (CrC6alkylamino)S(O)m, (CrC6dialkylamino)S(O)m wherein the alkyl groups are the same or different, (halo-CrC6dialkylamino)S(O)m wherein the alkyl groups are the same or different, CrC6alkylsulfonyloxy, halo-d-Cealkylsulfonyloxy, Crdalkyl- S(O)mamino; CrC6alkylS(O)mamino substituted by halogen, amino, CrC6alkylamino, CrC6dialkylamino, hydroxy, cyano, d-C4alkoxy or by formyl; CrC6alkoxy-CrCealkyl, halo- CrC6alkoxy-CrC6alkyl, CrC6alkoxy-CrC6alkyloxy, halo-CrC6alkoxy-CrC6alkyloxy, CrCδalkoxy-CrCealkylamino, halo-CrC6alkoxy-CrC6alkylamino, CrC6alkylS(O)m- d-C6alkyl, halo-CrC6alkylS(O)m-CrC6alkyl, CrC6alkylS(O)m-CrC6alkyloxy, halo- CrC6alkylS(O)m-C1-C6alkyloxy, Cι-C6alkylS(O)m-CrC6alkyIamino, halo-CrC6alkylS(O)m- CrC6alkylamino, d-C6alkylcarbonyl; CrC6alkylcarbonyl substituted by halogen, amino, CrC6alkylamino, CrC6dialkylamino, hydroxy, cyano, d-C4alkoxy or by formyl; d-C6alkoxy- carbonyl; CrC6alkoxycarbonyl substituted by halogen, amino, d-Cealkylamino, d-Cedialkylamino, hydroxy, cyano, Crdalkoxy or by formyl; d-C6alkylcarbonyloxy; CrCealkylcarbonyloxy substituted by halogen, amino, CrC6alkylamino, d-Cedialkylamino, hydroxy, cyano, Crdalkoxy or by formyl; formylamino, d-C6alkylcarbonylamino; d-C6alkylcarbonylamino substituted by halogen, amino, CrC6alkylamino, CrC6dialkylamino, hydroxy, cyano, Crdalkoxy or by formyl; d-C6alkylaminocarbonyl; CrCealkylaminocarbonyl substituted by halogen, amino, d-Cealkylamino, CrC6dialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; CrC6dialkylaminocarbonyl wherein the alkyl groups are the same or different; d-Cedialkylaminocarbonyl substituted by halogen, amino, CrC6alkylamino, d-Cedialkylamino, hydroxy, cyano, d-C4alkoxy or by formyl, wherein the alkyl groups are the same or different; C2-C6alkenyl, halo-C2-C6alkenyl, C3-C6alkenyloxy, halo-C3-C6alkenyloxy, (C2-C6alkenyl)S(O)m, (halo-C2-C6alkenyl)S(O)m, C3-C6alkenylamino, halo-C3-C6alkenylamino, C3-C6dialkenylamino wherein the alkenyl radicals are the same or different, halo- C3-C6dialkenylamino wherein the alkenyl radicals are the same or different, C3-C6cycloalkyl; C3-C6cycloalkyl substituted by halogen, amino, d-C6alkyIamino, CrCedialkylamino, hydroxy, cyano, Crdalkoxy or by formyl; tri(C1-C6a!kyl)siIyl; tri(C-|-C6alkyI)si!yI substituted by halogen, amino, CrC6alkylamino, CrCedialkylamino, hydroxy, cyano, C C4alkoxy or by formyl; pentafluorothio; C2-Cealkynyl, or C2-C6alkynyl substituted by halogen, amino, CrGealkylamino, CrC6dialkylamino, hydroxy, cyano, d-C4alkoxy, tri(CrC6alkyl)silyl or by formyl; C3-C6alkynyloxy, halo-C3-C6alkynyloxy, (C3-C6alkynyl)S(O)m, (halo-C3-C6alkynyl)S(O)m, C3-C6alkynylamino, haIo-C3-C6aIkynylamino, C3-C6dialkynylamino wherein the alkynyl radicals are the same or different, halo-C3-C6dialkynylamino wherein the alkynyl radicals are the same or different.
The non-aromatic heterocycles may, in addition, contain one or more carbonyl groups, for example 2-pyrrolidonyl(1'), succinimidyl(l'), gamma-butyrolactonyl(3'), ethylene- carbonatyl(4'), tetrahydrothiophen-3-onyl(2'), tetrahydro-2H-pyran-2-onyl(3'), tetrahydro-4H- pyran-4-onyl(3'), 2-piperidonyl(1 '), epsilon-caprolactamyl(l ').
Halogen, as a group perse or as a structural element in other substituents, for example in haloalkyl, haloalkenyl and haloalkynyl, is fluorine, chlorine, bromine or iodine, especially fluorine, chlorine or bromine, more especially fluorine or chlorine, very especially fluorine.
Halo-substituted substituents, such as haloalkyl, haloalkenyl and haloalkynyl, may be partially halogenated or perhalogenated, it being possible in the case of polyhalogenation for the halogen substituents to be the same or different. Examples of haloalkyl, as a group per se or as a structural element in other substituents such as haloalkenyl, are methyl substituted from one to three times by fluorine, chlorine and/or bromine, such as CHF2 or CF3; ethyl substituted from one to five times by fluorine, chlorine and/or bromine, such as CH2CF3, CF2CF3, CF2CCI3, CF2CHCI2, CF2CHF2) CF2CFCI2l CF2CHBr2, CF2CHCIF, CF2CHBrF or CCIFCHCIF; propyl or isopropyl substituted from one to seven times by fluorine, chlorine and/or bromine, such as CH2CHBrCH2Br, CF2CHFCF3, CH2CF2CF3, CF(CF3)2 or CH(CF3)2; and butyl or one of its isomers substituted from one to nine times by fluorine, chlorine and/or bromine, such as CF(CF3)CHFCF3 or CH2(CF2)2CF3. Haloalkenyl is, for example, CH2CH=CHCI, CH2CH=CCI2, CH2CF=CF2 or CH2CH=CHCH2Br. Haloalkynyl is, for example, CH2C≡CF, CH2C=CCH2CI or CF2CF2C≡CCH2F.
Compounds of formula I having at least one basic centre are capable of forming acid addition salts. Those acid addition salts are formed, for example, with strong inorganic acids, such as mineral acids, e.g. perchloric acid, sulfuric acid, nitric acid, nitrous acid, a phosphoric acid or a hydrohalic acid, with strong organic carboxylic acids, such as substituted, e.g. halo-substituted, CrC4alkanecarboxylic acids, e.g. acetic acid, saturated or unsaturated dicarboxylic acids, e.g. oxalic, malonic, succinic, maleic, fumaric and phthalic acid, hydroxycarboxylic acids, e.g. ascorbic, lactic, malic, tartaric and citric acid, or benzoic acid, or with organic sulfonic acids, such as unsubstituted or substituted, e.g. halo- substituted, d-C alkane- or aryl-sulfonic acids, e.g. methane- or p-toluene-sulfonic acid.
Furthermore, compounds of formula I having at least one acid group are capable of forming salts with bases. Suitable salts with bases are, for example, metal salts, such as alkali metal and alkaline earth metal salts, e.g. sodium, potassium and magnesium salts, and salts with ammonia or an organic amine, such as morpholine, piperidine, pyrrolidine, a mono-, di- or tri- lower alkylamine, e.g. ethyl-, diethyl-, triethyl- or dimethyl-propyl-amine, or a mono-, di- or tri- hydroxy-lower alkylamine, e.g. mono-, di- or tri-ethanolamine. In addition, corresponding internal salts may optionally be formed.
Preferred compounds of formula I are those wherein the substituent R4 is hydrogen.
A further group of preferred compounds of formula I comprises those wherein R is hydrogen and R3 is halogen or methyl.
Preference is also given to those compounds wherein R4 is hydrogen and R-\ is halogen, ha!o-d-C6alkyl or (CrC6alkyl)S(O)m, wherein m is 0, 1 or 2.
Preference is moreover given to compounds wherein R4 is hydrogen, R3 is bromine, chlorine or methyl, and Ri is halogen, halo-CrC6alkyl or (CrC6alkyl)S(O)m, wherein m is 0, 1 or 2.
Special significance is given to the compounds of formula I wherein R4 is hydrogen, R3 is bromine, chlorine or methyl, and RT is halogen or halo-d-C3alkyl. Very special significance is given to the compounds of formula I wherein R4 is hydrogen, R3 is bromine, chlorine or methyl, and R^ is CF3.
The compounds of formula I can be prepared by means of processes, known per se and described, for example, in WO 95/22543, wherein pyrimidines functionalised in the 5-position and imidazoles functionalised in the 4-position are linked catalytically or 5-(2-haloalkyl- carbonyl)-pyrimidines are cyclised with amidines, by, for example, reacting a suitable trialkyltin-imidazole with a suitable 5-bromo-pyrimidine under palladium catalysis. Instead of the trialkyltin-imidazoles, other imidazole compounds, e.g. imidazole-boronic acids, imidazole zinc compounds or imidazole magnesium compounds, can also be reacted with 5-halo- or 5- triflate-pyrimidines under transition metal catalysis, preferably palladium or nickel catalysis.
Figure imgf000015_0001
X = leaving group, e.g. Br, Cl, OSO2CF3 M = metal, e.g. Mg, Zn, Sn(alkyl)3 or B(OH)2 catalyst = transition metal, e.g. Pd or Ni, and suitable ligand, e.g. triphenylphosphine
The trialkyltin-imidazoles, imidazole-boronic acids, imidazole zinc compounds and imidazole magnesium compounds can be prepared using methods known per se from the imidazole unsubstituted in the 4-position by deprotonation using an organolithium compound, e.g. n- butyllithium, and subsequent transmetallation. In addition, the trialkyltin-imidazoles, imidazole-boronic acids, imidazole zinc compounds and imidazole magnesium compounds can be prepared by halogen-metal exchange starting from a 4-halo-imidazole and using an organolithium compound, e.g. n-butyllithium, or using magnesium or an organomagnesium compound and subsequent transmetallation.
A further method for the preparation of compounds of formula I is the reaction of 5-trialkyltin- pyrimidines, pyrimidine-5-boronic acids, pyrimidine-5-zinc compounds or pyrimidine-5- magnesium compounds with halo- or triflate-imidazoles under transition metal catalysis, preferably palladium or nickel catalysis.
Figure imgf000016_0001
= metal, e.g. Mg, Zn, Sn(alkyl)3 or B(OH)2 X = leaving group, e.g. Br, Cl, OSO2CF3 catalyst = e.g. Pd or Ni, and suitable ligand, e.g. triphenylphosphine
The 5-trialkyltin-pyrimidines, pyrimidine-5-boronic acids, pyrimidine-5-zinc compounds and pyrimidine-5-magnesium compounds can be prepared using methods known perse from the pyrimidine unsubstituted in the 5-position by deprotonation using an organolithium compound, e.g. n-butyllithium, and subsequent transmetallation. In addition, the 5-trialkyltin- pyrimidines, pyrimidine-5-boronic acids, pyrimidine-5-zinc compounds and pyrimidine-5- magnesium compounds can be prepared by halogen-metal exchange starting from a 5-haIo- pyrimidine and using an organolithium compound, e.g. n-butyllithium, or using magnesium or an organomagnesium compound and subsequent transmetallation.
Selective substitution at the 5-position of the imidazole (R-i and R2 are not hydrogen) can be achieved by deprotonation using a strong base, e.g. n-butyllithium, and subsequent reaction with an electrophile.
Figure imgf000016_0002
base = e.g. n-butyllithium electrophile = R3-X X = leaving group, e.g. Br, Cl, S02NMe2
The compounds of formula I can also be obtained by cyclisation of 5-(2-haloalkylcarbonyl)- pyrimidines, especially 5-(2-bromoalkylcarbonyl)-pyrimidines with amidines. The NH group of the imidazole can subsequently be derivatised with an electrophile. 15
desiccant solvent
Figure imgf000017_0001
X = leaving group, e.g. I, Br, Cl desiccant = e.g. Na2SO4
Figure imgf000017_0002
5-(2-Haloalkylcarbonyl)-pyrimidines are obtained, for example, by halogenation of 5- (alkylcarbonyl)-pyrimidines or 5-(2-hydroxyalkylcarbonyl)-pyrimidines using a halogenating agent.
halogenating agent solvent
Figure imgf000017_0003
Figure imgf000017_0004
Y = H, OH halogenating agent = e.g. HBr, Br2 X = I, Br, Cl
A further method for the preparation of 5-(alkylcarbonyl)-pyrimidines starts from 5-halo- pyrimidines, preferably 5-bromo-pyrimidines, which, under transition metal catalysis, preferably palladium or nickel catalysis, in the presence of carbon monoxide and an alcohol, are converted into the 5-alkyloxycarbonyl compounds. The 5-alkyloxycarbonyl compounds can be converted into the 5-(alkylcarbonyl)-pyrimidines by methods known perse, e.g. by reaction with malonic acid derivatives and subsequent hydrolysis.
Figure imgf000018_0001
alkyl-alcohol, CO
Figure imgf000018_0002
(solvent)
X= leaving group, e.g. Cl, Br, I, OS02CF3
Figure imgf000018_0003
catalyst = metal, e.g. Pd or Ni 1) base and ligand, e.g. triphenylphosphine 2) acid 3) heating alkyl-alcohol = e.g. ethanol solvent
Figure imgf000018_0004
base = e.g. triethylamine
Figure imgf000018_0005
The reactions resulting in compounds of formula I are advantageously carried out in aprotic, inert, organic solvents. Such solvents are hydrocarbons, e.g. benzene, toluene, xylene or cyclohexane, chlorinated hydrocarbons, e.g. dichloromethane, trichloromethane, tetrachloro- methane or chlorobenzene, ethers, e.g. diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran or dioxane, nitriles, e.g. acetonitrile or propionitrile, and amides, e.g. N,N-dimethylformamide, diethylformamide or N-methyl- pyrrolidinone. The reaction temperatures are preferably from -78°C to +120°C. The reactions are generally slightly exothermic and may usually be carried out at room temperature. In order to shorten the reaction time or else to initiate the reaction, brief heating up to the boiling point of the reaction mixture may be carried out, where appropriate. The reaction times may also be reduced by adding a few drops of base as reaction catalyst. Especially suitable bases are tertiary amines, e.g. trimethylamine, triethylamine, quinuclidine, 1 ,4- diazabicyclo[2.2.2]octane, 1 ,5-diazabicyclo[4.3.0]non-5-ene or 1 ,5-diazabicyclo[5.4.0]undec- 7-ene. It is, however, also possible for inorganic bases such as hydrides, e.g. sodium or calcium hydride, hydroxides, e.g. sodium or potassium hydroxide, carbonates, e.g. sodium or potassium carbonate, or hydrogen carbonates, e.g. potassium or sodium hydrogen carbonate, to be used as bases.
The compounds of formula I may be isolated in conventional manner by concentration and/or evaporation of the solvent and purified by recrystallisation or trituration of the solid residue in solvents in which they are not readily soluble, such as ethers, aromatic hydrocarbons or chlorinated hydrocarbons.
The present invention relates also to herbicidal compositions which, in addition to comprising customary inert formulation adjuvants, comprise as active ingredient a compound of formula I
Figure imgf000019_0001
wherein
R1 is hydrogen, halogen, cyano, amino, hydroxy, nitro, formyl, -COOH, -CONH2, -CSNH2, Crdalkyl, halo-d-C6alkyl, d-C6alkoxy, halo-C C6alkoxy, CrC6alkylamino, halo-d-dr alkylamino, CrCedialkylamino wherein the alkyl groups are the same or different or together with the nitrogen atom to which they are bonded form a 4- to 7-rrιembered ring which may be interrupted by a further N, O or S, halo-d-C6dialkyIamino wherein the alkyl groups are the same or different, (d-C6alkyl)S(O)m, (halo-CrC6alkyl)S(O)m, (d-Cealkylamino^O)™ (d- C6dialkyIamino)S(O)m wherein the alkyl groups are the same or different, (halo-d-C6dialkyl- amino)S(O)m wherein the alkyl groups are the same or different, Crdalkylsulfonyloxy, halo- d-Cealkylsulfonyloxy, CrC6alkylS(O)mamino; CrC6alkylS(O)mannino substituted by halogen, amino, CrC6alkylamino, d-Cedialkylamino, hydroxy, cyano, C C4alkoxy or by formyl; d-Cealkoxy-d-Cealkyl, halo-CrC6alkoxy-CrC6alkyl, CrC6alkoxy-CrC6alkyloxy, halo- d-C6alkoxy-CrC6alkyloxy, d-Cealkoxy-d-Cealkylamino, halo-C-ι-C6alkoxy-CrC6alkylamino, CrC6alkylS(O)m-CrC6a]kyl, halo-CrC6alkylS(O)m-CrC6alkyl, C1-C6alkylS(O)m-CrC6alkyloxy, halo-CrCealkylSCOm-CrCealkyloxy, CrC6alkylS(O)m-CrC6alkylamino, halo-d-C6alkylS(O)m- CrC6alkylamino, CrC6alkylcarbonyl; C C6alkylcarbonyl substituted by halogen, amino, CrC6alkylamino, CrC6dialkylamino, hydroxy, cyano, CrC4alkoxy or by formyl; d-C6alkoxy- carbonyl; d-C6alkoxycarbonyl substituted by halogen, amino, C-ι-C6alkylamino, CrCedialkylamino, hydroxy, cyano, C C alkoxy or by formyl; C C6alkylcarbonyloxy; d-C6alkylcarbonyl- oxy substituted by halogen, amino, CrC6alkylamino, CrC6dialkylamino, hydroxy, cyano, d-C4alkoxy or by formyl; formylamino, CrC6alkylcarbonylamino; CrC6alkylcarbonylamino substituted by halogen, amino, d-C6alkyIamino, d-Cedialkylamino, hydroxy, cyano, d-C4alkoxy or by formyl; CrC6alkylaminocarbonyl; CrC6alkylaminocarbonyl substituted by halogen, amino, CrC6alkylamino, d-Cedialkylamino, hydroxy, cyano, d-C4alkoxy or by formyl; d-Cedialkylaminocarbonyl wherein the alkyl groups are the same or different; d-Cedialkylaminocarbonyl substituted by halogen, amino, Cι-C6alkylamino, d-Cedialkylamino, hydroxy, cyano, d-C4alkoxy or by formyl, wherein the alkyl groups are the same or different; C2-C6alkenyl, halo-C2-C6alkenyl, C3-C6alkenyIoxy, halo-C3-CeaIkenyloxy, (C2-C6alkenyl)S(O)m, (halo-C2-C6alkenyl)S(O)m, C3-C6aIkenylamino, halo-C3-C6alkenylamino, C3-C6dialkenylamino wherein the alkenyl radicals are the same or different, halo- C3-C6dialkenylamino wherein the alkenyl radicals are the same or different, C3-C6cycloalkyl; C3-C6cycloalkyl substituted by halogen, amino, d-Cealkylamino, d-Cedialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; tri(d-C6alkyl)silyl; tri(d-C6alkyl)siIyl substituted by halogen, amino, CrC6alkylamino, d-Cedialkylamino, hydroxy, cyano, d-C alkoxy or by formyl; pentafluorothio, C2-C6alkynyl; C2-C6alkynyl substituted by halogen, amino, CrC6alkylamino, CrCedialkylamino, hydroxy, cyano, C C4alkoxy, tri(CrC6alkyl)silyI or by formyl; C3-C6alkynyloxy, halo-C3-C6alkynyloxy, (C3-C6alkynyl)S(O)m, (halo-C3-C6alkynyl)S(O)m, C3-C6alkynylamino, halo-C3-C6alkynylamino, C3-C6dialkynylamino wherein the alkynyl radicals are the same or different, halo-C3-C6dialkynylamino wherein the alkynyl radicals are the same or different, -Q or -A-Q;
R2 is hydrogen, cyano, hydroxy, amino, formyl, -CONH2, -CSNH2, CrC6alkyl; CrC6alkyl substituted by halogen, amino, d-Cealkylamino, d-Cedialkylamino, hydroxy, cyano, Crdalkoxy or by formyl; d-C6alkoxy; Crdalkoxy substituted by halogen, amino, CrCealkylamino, CrC6dialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; CrC6alkyIamino, halo- CrC6alkylamino, CrCedialkylamino wherein the alkyl groups are the same or different, halo- d-Cedialkylamino wherein the alkyl groups are the same or different, (CrCealkyl)S(O)m, (halo-CrC6alkyl)S(O)m, (CrC6alkylamino)S(O)m, (CrC6dialkylamino)S(O)m wherein the alkyl groups are the same or different, (halo-CrC6dialkylamino)S(O)m wherein the alkyl groups are the same or different, halo-CrC6alkoxy-CrC6alkyl, CrC6alkylS(O)m-CrC6alkyl, halo- CrC6alkylS(O)m-CrC6alkyl, d-C6alkylcarbonyl; CrC6alkylcatbonyl substituted by halogen, amino, CrC6alkylamino, CrCedialkylamino, hydroxy, cyano, d-C4alkoxy or by formyl; d-C6alkoxycarbonyl; CrC6alkoxycarbonyl substituted by halogen, amino, CrC6alkylamino, CrC6dialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; d-Cealkylcarbonyloxy; CrC6alkylcarbonyloxy substituted by halogen, amino, d-C6a!kylamino, CrC6dialkylamino, hydroxy, cyano, C C4alkoxy or by formyl; formylamino, CrCealkylcarbonylamino; d-C6alkyl- carbonylamino substituted by halogen, amino, CrC6alkylamino, CrC6dialkylamino, hydroxy, cyano, C C4alkoxy or by formyl; CrC6alkylaminocarbonyl; CrCealkylaminocarbonyl substituted by halogen, amino, d-C6alkylamino, CrCedialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; CrC6dialkylaminocarbonyl wherein the alkyl groups are the same or different; CrC6dialkylaminocarbonyl substituted by halogen, amino, Crdalkylamino, d-Cedialkylamino, hydroxy, cyano, d-dalkoxy or by formyl, wherein the alkyl groups are the same or different; C2-C6alkenyl, halo-C2-C6alkenyl, C2-C6aIkenyloxy, halo-C2-C6- alkenyloxy, (C2-C6alkenyl)S(O)m, (halo-C2-C6alkenyl)S(O)m, C3-C6cycloalkyl; C3-C6cycloalkyl substituted by halogen, amino, CrC6alkylamino, CrC6dialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; tri(CrC6alkyl)silyl; tri(CrC6alkyl)silyl substituted by halogen, amino, CrC6alkylamino, d-Cedialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; C2-C6alkynyl; C2-C6alkynyl substituted by halogen, amino, CrC6alkylamino, d-Cedialkylamino, hydroxy, cyano, C C4alkoxy or by formyl, -Q or -A-Q;
R3 is hydrogen, halogen, cyano, amino, hydroxy, nitro, formyl, -COOH, -CONH2, -CSNH2, Crdalkyl, halo-d-C6alkyl, CrC6alkoxy, halo-CrC6alkoxy, d-C6alkylamino, halo-C C6- alkylamino, CrC6dialkylamino wherein the alkyl groups are the same or different or together with the nitrogen atom to which they are bonded form a 4- to 7-membered ring which may be interrupted by a hetero atom such as N, O or S, halo-d-C6dialkylamino wherein the alkyl groups are the same or different, (CrC6alkyl)S(O)m, (halo-CrC6alkyl)S(O)m, (CrC6alkyl- amino)S(O)m, (CrC6dialkylamino)S(O)m wherein the alkyl groups are the same or different, (halo-CrC6diaikylamino)S(O)m wherein the alkyl groups are the same or different, d-C6- alkylsulfonyloxy, halo-d-C6alkylsulfonyloxy, CrC6alkylS(O)mamino; CrC6alkyIS(O)mamino substituted by halogen, amino, d-C6alkylamino, CrCedialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; CrCealkoxy-CrC6alkyl, halo-CrC6alkoxy-CrC6alkyl, CrC6alkoxy- d-C6alkyloxy, halo-CrCealkoxy-CrC6alkyloxy, d-Cealkoxy-CrCealkylamino. halo- CrC6alkoxy-d-C6alkylamino, CrC6alkylS(O)m-CrC6alkyl, halo-CrC6alkylS(0)m-CrC6alkyl, Cι-C6alkylS(O)m-CrC6alkyloxy, halo-CrC6alkylS(O)m-CrC6alkyloxy, d-C6alkylS(O)m- CrC6alkylamino, halo-CrC6alkylS(O)m-CrC6alkylamino, CrC6alkylcarbonyl; CrC6alkyl- carbonyl substituted by halogen, amino, d-Cealkylamino, CrC6dialkylamino. hydroxy, cyano, d-dalkoxy or by formyl; CrC6alkoxycarbonyl; Crdalkoxycarbonyl substituted by halogen, amino, CrC6alkylamino, CrC6dialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; d-C6alkylcarbonyloxy; d-C6alkylcarbonyloxy substituted by halogen, amino, CrC6alkylamino, CrC6dialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; formylamino, CrC6alkylcarbonylamino; CrCealkylcarbonylamino substituted by halogen, amino, d-Cealkylamino, d-Cedialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; CrCealkylaminocarbonyl; CrCealkylaminocarbonyl substituted by halogen, amino, CrC6alkylamino, CrC6dialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; d-Cedialkylaminocarbonyl wherein the alkyl groups are the same or different; d-Cedialkylaminocarbonyl substituted by halogen, amino, CrC6alkylamino, d-C6dialky!amino, hydroxy, cyano, Crdalkoxy or by formyl, wherein the alkyl groups are the same or different; C2-C6alkenyl, halo-C2-C6alkenyl, C3-C6alkenyloxy, haIo-C3-C6alkenyloxy, (C2-C6alkenyl)S(O)m, (halo-C2-C6alkenyI)S(O)m, C3-C6alkenylamino, halo-C3-C6alkenylamino, C3-C6dialkenylamino wherein the alkenyl radicals are the same or different, halo-C3-C6dialkenylamino wherein the alkenyl radicals are the same or different, C3-C6cycloalkyl; C3-C6cycloalkyl substituted by halogen, amino, CrC6alkylamino, d-Cedialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; tri(CrC6alkyl)silyl; tri(CrC6alkyl)silyl substituted by halogen, amino, CrC6alkylamino, CrCedialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; pentafluorothio, C2-C6alkynyl; C2-C6alkynyl substituted by halogen, amino, d-Cealkylamino, d-Cedialkylamino, hydroxy, cyano, d-dalkoxy, tri(C C6alkyl)silyl or by formyl; C3-C6alkynyloxy, halo-C3-C6alkynyloxy, (C3-C6alkynyl)S(O)m, (halo-C3-C6alkynyl)S(O)m, C3-C6a!kynylamino, halo-C3-C6alkynylamino, C3-C6dialkynylamino wherein the alkynyl radicals are the same or different, or halo-C3-C6- dialkynylamino wherein the alkynyl radicals are the same or different;
R4 is hydrogen, halogen, cyano, amino, nitro, formyl, -COOH, -CONH2, -CSNH2, d-C6alkyl, halo-d-C6alkyl, Crdalkoxy, halo-d-dalkoxy, d-Cealkylamino, CrCedialkylamino wherein the alkyl groups are the same or different or together with the nitrogen atom to which they are bonded form a 4- to 7-membered ring, halo-Crddialkylamino wherein the alkyl groups are the same or different, (CrCβalkyl)S(O)m> (halo-d-C6alkyl)S(O)m, Crdalkoxy-CrCealkyl, halo-CrC6alkoxy-CrC6alkyl, C C6alkylcarbonyl; d-dalkylcarbonyl substituted by halogen, amino, d-Cealkylamino, CrC6dialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; d-Cealkoxycarbonyl; CrC6alkoxycarbonyl substituted by halogen, amino, CrC6alkylamino, d-Cedialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; Crdalkylcarbonylamino; CrCealkylcarbonylamino substituted by halogen, amino, Crdalkylamino, CrCedialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; CrC6alkylaminocarbonyl; CrC6alkylaminocarbonyl substituted by halogen, amino, d-Cealkylamino, d-Cedialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; Ci-C6dialkylaminocarbonyl wherein the alkyl groups are the same or different; Crddialkylaminocarbonyl substituted by halogen, amino, Cι-C6alkylamino, CrC6dialkylamino, hydroxy, cyano, d-dalkoxy or by formyl, wherein the alkyl groups are the same or different; C2-C6alkenyl, halo-C2-C6alkenyl, C3-C6cycloalkyl; C3-C6cycloalkyl substituted by halogen, amino, d-dalkylamino, C C6dialkylamino, hydroxy, cyano, Crdalkoxy or by formyl; tri(d-C6alkyl)silyl, C2-C6alkynyl; or C2-C6alkynyl substituted by halogen, amino, CrC6alkylamino, d-Cedialkylamino, hydroxy, cyano, d-C4alkoxy, tri(d-C6alkyl)silyl or by formyl;
A is d-dalkylene; d-C4alkylene substituted by halogen, amino, d-Cealkylamino, d-Cedialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; d-C4oxyalkylene; C C4oxyalkylene substituted by halogen, amino, d-dalkylamino, Crddialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; d-dalkyleneoxy; d-dalkyleneoxy substituted by halogen, amino, CrC6alkylamino, CrC6dialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; d-C4oxy- alkyleneoxy; CrC oxyalkyleneoxy substituted by halogen, amino, d-Cealkylamino, Cn-C6di- alkylamino, hydroxy, cyano, d-dalkoxy or by formyl; d-daminoalkylene; d-damino- alkylene substituted by halogen, amino, Crdalkylamino, d-C6dialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; d-dalkyleneamino; Crdalkyleneamino substituted by halogen, amino, d-C6alkylamino, CrC6dialkylamino, hydroxy, cyano, d-dalkoxy or by formyl ; d-C4- aminoalkyleneamino; d-C4aminoalkyleneamino substituted by halogen, amino, d-C6alkyl- amino, d-Cedialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; d-C4thioalkylene; Crdthioalkylene substituted by halogen, amino, CrC6alkylamino, d-C6dialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; C3-C6cycloalkylene; C3-C6cycloalkylene substituted by halogen, amino, CrC6alkylamino, d-Cedialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; C2-C4alkenylene; C2-C alkenylene substituted by halogen, amino, CrC6alkylamino, CrCedialkylamino, hydroxy, cyano, C C4alkoxy or by formyl; C2-C4alkynylene; C2-C4alkynyl- ene substituted by halogen, amino, CrC6alkylamino, d-Cedialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; O, S, NH, formylamino, d-dalkylamino, S(O)m, oxysulfonyl, sulfonyloxy, aminosulfonyl, sulfonylamino, carbonyl, oxycarbonyl, carbonyloxy, oxycarbonyloxy, carbonylamino, aminocarbonyl, aminocarbonyloxy, oxycarbonylamino or aminocarbonylamino;
Q is aryl, aryl substituted one or more times by halogen, cyano, hydroxy, amino, nitro, formyl, -COOH, -CONH2, -CSNH2, d-dalkyl, halo-d-dalkyl, C C6alkoxy, haIo-Cι-C6alkoxy, CrC6alkylamino, halo-CrC6alkylamino, CrC6dialkylamino wherein the alkyl groups are the same or different or together with the nitrogen atom to which they are bonded form a 4- to 7- membered ring, halo-d-C6dialkylamino wherein the alkyl groups are the same or different, (d-C6alkyl)S(O)m, (halo-CrC6alkyl)S(O)m, (CrC6alkylamino)S(O)m, (CrC6dialkyl- amino)S(O)m wherein the alkyl groups are the same or different, (halo-Crddialkylamino)- S(O)m wherein the alkyl groups are the same or different, d-dalkylsulfonyloxy, halo-Crd- alkylsulfonyloxy, CrC6alkylS(O)mamino; CrC6alkylS(O)mamino substituted by halogen, amino, d-Cealkylamino, CrCedialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; d-Cealkoxy-d-Cealkyl, halo-CrC6alkoxy-CrC6alkyl, CrC6alkoxy-CrC6alkyloxy, halo- CrCealkoxy-CrC6alkyloxy, CrC6alkoxy-CrC6alkylamino, halo-CrC6alkoxy-CrC6alkylamino, Cι-C6alkylS(O)m-CrC6alkyl, halo-CrC6alkylS(O)m-CrC6alkyl, CrC6alkylS(O)m-CrC6alkyloxy, halo-CrC6alkylS(O)m-CrC6alkyloxy, CrC6alkylS(O)m-CrC6alkylamino, halo-CrC6alkylS(O)m- CrC6alkylamino, d-C6alkylcarbonyl; d-C6alkylcarbonyl substituted by halogen, amino, Crdalkylamino, CrC6dialkylamino, hydroxy, cyano, d-C alkoxy or by formyl; Crdalkoxy- carbonyl; d-C6alkoxycarbonyl substituted by halogen, amino, Crdalkylamino, CrCedialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; d-dalkylcarbonyloxy; d-C6a!kyl- carbonyloxy substituted by halogen, amino, d-dalkylamino, Crddialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; formylamino, CrCealkylcarbonylamino; CrCealkylcarbonylamino substituted by halogen, amino, Crdalkylamino, Crddialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; Crdalkylaminocarbonyl; CrCealkylaminocarbonyl substituted by halogen, amino, Crdalkylamino, Crddialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; d-ddialkylaminocarbonyl wherein the alkyl groups are the same or different; d-ddialkylaminocarbonyl substituted by halogen, amino, Crdalkylamino, d-Cedialkylamino, hydroxy, cyano, d-dalkoxy or by formyl, wherein the alkyl groups are the same or different; C2-C6alkenyl, halo-C2-C6alkenyl, C3-C6alkenyloxy, halo-C3-C6alkenyloxy, (C2-C6- alkenyl)S(O)m, (halo-C2-C6alkenyl)S(O)m, C3-C6alkenylamino, halo-C3-C6alkenylamino, C3-C6- dialkenylamino wherein the alkenyl radicals are the same or different, halo-C3-C6dialkenyl- amino wherein the alkenyl radicals are the same or different, C3-C6cycloalkyl; d-dcycloalkyl substituted by halogen, amino, Crdalkylamino, CrCedialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; tri(C1 -C6al kyl)sily I ; tri(d-C6alkyl)silyl substituted by halogen, amino, CrC6alkyIamino, d-Cedialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; pentafluoro- thio; d-dalkynyl, or C2-C6alkynyl substituted by halogen, amino, Crdalkylamino, CrCedialkylamino, hydroxy, cyano, d-dalkoxy, tri(CrC6alkyl)silyl or by formyl; C3-C6alkynyloxy, halo-C3-C6alkynyloxy, (C3-C6alkynyl)S(O)m, (halo-C3-C6alkynyJ)S(O)m, C3-C6alkynylamino, halo-C3-C6alkynylamino, C3-C6dialkynylamino wherein the alkynyl radicals are the same or different, halo-C3-C6dialkynylamino wherein the alkynyl radicals are the same or different, or Q is a monocyclic heterocycle, or a monocyclic heterocycle substituted one or more times by halogen, cyano, hydroxy, amino, nitro, formyl, -COOH, -CONH2, -CSNH2, d-dalkyl, halo-d-dalkyl, d-dalkoxy, halo-d-dalkoxy, Crdalkylamino, halo-Crdalkylamino, Crddialkylamino wherein the alkyl groups are the same or different or together with the nitrogen atom to which they are bonded form a 4- to 7-membered ring, halo-Crddialkyl- amino wherein the alkyl groups are the same or different, (CrC6alkyl)S(O)m, (halo-d-C6- alkyl)S(O)m> (CrC6alkylamino)S(O)m, (CrC6dialkylamino)S(O)m wherein the alkyl groups are the same or different, (halo-d-C6dialkylamino)S(O)m wherein the alkyl groups are the same or different, d-dalkylsulfonyloxy, halo-CrC6alkylsulfonyloxy, CrC6alkylS(O)mamino; CrC6alkylS(O)mamino substituted by halogen, amino, d-dalkylamino, CrCedialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; Crdalkoxy-d-dalkyl, halo-CrC6alkoxy-d-C6- alkyl, d-dalkoxy-Crdalkyloxy, halo-CrC6alkoxy-CrC6alkyloxy, Crdalkoxy-Crdalkyl- amino, halo-Crdalkoxy-Crdalkylamino, CrC6alkylS(O)m-Cι-C6alkyl, halo-d-C6alkylS(O)m- d-C6alkyl, CrC6alkylS(O)m-CrC6aikyloxy, halo-CrC6alkylS(O)m-CrC6alkyloxy, d-dalkyl- S(O)m-CrC6alkylamino, halo-CrC6alkylS(O)m-Cι-C6alkylamino, d-C6alkylcarbonyl; d-C6alkylcarbonyl substituted by halogen, amino, Crdalkylamino, CrCedialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; Crdalkoxycarbonyl; d-dalkoxycarbonyl substituted by halogen, amino, Crdalkylamino, CrCedialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; d-dalkylcarbonyloxy; d-C6alkylcarbonyloxy substituted by halogen, amino, d-dalkylamino, d-Cedialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; formylamino, d-dalkylcarbonylamino; Crdalkylcarbonylamino substituted by halogen, amino, d-dalkylamino, d-C6dialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; CrCealkylaminocarbonyl; Crdalkylaminocarbonyl substituted by halogen, amino, d-dalkylamino, Crddialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; d-ddialkylaminocarbonyl wherein the alkyl groups are the same or different; d-Cedialkylaminocarbonyl substituted by halogen, amino, d-dalkylamino, d-Cedialkylamino, hydroxy, cyano, d-dalkoxy or by formyl, wherein the alkyl groups are the same or different; C2-C6alkenyl, halo-C2-C6alkenyl, C3-C6alkenyloxy, halo-C3-C6alkenyloxy, (C2-C6alkenyl)- S(O)m, (halo-C2-C6alkenyl)S(O)m, C3-C6alkenylamino, halo-C3-C6alkenylamino, d-ddialkenylamino wherein the alkenyl radicals are the same or different, halo- C3-C6dialkenylamino wherein the alkenyl radicals are the same or different, C3-C6cycloalkyl; C3-C6cycloalkyl substituted by halogen, amino, d-dalkylamino, CrCedialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; tri(CrC6alkyl)silyl; tri(CrC6alkyl)silyl substituted by halogen, amino, d-dalkylamino, CrCedialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; pentafluorothio; d-dalkynyl, or C2-C6alkynyl substituted by halogen, amino, d-Cealkylamino, CrCedialkylamino, hydroxy, cyano, d-dalkoxy, tri(CrC6alkyl)siIyI or by formyl; C3-C6alkynyloxy, halo-C3-C6alkynyloxy, (C3-C6alkynyl)S(O)m, (halo-C3-C6alkynyl)S(O)m, C3-C6alkynylamino, halo-C3-C6alkynylamino, C3-C6diaIkynylamino wherein the alkynyl radicals are the same or different, halo-C3-C6dialkynylamino wherein the alkynyl radicals are the same or different, and m is 0, 1 or 2, or an enantiomer, a mixture of enantiomers, a tautomer, a mixture of tautomers, or an agrochemically acceptable salt of a compound of formula I, an N-oxide of such a compound or an enantiomer, a mixture of enantiomers, a tautomer, a mixture of tautomers or an agrochemically acceptable salt thereof.
For the use according to the invention of the compounds of formula I, or of compositions comprising them, there come into consideration all methods of application customary in agriculture, for example pre-emergence application, post-emergence application and seed dressing, and also various methods and techniques such as, for example, the controlled release of active ingredient. For that purpose a solution of the active ingredient is applied to mineral granule carriers or polymerised granules (urea/formaldehyde) and dried. If required, it is also possible to apply a coating (coated granules), which allows the active ingredient to be released in metered amounts over a specific period of time.
The compounds of formula I may be used as herbicides in their unmodified form, that is to say as obtained in the synthesis, but they are preferably formulated in customary manner together with the adjuvants conventionally employed in formulation technology, for example into emulsifiable concentrates, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granules or microcapsules. Such formulations are described, for example, on pages 9 to 13 of WO 97/34485. As with the nature of the compositions, the methods of application, such as spraying, atomising, dusting, wetting, scattering or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances.
The formulations, that is to say the compositions, preparations or mixtures comprising the compound (active ingredient) of formula I, or at least one compound of formula I, and, usually, one or more solid or liquid formulation adjuvants, are prepared in known manner, e.g. by homogeneously mixing and/or grinding the active ingredient(s) with the formulation adjuvants, for example solvents or solid carriers. Surface-active compounds (surfactants) may also be used in addition in the preparation of the formulations. Examples of solvents and solid carriers are given, for example, on page 6 of WO 97/34485.
Depending upon the nature of the compound of formula I to be formulated, suitable surface- active compounds are non-ionic, cationic and/or anionic surfactants and surfactant mixtures having good emulsifying, dispersing and wetting properties.
Examples of suitable anionic, non-ionic and cationic surfactants are listed, for example, on pages 7 and 8 of WO 97/34485. In addition, the surfactants conventionally employed in formulation technology, which are described, inter alia, in "McCutcheon's Detergents and Emulsifiers Annual" MC Publishing Corp., Ridgewood New Jersey, 1981 , Stache, H., "Tensid-Taschenbuch", Carl Hanser Verlag, Munich/Vienna, 1981 , and M. and J. Ash, "Encyclopedia of Surfactants", Vol. I-III, Chemical Publishing Co., New York, 1980-81 , are also suitable for the preparation of the herbicidal compositions according to the invention.
The herbicidal formulations generally contain from 0.1 to 99 % by weight, especially from 0.1 to 95 % by weight, of herbicide, from 1 to 99.9 % by weight, especially from 5 to 99.8 % by weight, of a solid or liquid formulation adjuvant, and from 0 to 25 % by weight, especially from 0.1 to 25 % by weight, of a surfactant. Whereas commercial products will preferably be in the form of concentrates, the end user will normally employ dilute formulations. The compositions may also comprise further ingredients, such as stabilisers, for example vegetable oils or epoxidised vegetable oils (epoxidised coconut oil, rapeseed oil or soybean oil), anti-foams, for example silicone oil, preservatives, viscosity regulators, binders, tackifiers, and also fertilisers or other active ingredients.
The compounds of formula I are generally applied to the plant or the locus thereof at rates of application of from 0.001 to 4 kg/ha, especially from 0.005 to 2 kg/ha. The concentration required to achieve the desired effect can be determined by experiment. It is dependent on the nature of the action, the stage of development of the cultivated plant and of the weed and on the application (place, time, method) and may vary within wide limits as a function of those parameters.
The compounds of formula I are distinguished by herbicidal and growth-inhibiting properties, allowing them to be used in crops of useful plants, especially cereals, cotton, soybeans, sugar beet, sugar cane, plantation crops, rape, maize and rice, and also for non-selective weed control. The term "crops" is to be understood as including also crops that have been made tolerant to herbicides or classes of herbicides as a result of conventional methods of breeding or genetic engineering techniques. The weeds to be controlled may be either monocotyledonous or dicotyledonous weeds, such as, for example, Stellaria, Nasturtium, Agrostis, Digitaria, Avena, Setaria, Sinapis, Lolium, Solanum, Echinochloa, Scirpus, Monochoria, Sagittaria, Bromus, Alopecurus, Sorghum halepense, Rottboellia, Cyperus, Abutilon, Sida, Xanthium, Amaranthus, Chenopodium, Ipomoea, Chrysanthemum, Galium, Viola and Veronica.
The following Examples further illustrate the invention, without limiting it.
Preparation Examples:
Example P-1 A: Preparation of 5-chloro-1-methy!-2-trifluoromethyl-1 H-imidazole
Figure imgf000028_0001
24 g of 1 -methyl-2-trif luoromethyl-1 H-imidazole are dissolved in THF (about 80 ml) and, at -70°C, 100 ml of n-butyllithium (about 1.6M in hexane) are added. After 10 minutes, 23 g of N,N-dimethylsulfamoyl chloride are added. After a further 10 minutes, acetic acid (25 ml) is added and the mixture is allowed to come to room temperature. Extraction by shaking with hexane and water is carried out and also washing with saturated NaHCO3 solution, drying (MgSO4) and concentrating. 29.5 g of crude product are obtained. Distillation at 100-110°C (high vacuum) yields 18.6 g of 5-chloro-1 -methyl-2-trif luoromethyl-1 H-imidazole. 1H NMR (300 MHz, CDCI3) 3.74 (s, 3H, CH3); 7.04 (s, 1H, H-C(4)) Example P-1 B: Preparation of 5-(5-chloro-1 -methyl-2-trif luoromethyl-1 H-imidazol-4-yl)- pyrimidine
Figure imgf000029_0001
To 1.1 g of 5-chloro-1 -methyl-2-trif luoromethyl-1 H-imidazole in 180 ml of THF, under an argon atmosphere at -78°C, there are added first 72 ml of 2M lithium diisopropylamide solution and then 120 ml of 1 M ZnCI2 solution in THF. After one hour at -78°C, 6.9 g of tetrakis(triphenylphosphine)palladium(0) and 11.4 g of 5-bromopyrimidine are added. The reaction mixture is allowed to come to room temperature and is stirred for 16 hours at room temperature. The reaction mixture is concentrated and the residue is taken up in ethyl acetate. The organic phase is washed with EDTA2Na solution and 10 % NaHCO3 solution, dried and concentrated. After chromatography of the crude product on silica gel using ethyl acetate/hexane (1 :3), 7.6 g of the title product having a melting point of 90-91 °C (compound 1-1.) are obtained.
Example P-2: Preparation of 2-amino-5-(5-chloro-1 -methyI-2-trifluoromethyl-1 H-imidazol-4- yl)-pyrimidine
Figure imgf000029_0002
To 0.55 g of 5-chloro-1-methyl-2-trifluoromethyl-1H-imidazoIe in 24 ml of THF, under an argon atmosphere at -78°C, there are added first 1.5 ml of 2M lithium diisopropylamide solution and then 6 ml of 1 M ZnCI2 solution in THF. After one hour at -78°C, there are added 0.35 g of tetrakis(triphenylphosphine)palladium(0) and 0.52 g of 2-amino-5-bromopyrimidine. The reaction mixture is allowed to come to room temperature and is stirred for 36 hours at room temperature. The reaction mixture is concentrated and the residue is taken up in ethyl acetate. The organic phase is washed with saturated EDTA"2Na solution and 10 % NaHCO3 solution, dried and concentrated. After chromatography of the crude product on silica gel using diethyl ether/hexane (2:1), 59 mg of the title product having a melting point of 262- 263°C (compound 1 -2.) are obtained.
Example P-3: Preparation of 5-(5-chIoro-1 -methyl-2-trif luoromethyl-1 H-imidazol-4-yl)- pyrimidine 1 -oxide
Figure imgf000030_0001
To 0.79 g of 5-(5-chloro-1 -methyl-2-trif luoromethyl-1 H-imidazol-4-yl)-pyrimidine and 0.37 g of urea-hydrogen peroxide complex in 24 ml of methylene chloride, at 0°C, there is added 0.54 ml of trifluoroacetic anhydride and stirring is carried out for 48 hours at room temperature. The reaction mixture is diluted with methylene chloride and is washed with 10 % NaHCO3 solution, dried and concentrated. After chromatography of the crude product on silica gel using ethyl acetate/hexane (1 :1), 0.12 g of the title product having a melting point of 90-91 °C (compound 2-1.) is obtained.
Example P-4: Preparation of 2-chloro-5-(5-chloro-1-methyl-2-trifluoromethyl-1 H-imidazol-4~ yl)-pyrimidine
Figure imgf000030_0002
To 0.11 g of 5-(5-chloro-1-methyl-2-trifluoromethyl-1 H-imidazol-4-yl)-pyrimidine 1 -oxide in 2 ml of ethylene dichloride, at room temperature, there is added 0.073 ml of phosphorus oxychloride and stirring is carried out for 24 hours at 80°C. The reaction mixture is diluted with ethyl acetate and is washed with 10 % NaHCO3 solution, dried and concentrated. After chromatography of the crude product on silica gel using methylene chloride/hexane (1 :1), 32 mg of the title product having a melting point of 128-129°C (compound 1 -4.) are obtained.
Example P-5 A: Preparation of 5-propionyl-pyrimidine
Figure imgf000031_0001
5.6 g of pyrimidine-5-carboxaldehyde in 100 ml of ether are slowly added dropwise, at 0-5°C, to 18 ml of 3M ethylmagnesium bromide solution in ether. The yellowish suspension is stirred for 1 hour at 5°C and then 30 ml of saturated NH4CI are added, with cooling. The phases are separated and the reaction solution is extracted 3 times with diethyl ether. The combined organic phases are washed with brine, filtered and concentrated. 3.14 g of a yellow oil are obtained, which - as the crude product - is reacted further.
The intermediate is dissolved in 100 ml of methylene chloride and, after adding 10.26 g (1.2 eq.) of pyridinium dichromate, is stirred for 20 hours at room temperature. The reaction mixture is filtered over Hyflo. The organic phase is washed with H2O/brine, dried and concentrated. After chromatography of the crude product on silica gel using ethyl acetate/hexane (1 :2), 0.95 g of the title product is obtained in the form of a colourless oil.
Example P-5 B: Preparation of 5-(2-bromo-propionyl)-pyrimidine
Figure imgf000031_0002
To 950 mg of 5-propionyl-pyrimidine in 10 ml of 30 % HBr in AcOH there is added dropwise, at 0 - 5°C, 0.32 ml of Br2. The reaction solution is stirred for one hour and is then poured into ice-water. Extraction with ethyl acetate, washing and drying yield 910 mg of 5-(2-bromo- propiony])-pyrimidine in the form of a brown oil. Example P-5 C: Preparation of 5-(5-methyl-2-trifluoromethyl-1 H-imidazol-4-yl)-pyrimidine
Figure imgf000032_0001
To a suspension of 910 mg of 5-(2-bromo-propionyl)-pyrimidine and 2.4 g of sodium sulfate in 50 ml of acetonitrile there are added 2.76 g of trifluoroacetamidine (3 eq., 85 %). The reaction mixture is stirred for one hour in an ultrasonic bath and then for 60 hours at RT. The reaction mixture is filtered, concentrated and dried. 1.54 g of 5-(5-methyl-2-trifluoromethyl- 1 H-imidazol-4-yl)-pyrimidine are obtained in the form of a brown oil. The product is reacted further without purification.
Example P-5 D: Preparation of 5-(1 ,5-dimethyl-2-trifluoromethyl-1 H-imidazol-4-yl)-pyrimidine
Figure imgf000032_0002
1.54 g of 5-(5-methyl-2-trifluoromethyl-1 H-imidazol-4-yl)-pyrimidine are dissolved in 50 ml of acetone, and 1.87 g of potassium carbonate and 2.52 ml of methyl iodide are added. The reaction mixture is stirred for 6 hours at RT and is then poured into water. The aqueous phase is extracted with ethyl acetate, washed, dried and concentrated. After chromatography of the crude product on silica gel using ethyl acetate, 0.33 g of the title product (compound 1-92.) is obtained in the form of an oil. The compounds listed in the following Tables can be prepared in analogous manner. Table 1 : Compounds of formula I:
Figure imgf000033_0001
Cmp. R1 R2 R3 R4 Phys. data
1 -1. CF3 H H H m.p. 204-206°C
1-2. CF3 H Cl H m.p. 187-189°C
1-3. CF3 CH3 Cl H m.p. 90-91 °C
1 -4. CF3 CH3 Cl NH2 m.p. 262-263°C
1-5. CF3 CH3 Cl F m.p. 97-98°C
1-6. CF3 CH3 Cl Cl m.p. 128-129°C
1 -7. CF3 CH3 Cl Br m.p. 107-108°C
1-8. CF3 CH3 Cl l m.p. 115-116°C
1-9. CF3 CH3 Cl CN m.p. 91 -93°C
1 -10. CF3 CH3 Cl CH3 resin
1-11. CF3 CH3 Cl CH2CH3
1 -12. CF3 CH3 Cl OH m.p. 230°C
1-13. CF3 CH3 Cl OCH3 m.p. 121-122°C
1 -14. CF3 CH3 Cl O(CH2)2CH3
1-15. CF3 CH3 Cl SCH3 m.p. 102-103°C
1-16. CF3 CH3 Cl SOCH3
1-17. CF3 CH3 Cl SO2CH3 m.p. 166-167°C
1 -18. CF3 CH3 Cl N(C2H3)2 m.p. 57-58°C
1-19. CF3 CH3 Cl' trimethylsilyl- m.p. 57-58°C ethynyl
1 -20. CF3 CH3 Cl ethynyl resin
1-21. CF3 CHg Cl NHSO2CH3
1 -22. CF3 CH3 Cl NO2
1 -23. CF3 CH3 Cl morpholinyl(4') m.p. 152-153°C Cmp. R1 R2 R3 R4 Phys. data
1 -24. CF3 CH3 Cl CF3
1-25. CF3 CH3 Cl OCF3
1 -26. CF3 CH3 Cl NHC(O)H
1 -27. CF3 CH3 Cl NH(CH2)3F
1-28. CF3 CH3 Cl OCH2OCH3
1-29. CF3 CH3 Cl OCH2SCH3
1 -30. CF3 CH3 Cl CO2H m.p. 217-218°C
1-31. CF3 CH3 Cl CO2CH3 m.p. 136-137°C
1 -32. CF3 CH3 Cl CO2CH CH3 m.p. 71-72°C
1 -33. CF3 CH3 Cl CONH2 m.p. 248-250°C
1-34. CF3 CH3 Cl OCOCHg
1 -35. CF3 CH3 Cl NHC(O)CH3
1 -36. CF3 CH3 Cl NHC(O)CF3 m.p. 211-215°C
Figure imgf000034_0001
1-38. CF3 CH3 Cl CH2CH=CCI2
1-39. CF3 CH3 Cl OCH2CH=CH2
1 -40. CF3 CH3 Cl cyclopropyl
1-41. CF3 CH3 SCH3 H m.p. 93-94°C
1 -42. CF3 CH3 SO2CH3 H m.p. 211-213°C
1-43. CF3 CH3 CO2H H m.p. 235-237°C
1-44. CF3 CH3 CO2CH3 H m.p. 99-100°C
1-45. CF3 CH3 CO2CH2CH3 H resin
1-46. CF3 CH3 CONHg H m.p. 236-237°C
1 -47. CF3 CH3 CN H m.p. 89-90°C
1-48. CF3 CH3 CO2CH2CH3 CO2CH2CH3 resin
1-49. CF3 CH3 CO2CH2CH3 N(CH2CH3)2 resin
1-50. CF3 CH3 CO2CH2CH3 OCH2CH3 resin
1 -51. CF3 CH3 CH3 H oil
1-52. CF3 CHF2 CH3 H
1-53. CF3 propargyl CH3 H
1 -54. CF3 SO2CH3 CH3 H
1-55. CF3 acetyl CH3 H
1-56. CF3 CH3 Et H
1 -57. CF3 CH3 cyclopropyl H Cmp. R1 R2 R3 R4 Phys. data
1-58. CF3 CH3 propargyl H
1-59. CF3 CH3 phenyl H m.p. 111 -114°C
1-60. CF3 CH2OCH2CH3 4-CI-phenyl H solid
1-61. CF3 CH3 H H m.p. 80-82°C
1-62. CF3 CH2CH3 H H oil
1 -63. CF3 CH2CN H H
1-64. CF3 CH2COOCH3 H H
1-65. CF3 CH OCH2CH3 H H
1-66. CF3 CH2CH2OCH3 H H
Figure imgf000035_0001
1-68. CF3 (CH2)4CO2CH CH3 H H
1-69. CF3 CHF2 H H
1-70. CF3 allyl H H oil
1-71. CF3 propargyl H H
1-72. CF3 acetyl H H
1-73. CF3 SO2CH3 H H
1-74. CF3 CH2phenyl H H m.p. 137-138°C
1-75. CF3 CH2CH2phenyl H H
1-76. CF3 (CH2)3phenyl H H
1-77. CF3 CH2-(3-CF3-phenyl) H H
1-78. CF3 CH2OCH2phenyl H H oil
1-79. CF3 CH2OCH2-(2-CI- H H phenyl)
1 -80. CF3 CH2OCH2-(3-CI- H H phenyl)
1-81. CF3 CH2OCH2-(4-CI- H H phenyl)
1-82. CF3 CH2CH3 Cl H m.p. 52-53°C
1-83. CF3 CH2CN Cl H oil
1-84. CF3 CH2COOCH3 Cl H resin
1-85. CF3 CH2OCH CH3 Cl H m.p. 54-57°C
1-86. CF3 CH2CH2OCH3 Cl H m.p. 65-66°C
1-87. CF3 (CH2)gCH3 Cl H oil
1-88. CF3 (CH2) CO2CH2CH3 Cl H oil Cmp. R1 R2 R3 R4 Phys. data
1-89. CF3 CHF2 Cl H
1-90. CF3 allyl Cl H solid
1 -91. CF3 propargyl Cl H oil
1 -92. CF3 acetyl Cl H
1-93. CF3 SO2CH3 Cl H
1-94. CF3 CH2phenyl Cl H m.p. 114-116°C
1-95. CF3 CH2CH2phenyl Cl H m.p. 85-87°C
1-96. CF3 (CH2)3phenyl Cl H oil
1 -97. CF3 CH2-(3-CF3-phenyl) Cl H m.p. 96-98°C
1 -98. CF3 CH2OCH2phenyl Cl H oil
1-99. CF3 CH2OCH2-(2-CI- Cl H solid phenyl)
1 -100. CF3 CH2OCH2-(3-CI- Cl H m.p. 101-103°C phenyl)
1-101. CF3 CH2OCH2-(4-CI- Cl H m.p. 126-129°C phenyl)
1-102. CF3 CH3 Br H m.p. 109-111 °C
1-103. CF3 CHF2 Br H
1-104. CF3 acetyl Br H
1-105. CF3 propargyl Br H
1-106. CF3 SO2CH3 Br H
1 -107. CF3 CH2CH3 Br H
1 -108. CF2CF3 CH3 H H
1 -109. CF2CF3 CH3 Cl H
1-110. CF2CF3 CH3 Br H
1-111. CF2COOCH2CH3 CH3 H H
1-112. CF2COOCH2CH3 CH3 Cl H solid
1-113. CH3 CH2OCH2phenyl H H m.p. 121-123°C
1-114. CH3 CH3 CH3 H
1 -115. CH3 CHF2 CH3 H
1-116. CH3 propargyl CH3 H
1-117. CH3 SO2CH3 CH3 H
1-118. CH3 acetyl CH3 H
1 -119. CH3 CH3 H H m.p. 108-109°C Cmp. R1 R2 R3 R4 Phys. data
1-120. CH3 CHF2 H H
1 -121. CH3 acetyl H H
1 -122. CH3 propargyl H H
1 -123. CH3 SO2CH3 H H
1-124. CH3 SO2N(CH3)2 H H m.p. 120-122°C
1-125. CH3 CH2CH3 H H
1-126. CH3 H Cl H solid
1-127. CH3 CH3 Cl H
1-128. CH3 CHF2 Cl H
1-129. CH3 acetyl Cl H
1 -130. CH3 propargyl Cl H
1-131. CH3 SO2CH3 Cl H
1-132. CH3 CH2CH3 Cl H
1-133. CH3 CH2OCH2phenyl Cl H solid
1-134. CH3 H Br H m.p. 201-202°C
1-135. CH3 CH3 Br H m.p. 207-208°C
1-136. CH3 CHF2 Br H m.p. 197-199°C
1 -137. CH3 acetyl Br H
1 -138. CH3 propargyl Br H m.p. 138-139°C
1-139. CH3 SO2CH3 Br H resin
1 -140. CH3 CH2CH3 Br H
1-141. CH2CI H H H
1-142. CH2CI H Cl H
1-143. CH2CI CH3 H H
1-144. CH2CI CH3 Cl H m.p. 104-107°C
1 -145. CH2OCH3 H H H
1 -146. CH2OCH3 H Cl H
1 -147. CH2OCH3 CH3 H H
1-148. CH2OCH3 CH3 Cl H m.p. 123-125°C
1-149. phenyl CH3 H H
1 -150. phenyl CHF2 H H
1 -151. phenyl acetyl H H
1-152. phenyl propargyl H H
1-153. phenyl SO2CH3 H H Cmp. R1 R2 R3 R4 Phys. data
1-154 phenyl CH CH3 H H
1 -155 phenyl CH3 Cl H m.p. 110-113°C
1-156 phenyl CHF2 Cl H
1 -157 phenyl acetyl Cl H
1 -158 phenyl propargyl Cl H
1 -159 phenyl SO2CH3 Cl H
1 -160 phenyl CH2CH3 Cl H
1-161 phenyl CH3 Br H
1 -162 phenyl CHF2 Br H
1-163 phenyl acetyl Br H
1-164 phenyl propargyl Br H
1-165 phenyl SO2CH3 Br H
1-166 phenyl CH2CHg Br H
1 -167 cyclopropyl CHF2 H H
1 -168 cyclopropyl acetyl H H
1-169 cyclopropyl propargyl H H
1-170 cyclopropyl SO2CH3 H H
1-171 cyclopropyl CH2CHg H H
1 -172 cyclopropyl CH3 Cl H
1-173 cyclopropyl CHF2 Cl H
1 -174 cyclopropyl acetyl Cl H
1-175 cyclopropyl propargyl Cl H
1-176 cyclopropyl SO2CH3 Cl H
1-177 cyclopropyl CH2CH3 Cl H
1 -178 cyclopropyl CH3 B H
1-179 cyclopropyl CHF2 B H
1 -180 cyclopropyl acetyl B H
1-181 cyclopropyl propargyl B H
1-182 cyclopropyl SO2CH3 B H
1-183 cyclopropyl CH2CHg B H
1-184 cyclopropyl CHF2 H H
Figure imgf000038_0001
1-187 SCF3 acetyl H H Cmp. R1 R2 R3 R4 Phys. data
1-188. SCF3 propargyl H H
1-189. SCF3 SO2CH3 H H
Figure imgf000039_0001
1-191. SCFg CH3 Cl H m.p. 97-98°C
Figure imgf000039_0002
1-193. SCFg acetyl Cl H
1-194. SCFg propargyl Cl H
Figure imgf000039_0003
1-197. SCF3 CH3 Br H
Figure imgf000039_0004
1-199. SCFg acetyl Br H
1-200. SCFg propargyl Br H
Figure imgf000039_0005
1-203. SCF3 CHF2 Br H
1-204. SCH3 CH3 Cl H m.p. 128-129°C
Figure imgf000039_0006
1-206. SO2CH3 CHg Cl H m.p. 173-175°C
1-207. SCH3 cyclopropyl CO2CH2CH3 H m.p. 92-94°C
1-208. SOCH3 cyclopropyl CO2CH2CH3 H m.p. 110-112°C
1-209. SO2CH3 cyclopropyl CO2CH2CH3 H m.p. 119-122°C
1-210. SOCFg CHg Cl H
Figure imgf000039_0007
1-212. OCH3 CHg Cl H m.p. 144-146°C
1-213. OCH2CH3 CHg Cl H m.p. 107-110°C
1-214. CN CHg Cl H solid
1-215. COCFg CHg Cl H
1-216. CO2CH2CH3 CH3 Cl H solid
1-217. C(O)H CHg H H m.p. 175-178°C
1-218. C(O)CH3 CHg H H m.p. 194-195°C
1-219. C(O)phenyl CH3 H H m.p. 180-182°C
1-220. C(O)H CH3 Cl H m.p. 180-182°C
1-221. C(O)CH3 CH3 Cl H m.p. 126-127°C Cmp. R1 R2 R3 R4 Phys. data
1-222. C(O)phenyl CHg Cl H m.p. 125-127°C
1-223. Br CHg H H resin
1-224. Br CH3 Cl H
1-225. Br CH3 Br H m.p. 139-141°C
1-226. Cl CH3 H H resin
1-227. Cl CH3 Cl H m.p. 108-111°C
1 -228. Cl CH2OCH3 Cl H oil
1-229. Cl CH3 Br H
1 -230. H CH3 H H m.p. 160-163°C
1-231. H CH2OCH3 H H m.p. 116-118°C
1 -232. NO2 CHg H H m.p. 191-192°C
1 -233. NO2 CHg Cl H m.p. 135-137°C
1 -234. 3-CF3-phenyl CH3 H H
1-235. 3-CF3-phenyl CH3 Cl H m.p. 114-117°C
1 -236. 4-CF3-phenyl CHg H H
1 -237. 4-CFg-phenyl CH3 Cl H m.p. 144-147°C
1 -238. 3,4,5-trifluoro- CH3 H H phenyl
1 -239. 3,4,5-trifluoro- CH3 Cl H m.p. 161 -163°C phenyl
1 -240. 3-pyridyl CH3 H H solid
1 -241. 3-pyridyl CHg Cl H m.p. 197-200°C
1 -242. 3-pyridyl allyl H H m.p. 168°C
1 -243. 3-pyridyl allyl Cl H m.p. 92-94°C
1 -244. 3-pyridyl CH2phenyl H H solid
1 -245. 3-pyridyl CH2phenyl Cl H amorphous
1 -246. 5-pyrimidinyl CH3 H H
1 -247. 5-pyrimidinyl CHg Cl H m.p. 226-229°C
1-248. 2-thiophenyl CH3 H H
1 -249. 2-thiophenyl CH3 Cl H m.p. 128-130°C
1-250. 3-thiophenyl CH3 H H
1 -251. 3-thiophenyl CH3 Cl H m.p. 143-145°C Table 2:
Compounds of formula II A:
Figure imgf000041_0001
Cmp. R1 R2 R3 R4 Phys. data 2-1. CF3 CHg Cl H m.p. 145-147°C
Figure imgf000041_0002
2-3. CF3 CH3 Cl Cl 2-4. CF3 CH3 Cl Br 2-5. CF3 CH3 Cl I 2-6. CF3 CH3 Cl CN
Figure imgf000041_0003
2-9. CF3 CH3 Cl OCH3
Figure imgf000041_0004
Biological Examples
Example B1 : Herbicidal action prior to emergence of the plants (pre-emerqence action) Monocotyledonous and dicotyledonous test plants are sown in standard soil in pots. Immediately after sowing, the test compounds, in the form of an aqueous suspension (prepared from a wettable powder (Example F3, b) according to WO 97/34485) or in the form of an emulsion (prepared from an emulsifiable concentrate (Example F1 , c) according to WO 97/34485), are applied by spraying, in an optimum concentration (500 litres of water per ha). The test plants are then grown in a greenhouse under optimum conditions. The test is evaluated after a test duration of 4 weeks. The compounds according to Tables 1 and 2 exhibit good to very good herbicidal action. The same results are obtained when the compounds of formula I are formulated in accordance with the other Examples according to WO 97/34485.
Example B2: Post-emergence herbicidal action
Monocotyledonous and dicotyledonous test plants are sown in standard soil in pots. When the test plants are at the 2- to 3-leaf stage, the test compounds, in the form of an aqueous suspension (prepared from a wettable powder (Example F3, b) according to WO 97/34485) or in the form of an emulsion (prepared from an emulsifiable concentrate (Example F1 , c) according to WO 97/34485), are applied by spraying, in an optimum concentration (500 litres of water per ha). The test plants are then grown on in a greenhouse under optimum conditions.
The test is evaluated after a test duration of 2 to 3 weeks. The compounds according to
Tables 1 and 2 exhibit good to very good herbicidal action.
The same results are obtained when the compounds of formula I are formulated in accordance with the other Examples according to WO 97/34485.
Example B3: Microscreen
Monocotyledonous and dicotyledonous test plants are sown in sterilised standard soil in seed trays each having 96 cells. After about 9 days' cultivation under controlled conditions in a climatic chamber (cultivation at 17/23°C; 13 hours' light; 50-60 % humidity; after application at 19/24°C), the plants Digitaria sanguinalis and Setaria italica are treated with an aqueous spray solution of 1 g/l, 0.250 g/l or 0.063 g/l of the active ingredient used, including 10 % DMSO as solvent (rate of application corresponding to 1000, 250 and 63 g/ha, respectively). The plants are grown on in the climatic chamber until the test is evaluated (100 % = total damage to plant, 0 % = no damage to plant) after 8 days.
Table B3: Damage at 1000 g/ha
Figure imgf000042_0001
Figure imgf000043_0001
The compounds tested exhibit good to very good control of Digitaria sanguinalis and Setaria italica.

Claims

What is claimed is:
1. A compound of formula
Figure imgf000044_0001
wherein
Ri is hydrogen, halogen, cyano, amino, hydroxy, nitro, formyl, -COOH, -CONH2, -CSNH2, d-dalkyl, halo-d-dalkyl, CrC6alkoxy, halo-CrC6alkoxy, CrC6alkylamino, halo-d-d- alkylamino, CrC6dialkylamino wherein the alkyl groups are the same or different or together with the nitrogen atom to which they are bonded form a 4- to 7-membered ring which may contain a further hetero atom selected from N, O and S, halo-d-ddialkylamino wherein the alkyl groups are the same or different, (d-C6alkyl)S(O)m, (halo-CrC6alkyl)S(O)m, (CrCealkylamino)S(O)m, (CrC6dialkylamino)S(O)m wherein the alkyl groups are the same or different, (halo-CrC6dialkylamino)S(O)m wherein the alkyl groups are the same or different, d-dalkylsulfonyloxy, halo-d-dalkylsulfonyloxy, CrC6alkylS(O)mamino; d-C6alkyl- S(O)mamino substituted by halogen, amino, d-dalkylamino, d-Cedialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; CrC6alkoxy-CrC6alkyl, halo-Crdalkoxy-Crdalkyl, Crdalkoxy-Crdalkyloxy, halo-Crdalkoxy-Crdalkyloxy, CrC6alkoxy-CrC6alkylamino, halo-CrCealkoxy-Crdalkylamino, Cι-C6alkylS(O)m-CrC6alkyl, halo-d-C6alkylS(O)m- d-dalkyl, CrC6alkylS(O)m-CrC6alkyloxy, halo-CrC6alkylS(O)m-CrC6alkyloxy, d-dalkyl- S(O)m-CrC6alkylamino, halo-CrC6alkylS(O)m-CrCealkylamino, CrC6alkylcarbonyl; CrC6alkylcarbonyl substituted by halogen, amino, d-dalkylamino, Crddialkylamino, hydroxy, cyano, C C4alkoxy or by formyl; d-dalkoxycarbonyl; C C6alkoxycarbonyl substituted by halogen, amino, Crdalkylamino, Crddialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; d-dalkylcarbonyloxy; CrC6alkylcarbonyloxy substituted by halogen, amino, Crdalkylamino, CrCedialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; formylamino, CrC6alkylcarbonylamino; Crdalkylcarbonylamino substituted by halogen, amino, d-dalkylamino, d-Cedialkylamino, hydroxy, cyano, C C alkoxy or by formyl; CrCealkylaminocarbonyl; CrCealkylaminocarbonyl substituted by halogen, amino, CrC6alkyIamino, CrC6dialkylamino, hydroxy, cyano, d-C4alkoxy or by formyl; d-Cedialkylaminocarbonyl wherein the alkyl groups are the same or different; CrC6dialkylaminocarbonyl substituted by halogen, amino, d-Cealkylamino, CrCedialkylamino, hydroxy, cyano, d-C alkoxy or by formyl, wherein the alkyl groups are the same or different; C2-C6alkenyl, haIo-C2-C6alkenyl, C3-C6alkenyloxy, halo-C3-C6alkenyloxy, (C2-C6alkenyl)S(O)m, (halo- C2-C6alkenyl)S(O)m, C3-C6alkenylamino, halo-C3-C6alkenylamino, C3-C6diaIkenylamino wherein the alkenyl radicals are the same or different, halo-Cg-C6dialkenylamino wherein the alkenyl radicals are the same or different, C3-C6cycloalkyl; C3-C6cycloalkyl substituted by halogen, amino, Crdalkylamino, Crddialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; tri(CrC6alkyl)silyl; tri(CrC6alkyl)silyl substituted by halogen, amino, Crdalkylamino, CrCedialkylamino, hydroxy, cyano, C C4alkoxy or by formyl; pentafluorothio, C2-C6alkynyl; C2-C6alkynyl substituted by halogen, amino, Crdalkylamino, CrCedialkylamino, hydroxy, cyano, d-dalkoxy, tri(CrC6alkyl)silyl or by formyl; C3-C6alkynyloxy, halo-C3-C6alkynyloxy, (C3-C6alkynyI)S(O)m, (haIo-C3-C6alkynyl)S(O)m, C3-C6alkynylamino, halo-C3-C6alkynylamino, C3-C6dialkynylamino wherein the alkynyl radicals are the same or different, halo- C3-C6dialkynylamino wherein the alkynyl radicals are the same or different, -Q or -A-Q;
R2 is hydrogen, cyano, hydroxy, amino, formyl, -CONH2, -CSNH2, CrC6alkyl; CrC6alkyl substituted by halogen, amino, d-dalkylamino, CrCedialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; d-dalkoxy; d-dalkoxy substituted by halogen, amino, d-dalkylamino, CrCedialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; Crdalkylamino, halo- Crdalkylamino, Crddialkylamino wherein the alkyl groups are the same or different, halo- Crddialkylamino wherein the alkyl groups are the same or different, (d-C6alkyl)S(O)m, (halo-CrC6alkyl)S(O)m, (CrC6alkylamino)S(O)rτl, (CrC6dialkylamino)S(O)m wherein the alkyl groups are the same or different, (halo-CrC6dialkylamino)S(O)m wherein the alkyl groups are the same or different, halo-d-dalkoxy-Crdalkyl, CrC6alkylS(O)m-CrCealkyl, halo- CrC6alkylS(O)m-CrC6alkyl, d-C6alkylcarbonyl; d-C6alkylcarbonyl substituted by halogen, amino, CrGealkylamino, CrC6dialkylamino, hydroxy, cyano, d-C alkoxy or by formyl; CrC6alkoxycarbonyl; d-dalkoxycarbonyl substituted by halogen, amino, Crdalkylamino, CrCedialkylamino, hydroxy, cyano, d-C alkoxy or by formyl; d-C6alkylcarbonyloxy; CrC6alkylcarbonyloxy substituted by halogen, amino, CrC6alkylamino, CrC6dialkylamino, hydroxy, cyano, d-C4alkoxy or by formyl; formylamino, CrCealkylcarbonylamino; CrCealkylcarbonylamino substituted by halogen, amino, Crdalkylamino, d-Cedialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; Crdalkylaminocarbonyl; d-dalkylaminocarbonyl substituted by halogen, amino, d-dalkylamino, Crddialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; Crddialkylaminocarbonyl wherein the alkyl groups are the same or different; Crddialkylaminocarbonyl substituted by halogen, amino, d-dalkylamino, d-ddialkylamino, hydroxy, cyano, d-dalkoxy or by formyl, wherein the alkyl groups are the same or different; C2-C6alkenyl, halo-C2-C6alkenyl, C2-C6aIkenyloxy, halo-C2-C6- alkenyloxy, (C2-C6alkenyl)S(O)m, (halo-C2-C6alkenyl)S(O)m, C3-C6cycloalkyl; C3-C6cycloalkyl substituted by halogen, amino, Crdalkylamino, Crddialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; tri(d-C6alkyl)silyl; tri(Cι-C6aikyl)silyl substituted by halogen, amino, d-dalkylamino, Crddialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; C2-C6alkynyl; C2-C6alkynyl substituted by halogen, amino, Crdalkylamino, CrC6dialkylamino, hydroxy, cyano, d-dalkoxy or by formyl, -Q or -A-Q;
R3 is hydrogen, halogen, cyano, amino, hydroxy, nitro, formyl, -COOH, -CONH2, -CSNH2, Crdalkyl, halo-d-C6alkyl, d-dalkoxy, halo-d-C6alkoxy, d-dalkylamino, halo-d-d- alkylamino, Crddialkylamino wherein the alkyl groups are the same or different or together with the nitrogen atom to which they are bonded form a 4- to 7-membered ring which may be interrupted by a hetero atom such as N, O or S, halo-Crddialkylamino wherein the alkyl groups are the same or different, (CrC6alkyl)S(O)m, (halo-d-C6alkyl)S(O)m, (d-dalkyl- amino)S(O)m, (CrC6dialkylamino)S(O)m wherein the alkyl groups are the same or different, (halo-CrC6dialkylamino)S(O)m wherein the alkyl groups are the same or different, d-dalkylsulfonyloxy, halo-d-dalkylsulfonyloxy, CrC6alkylS(O)mamino; d-C6alkyl- S(O)mamino substituted by halogen, amino, d-dalkylamino, Crddialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; d-dalkoxy-d-dalkyl, halo-d-Cealkoxy-Crdalkyl, Crdalkoxy-Crdalkyloxy, halo-d-dalkoxy-Crdalkyloxy, Crdalkoxy-d-dalkylamino, halo-d-Cealkoxy-d-Cealkylamino, CrC6alkylS(O)rn-C1-C6alkyl, halo-CrC6alkylS(O)m- d-dalkyl, CrdalkylS^m-Crdalkyloxy, halo-CrC6alkylS(O)m-CrC6alkyloxy, d-dalkyl- S(O)m-CrC6alkylamino, halo-CrC6alkylS(O)m-CrC6alkylamino, C C6alkylcarbonyl; d-C6alkylcarbonyl substituted by halogen, amino, Crdalkylamino, Crddialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; d-C6alkoxycarbonyl; d-dalkoxycarbonyl substituted by halogen, amino, d-dalkylamino, Crddialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; Crdalkylcarbonyloxy; CrCβalkylcarbonyloxy substituted by halogen, amino, CrC6alkylamino, CrC6dialkylamino, hydroxy, cyano, d-C alkoxy or by formyl; formylamino, CrC6alkylcarbonylamino; CrCealkylcarbonylamino substituted by halogen, amino, CrC6alkylamino, d-Cedialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; CrCealkylaminocarbonyl; C C6alkylaminocarbonyl substituted by halogen, amino, Crdalkylamino, d-Cedialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; d-Cedialkylaminocarbonyl wherein the alkyl groups are the same or different; d-ddialkylaminocarbonyl substituted by halogen, amino, d-dalkylamino, CrCedialkylamino, hydroxy, cyano, d-dalkoxy or by formyl, wherein the alkyl groups are the same or different; C2-C6alkenyl, halo-C2-C6alkenyl, C3-C6alkenyloxy, halo-C3-C6alkenyloxy, (C2-C6alkenyl)S(O)m, (halo- C2-C6alkenyl)S(O)m, C3-C6alkenylamino, halo-C3-C6alkenylamino, C3-C6dialkenylamino wherein the alkenyl radicals are the same or different, haIo-C3-C6dialkenylamino wherein the alkenyl radicals are the same or different, C3-C6cycloalkyl; C3-C6cycloalkyl substituted by halogen, amino, CrC6alkylamino, d-Cedialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; tri(Crdalkyl)silyl; tri(CrC6alkyl)silyl substituted by halogen, amino, d-dalkylamino, Crddialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; pentafluorothio, C2-C6alkynyl; C2-C6alkynyl substituted by halogen, amino, d-dalkylamino, Crddialkylamino, hydroxy, cyano, d-dalkoxy, tri(C1-C6alkyl)silyl or by formyl; C3-C6alkynyloxy, halo-C3-C6alkynyloxy, (Cg-C6alkynyl)S(O)m, (halo-C3-C6alkynyl)S(O)m, C3-C6alkynylamino, halo-C3-C6alkynylamino, C3-C6dialkynylamino wherein the alkynyl radicals are the same or different, or halo- C3-C6dialkynylamino wherein the alkynyl radicals are the same or different;
R4 is hydrogen, halogen, cyano, amino, nitro, formyl, -COOH, -CONH2, -CSNH2, d-dalkyl, halo-d-dalkyl, d-C6alkoxy, halo-d-dalkoxy, CrC6alkylamino, CrC6dialkylamino wherein the alkyl groups are the same or different or together with the nitrogen atom to which they are bonded form a 4- to 7-membered ring, halo-C C6dialkylamino wherein the alkyl groups are the same or different, (CrC6alkyl)S(O)m, (halo-CrC6alkyl)S(O)m, CrC6alkoxy-CrC6alkyl, halo-CrC6alkoxy-CrC6alkyI, d-C6alkylcarbonyl; d-dalkylcarbonyl substituted by halogen, amino, Crdalkylamino, CrCedialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; d-dalkoxycarbonyl; d-dalkoxycarbonyl substituted by halogen, amino, d-dalkylamino, CrCedialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; d-dalkylcarbonylamino; Crdalkylcarbonylamino substituted by halogen, amino, d-dalkylamino, Crddialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; Crdalkylaminocarbonyl; d-dalkylaminocarbonyl substituted by halogen, amino, d-dalkylamino, d-Cedialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; d-Cedialkylaminocarbonyl wherein the alkyl groups are the same or different; d-ddialkylaminocarbonyl substituted by halogen, amino, d-dalkylamino, d-Cedialkylamino, hydroxy, cyano, d-dalkoxy or by formyl, wherein the alkyl groups are the same or different; C2-C6alkenyl, halo-C2-C6alkenyl, C3-C6cycloalkyl; C3-C6cycIoalkyl substituted by halogen, amino, d-dalkylamino, d-Cedialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; tri(CrC6alkyl)silyl, C2-C6alkynyl; or C2-C6alkynyl substituted by halogen, amino, d-Cealkylamino, CrCedialkylamino, hydroxy, cyano, d-dalkoxy, tri(d-C6alkyl)silyl or by formyl;
A is d-dalkylene; d-dalkylene substituted by halogen, amino, d-dalkylamino, CrCedialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; d-doxyalkylene; C C4oxyalkylene substituted by halogen, amino, Crdalkylamino, Crddialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; d-dalkyleneoxy; d-dalkyleneoxy substituted by halogen, amino, d-C6alkylamino, Crddialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; d-doxy- alkyleneoxy; d-doxyalkyleneoxy substituted by halogen, amino, Crdalkylamino, CrCedialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; d-daminoalkylene; d-C amino- alkylene substituted by halogen, amino, d-dalkylamino, CrCedialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; d-C4alkyleneamino; d-dalkyleneamino substituted by halogen, amino, d-Cealkylamino, d-ddialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; d-C4- aminoalkyleneamino; d-C4aminoalkyleneamino substituted by halogen, amino, d-Cealkylamino, CrCedialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; C C4thioalkylene; d-dthioalkylene substituted by halogen, amino, d-dalkylamino, d-Cedialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; C3-C6cycloalkylene; C3-C6cycloalkylene substituted by halogen, amino, Crdalkylamino, d-ddialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; C2-C alkenylene; C2-C4alkenylene substituted by halogen, amino, Crdalkylamino, CrCedialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; C2-C alkynylene; C2-C4alkynyl- ene substituted by halogen, amino, Crdalkylamino, CrCedialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; O, S, NH, formylamino, d-dalkylamino, S(O)m, oxysulfonyl, sulfonyloxy, aminosulfonyl, sulfonylamino, carbonyl, oxycarbonyl, carbonyloxy, oxycarbonyloxy, carbonylamino, aminocarbonyl, aminocarbonyloxy, oxycarbonylamino or aminocarbonylamino;
Q is aryl, aryl substituted one or more times by halogen, cyano, hydroxy, amino, nitro, formyl, -COOH, -CONH2, -CSNH2, Crdalkyl, halo-d-dalkyl, Crdalkoxy, halo-d-dalkoxy, Crdalkylamino, halo-Crdalkylamino, d-ddialkylamino wherein the alkyl groups are the same or different or together with the nitrogen atom to which they are bonded form a 4- to 7- membered ring, halo-Crddialkylamino wherein the alkyl groups are the same or different, (d-C6alkyl)S(O)m, (halo-CrC6alkyl)S(O)m, (CrC6alkylamino)S(O)m, (d-ddialkyl- amino)S(O)m wherein the alkyl groups are the same or different, (halo-Crddialkylamino)- S(O)m wherein the alkyl groups are the same or different, d-dalkylsulfonyloxy, halo-d-d- alkylsulfonyloxy, CrC6alkylS(O)mamino; CrC6alkylS(O)mamino substituted by halogen, amino, Crdalkylamino, Crddialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; Crdalkoxy-Crdalkyl, halo-d-dalkoxy-Crdalkyl, CrC6alkoxy-CrC6alkyloxy, halo- CrCealkoxy-d-Cealkyloxy, d-Cealkoxy-d-Cealkylamino, halo-CrC6alkoxy-CrCealkylamino, CrC6alkylS(O)m-CrC6alkyl, halo-CrC6alkylS(O)m-CrC6alkyl, CrC6alkylS(O)m-CrC6alkyloxy, halo-CrC6alkylS(O)m-CrC6alkyloxy, CrC6alkylS(O)m-CrC6alkylamino, halo-d-C6alkylS(O)m- CrC6alkylamino, d-C6alkylcarbonyl; CrC6alkylcarbonyl substituted by halogen, amino, CrC6alkylamino, Crddialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; d-dalkoxycarbonyl; d-dalkoxycarbonyl substituted by halogen, amino, d-dalkylamino, CrCedialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; d-dalkylcarbonyloxy; d-dalkyl- carbonyloxy substituted by halogen, amino, d-dalkylamino, CrCedialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; formylamino, CrCealkylcarbonylamino; CrCealkylcarbonylamino substituted by halogen, amino, d-dalkylamino, d-Cedialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; CrCealkylaminocarbonyl; CrCealkylaminocarbonyl substituted by halogen, amino, Crdalkylamino, CrCedialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; d-ddialkylaminocarbonyl wherein the alkyl groups are the same or different; d-ddialkylaminocarbonyl substituted by halogen, amino, d-dalkylamino, CrCedialkylamino, hydroxy, cyano, d-dalkoxy or by formyl, wherein the alkyl groups are the same or different; C2-C6alkenyl, halo-C2-C6alkenyl, C3-C6alkenyloxy, halo-C3-C6alkenyloxy, (C2-C6- alkenyl)S(O)m, (halo-C2-C6alkenyl)S(O)m, C3-C6alkenylamino, halo-C3-C6alkenylamino, C3-C6- dialkenylamino wherein the alkenyl radicals are the same or different, halo-C3-C6dialkenyl- amino wherein the alkenyl radicals are the same or different, C3-C6cycloalkyl; C3-C6cycloalkyl substituted by halogen, amino, d-dalkylamino, d-Cedialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; tri(d-C6alkyl)silyl; tri(CrC6alkyl)silyl substituted by halogen, amino, CrC6alkylamino, CrC6dialkylamino, hydroxy, cyano, C C4alkoxy or by formyl; pentafluoro- thio; C2-C6alkynyl, or C2-C6alkynyl substituted by halogen, amino, CrC6alkylamino, CrCedialkylamino, hydroxy, cyano, C C alkoxy, tri(d-C6alkyl)silyl or by formyl; C3-C6alkynyloxy, halo-C3-C6alkynyloxy, (C3-C6alkynyl)S(O)m, (halo-C3-C6alkynyl)S(O)m, C3-C6alkynylamino, halo-C3-C6alkynyIamino, C3-C6dialkynylamino wherein the alkynyl radicals are the same or different, halo-C3-C6dialkynylamino wherein the alkynyl radicals are the same or different, or Q is a monocyclic heterocycle, or a monocyclic heterocycle substituted one or more times by halogen, cyano, hydroxy, amino, nitro, formyl, -COOH, -CONH2, -CSNH2, d-dalkyl, halo-d-C6alkyl, d-dalkoxy, halo-C C6alkoxy, d-dalkylamino, halo-d-dalkylamino, CrCedialkylamino wherein the alkyl groups are the same or different or together with the nitrogen atom to which they are bonded form a 4- to 7-membered ring, halo-d-ddialkyl- amino wherein the alkyl groups are the same or different, (CrC6alkyl)S(O)m, (halo-d-d- alkyl)S(O)m, (CrC6alkylamino)S(O)m, (CrC6dialkylamino)S(O)m wherein the alkyl groups are the same or different, (halo-Crddialkylamino)S(O)m wherein the alkyl groups are the same or different, d-dalkylsulfonyloxy, halo-d-C6alkylsulfonyloxy, CrC6alkylS(O)mamino; CrC6alkylS(O)mamino substituted by halogen, amino, Crdalkylamino, d-ddialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; Crdalkoxy-d-dalkyl, halo-Crdalkoxy-Crd- alkyl, Crdalkoxy-Crdalkyloxy, halo-d-dalkoxy-Crdalkyloxy, Crdalkoxy-d-Cealkyl- amino, halo-Crdalkoxy-d-dalkylamino,
Figure imgf000050_0001
halo-CrC6alkylS(O)m- C C6alkyl, CrC6alkylS(O)m-CrC6alkyloxy, halo-CrC6alkylS(O)m-CrC6alkyloxy, C C6alkyl- S(O)m-CrdaIkylamino, halo-CrC6alkylS(O)m-CrC6alkylamino, C C6alkylcarbonyl; CrC6alkylcarbonyl substituted by halogen, amino, d-dalkylamino, CrCedialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; d-dalkoxycarbonyl; d-dalkoxycarbonyl substituted by halogen, amino, Crdalkylamino, d-ddialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; d-dalkylcarbonyloxy; d-dalkylcarbonyloxy substituted by halogen, amino, CrC6alkylamino, CrCedialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; formylamino, CrCealkylcarbonylamino; d-dalkylcarbonylamino substituted by halogen, amino, d-Cealkylamino, CrCedialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; d-dalkylaminocarbonyl; Crdalkylaminocarbonyl substituted by halogen, amino, CrC6alkylamino, CrCedialkylamino, hydroxy, cyano, d-C4alkoxy or by formyl; d-Cedialkylaminocarbonyl wherein the alkyl groups are the same or different; d-Cedialkylaminocarbonyl substituted by halogen, amino, CrC6alkylamino, CrC6dialkylamino, hydroxy, cyano, d-dalkoxy or by formyl, wherein the alkyl groups are the same or different; C2-C6alkenyl, halo-C2-C6alkenyl, C3-C6alkenyloxy, halo-C3-C6alkenyloxy, (C2-C6alkenyl)- S(O)m, (halo-C2-C6alkenyl)S(O)m, C3-C6alkenylamino, halo-C3-C6alkenylamino, C3-C6dialkenylamino wherein the alkenyl radicals are the same or different, halo- C3-C6dialkenylamino wherein the alkenyl radicals are the same or different, C3-C6cycloalkyl; C3-C6cycloalkyl substituted by halogen, amino, Crdalkylamino, CrCedialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; tri(CrC6alkyl)silyl; tri(C -C6alkyl)silyl substituted by halogen, amino, Crdalkylamino, d-ddialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; pentafluorothio; C2-C6alkynyl, or C2-C6alkynyl substituted by halogen, amino, d-Cealkylamino, d-ddialkylamino, hydroxy, cyano, d-dalkoxy, tri(d-C6alkyl)silyl or by formyl; C3-C6alkynyloxy, halo-C3-C6alkynyloxy, (C3-C6alkynyl)S(O)m, (halo-C3-C6alkynyl)S(O)m, C3-C6alkynylamino, halo-C3-C6alkynylamino, C3-C6dialkynylamino wherein the alkynyl radicals are the same or different, halo-C3-C6dialkynylamino wherein the alkynyl radicals are the same or different, and m is 0, 1 or 2, or an enantiomer, a mixture of enantiomers, a tautomer, a mixture of tautomers or an agrochemically acceptable salt of a compound of formula I, an N-oxide of such a compound or an enantiomer, a mixture of enantiomers, a tautomer, a mixture of tautomers or an agrochemically acceptable salt thereof, with the exclusion of 5-(2-butyl-3H-imidazol-4-yl)- pyrimidine, 5-(5-ethyl-2-(4-fluorophenyl)-1 H-imidazol-4-yl)-pyrimidine hydrochloride, N-{5-[2- (4-fluorophenyl)-5-propyl-1 H-imidazol-4-yl]-pyrimidin-2-yl}-acetamide dihydrochloride, 5-(1 H- imidazol-4-yl)-pyrimidine dihydrochloride and 4-(4-pyrimidin-5-yl-imidazol-1 -yl)-butylamine.
2. A process for the preparation of a compound of formula I according to claim 1 , which comprises coupling together a pyrimidine functionalised in the 5-position and an imidazole functionalised in the 4-position by means of transition metal catalysis.
3. A process for the preparation of a compound of formula I according to claim 1 , which comprises cyclising a 5-(2-haloalkylcarbonyl)-pyrimidine with an amidine.
4. A herbicidal and plant-growth-inhibiting composition which comprises, on an inert carrier, a herbicidally effective amount of a compound of formula I
Figure imgf000052_0001
wherein
Ri is hydrogen, halogen, cyano, amino, hydroxy, nitro, formyl, -COOH, -CONH2, -CSNH2, d-C6alkyl, halo-C C6alkyl, d-dalkoxy, halo-d-dalkoxy, Cι-C6aIkylamino, halo-d-C6- alkylamino, d-C6dialkylamino wherein the alkyl groups are the same or different or together with the nitrogen atom to which they are bonded form a 4- to 7-membered ring which may contain a further hetero atom selected from N, O and S, halo-d-ddialkylamino wherein the alkyl groups are the same or different, (CrC6alkyl)S(O)m, (halo-CrC6alkyl)S(O)m, (CrC6alkyIamino)S(O)m, (CrC6dialkylamino)S(O)m wherein the alkyl groups are the same or different, (halo-Crddialkylamino)S(O)m wherein the alkyl groups are the same or different, d-dalkylsulfonyloxy, halo-Crdalkylsulfonyloxy, CrdalkylS(O)mamino; d-dalkyl- S(O)mamino substituted by halogen, amino, d-dalkylamino, d-ddialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; d-dalkoxy-Crdalkyl, halo-d-Cealkoxy-Crdalkyl, d-dalkoxy-Crdalkyloxy, halo-Crdalkoxy-Crdalkyloxy, Crdalkoxy-Crdalkylamino, halo-d-Cealkoxy-d-Cealkylamino, Cι-C6alkylS(O)m-CrC6alkyl, halo-CrC6alkylS(O)m- d-C6alkyl, CrC6alkylS(O)m-CrC6alkyloxy, halo-CrC6alkylS(O)m-CrC6alkyloxy, d-CealkylS^m-d-Cealkylamino, halo-CrC6alkylS(O)m-CrC6alkylamino, d-Cealkylcarbonyl; d-dalkylcarbonyl substituted by halogen, amino, d-dalkylamino, d-ddialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; d-dalkoxycarbonyl; d-dalkoxycarbonyl substituted by halogen, amino, d-dalkylamino, CrCedialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; d-dalkylcarbonyloxy; d-dalkylcarbonyloxy substituted by halogen, amino, Crdalkylamino, Crddialkylamino, hydroxy, cyano, CrC4alkoxy or by formyl; formylamino, Crdalkylcarbonylamino; d-dalkylcarbonylamino substituted by halogen, amino, Crdalkylamino, d-Cedialkylamino, hydroxy, cyano, C C alkoxy or by formyl; d-dalkylaminocarbonyl; d-dalkylaminocarbonyl substituted by halogen, amino, Crdalkylamino, d-Cedialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; d-Cedialkylaminocarbonyl wherein the alkyl groups are the same or different; d-Cedialkylaminocarbonyl substituted by halogen, amino, Crdalkylamino, d-Cedialkylamino, hydroxy, cyano, d-dalkoxy or by formyl, wherein the alkyl groups are the same or different; C2-C6alkenyl, halo-C2-C6alkenyl, C3-C6alkenyloxy, halo-C3-C6alkenyloxy, (C2-C6alkenyl)S(O)m, (halo- C2-C6alkenyl)S(O)m, C3-C6alkenylamino, halo-C3-C6alkenylamino, C3-C6dialkenylamino wherein the alkenyl radicals are the same or different, halo-C3-C6dialkenylamino wherein the alkenyl radicals are the same or different, C3-C6cycloalkyl; C3-C6cycloalkyl substituted by halogen, amino, Crdalkylamino, d-Cedialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; tri(C1-C6alkyl)silyl; tri(CrC6alkyl)silyl substituted by halogen, amino, Crdalkylamino, Crddialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; pentafluorothio, C2-C6alkynyl; C2-C6alkynyl substituted by halogen, amino, Crdaikylamino, CrCedialkylamino, hydroxy, cyano, d-dalkoxy, tri(d-C6alkyl)siIyI or by formyl; C3-C6alkynyloxy, halo-C3-C6alkynyloxy, (C3-C6alkynyl)S(O)m, (halo-C3-C6alkynyl)S(O)m, C3-C6alkynylamino, halo-C3-C6alkynylamino, C3-C6dialkynylamino wherein the alkynyl radicals are the same or different, halo- d-ddialkynylamino wherein the alkynyl radicals are the same or different, -Q or -A-Q;
R2 is hydrogen, cyano, hydroxy, amino, formyl, -CONH2, -CSNH2, d-dalkyl; d-dalkyl substituted by halogen, amino, d-dalkylamino, d-ddialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; d-dalkoxy; d-dalkoxy substituted by halogen, amino, CrGealkylamino, CrCedialkylamino, hydroxy, cyano, d-C4alkoxy or by formyl; CrC6alkylamino, halo- CrC6alkylamino, CrCedialkylamino wherein the alkyl groups are the same or different, halo- CrC6dialkylamino wherein the alkyl groups are the same or different, (CrC6alkyl)S(O)m, (halo-Crdalkyl)S(O)m, (CrC6alkylamino)S(O)m, (CrC6dialkylamino)S(O)m wherein the alkyl groups are the same or different, (halo-CrCedialkylamino)S(O)m wherein the alkyl groups are the same or different, halo-Crdalkoxy-d-dalkyl, CrC6alkylS(O)m-CrCealkyl, halo- CrC6alkylS(O)m-C1-C6alkyl, d-dalkylcarbonyl; d-C6alkylcarbonyl substituted by halogen, amino, Crdalkylamino, d-ddialkylamino, hydroxy, cyano, Crdalkoxy or by formyl; d-dalkoxycarbonyl; d-dalkoxycarbonyl substituted by halogen, amino, Crdalkylamino, d-ddialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; d-dalkylcarbonyloxy; d-dalkylcarbonyloxy substituted by halogen, amino, d-dalkylamino, d-ddialkylamino, hydroxy, cyano, C C4alkoxy or by formyl; formylamino, CrCealkylcarbonylamino; CrCealkylcarbonylamino substituted by halogen, amino, d-dalkylamino, d-Cedialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; d-dalkylaminocarbonyl; d-dalkylaminocarbonyl substituted by halogen, amino, d-dalkylamino, d-ddialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; Crddialkylaminocarbonyl wherein the alkyl groups are the same or different; d-ddialkylaminocarbonyl substituted by halogen, amino, d-dalkylamino, CrCedialkylamino, hydroxy, cyano, d-dalkoxy or by formyl, wherein the alkyl groups are the same or different; C2-C6alkenyl, halo-C2-C6alkenyl, C2-C6alkenyloxy, halo-C2-C6- alkenyloxy, (C2-C6alkenyl)S(O)m, (halo-C2-C6alkenyl)S(O)m, C3-C6cycloalkyl; C3-C6cycloalkyl substituted by halogen, amino, d-dalkylamino, CrCedialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; tri(CrC6alkyl)silyl; tri(CrC6alkyl)silyl substituted by halogen, amino, d-dalkylamino, CrCedialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; C2-C6alkynyl; C2-C6alkynyl substituted by halogen, amino, d-dalkylamino, d-Cedialkylamino, hydroxy, cyano, d-dalkoxy or by formyl, -Q or -A-Q;
R3 is hydrogen, halogen, cyano, amino, hydroxy, nitro, formyl, -COOH, -CONH2, -CSNH2, d-dalkyl, halo-d-dalkyl, d-dalkoxy, halo-d-dalkoxy, d-dalkylamino, halo-Crd- alkylamino, d-ddialkylamino wherein the alkyl groups are the same or different or together with the nitrogen atom to which they are bonded form a 4- to 7-membered ring which may be interrupted by a hetero atom such as N, O or S, halo-d-ddialkylamino wherein the alkyl groups are the same or different, (d-C6alkyl)S(O)m, (halo-CrC6alkyl)S(O)mj (d-C6alkyl- amino)S(O)m, (CrC6dialkylamino)S(O)m wherein the alkyl groups are the same or different, (halo-CrC6dialkylamino)S(O)m wherein the alkyl groups are the same or different, d-d- alkylsulfonyloxy, halo-d-dalkylsulfonyloxy, CrdalkylS^mamino; CrC6alkylS(O)mamino substituted by halogen, amino, Crdalkylamino, d-Cedialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; Crdalkoxy-Crdalkyl, halo-Crdalkoxy-Crdalkyl, C C6aIkoxy- d-dalkyloxy, halo-d-dalkoxy-Crdalkyloxy, Crdalkoxy-Crdalkylamino, halo- CrCealkoxy-d-Cealkylamino, CrC6alkylS(O)m-CrC6alkyl, halo-CrC6alkylS(O)m-CrC6alkyl, CrC6alkylS(O)m-CrC6alkyloxy, halo-CrC6alkylS(O)m-CrC6alkyloxy, d-C6alkylS(O)m- d-dalkylamino, halo-CrC6aIkylS(O)m-CrC6alkylamino, d-C6alkylcarbonyl; d-dalkyl- carbonyl substituted by halogen, amino, d-dalkylamino, d-ddialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; d-dalkoxycarbonyl; d-dalkoxycarbonyl substituted by halogen, amino, d-dalkylamino, d-ddialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; d-dalkylcarbonyloxy; d-dalkylcarbonyloxy substituted by halogen, amino, Crdalkylamino, d-Cedialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; formylamino, Crdalkylcarbonylamino; d-dalkylcarbonylamino substituted by halogen, amino, d-dalkylamino, d-Cedialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; d-dalkyl- aminocarbonyl; d-dalkylaminocarbonyl substituted by halogen, amino, Crdalkylamino, d-ddialkylamino, hydroxy, cyano, Crdalkoxy or by formyl; d-Cedialkylaminocarbonyl wherein the alkyl groups are the same or different; d-ddialkylaminocarbonyl substituted by halogen, amino, Crdalkylamino, d-Cedialkylamino, hydroxy, cyano, d-dalkoxy or by formyl, wherein the alkyl groups are the same or different; C2-C6alkenyl, halo-C2-C6alkenyl, d-dalkenyloxy, halo-C3-C6alkenyloxy, (C2-C6alkenyl)S(O)m, (halo-C2-C6alkenyl)S(O)m, C3-C6alkenyIamino, halo-C3-C6alkenylamino, C3-C6dialkenylamino wherein the alkenyl radicals are the same or different, halo-C3-C6dialkenylamino wherein the alkenyl radicals are the same or different, C3-C6cycloalkyl; C3-C6cycloalkyl substituted by halogen, amino, d-dalkylamino, d-ddialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; tri(CrC6alkyl)silyl; tri(C1-C6alkyl)silyl substituted by halogen, amino, d-dalkylamino, CrCedialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; pentafluorothio, C2-C6alkynyl; C2-C6alkynyl substituted by halogen, amino, d-daikylamino, d-ddialkylamino, hydroxy, cyano, d-dalkoxy, tri(CrC6alkyl)silyl or by formyl; C3-C6alkynyloxy, halo-C3-C6alkynyIoxy, (C3-C6alkynyl)S(O)m, (halo-Cg-C6alkynyl)S(O)m, C3-C6alkynylamino, halo-C3-C6aIkynylamino, C3-C6dialkynylamino wherein the alkynyl radicals are the same or different, or halo-C3-C6- dialkynylamino wherein the alkynyl radicals are the same or different;
R4 is hydrogen, halogen, cyano, amino, nitro, formyl, -COOH, -CONH2, -CSNH2, d-dalkyl, halo-d-dalkyl, d-dalkoxy, halo-d-C6alkoxy, d-dalkylamino, d-ddiaikylamino wherein the alkyl groups are the same or different or together with the nitrogen atom to which they are bonded form a 4- to 7-membered ring, halo-Crddialkylamino wherein the alkyl groups are the same or different, (CrC6alkyl)S(O)m, (halo-CrC6alkyI)S(O)m, d-dalkoxy-Crdalkyl, halo-d-dalkoxy-Crdalkyl, d-dalkylcarbonyl; d-dalkylcarbonyl substituted by halogen, amino, d-dalkylamino, d-ddialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; d-dalkoxycarbonyl; d-dalkoxycarbonyl substituted by halogen, amino, Crdalkylamino, d-ddialkylamino, hydroxy, cyano, Crdalkoxy or by formyl; CrCealkylcarbonylamino; d-dalkylcarbonylamino substituted by halogen, amino, d-dalkylamino, Crddialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; d-dalkylaminocarbonyl; d-dalkylaminocarbonyl substituted by halogen, amino, Crdalkylamino, CrCedialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; Crddialkylaminocarbonyl wherein the alkyl groups are the same or different; d-Cedialkylaminocarbonyl substituted by halogen, amino, d-dalkylamino, d-ddialkylamino, hydroxy, cyano, C C4alkoxy or by formyl, wherein the alkyl groups are the same or different; C2-C6alkenyl, halo-C2-C6alkenyl, C3-C6cycloalkyl; C3-C6cycloalkyl substituted by halogen, amino, d-dalkylamino, d-Cedialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; tri(CrCealkyl)silyl, C2-C6alkynyl; or C2-C6alkynyl substituted by halogen, amino, Crdalkylamino, CrCedialkylamino, hydroxy, cyano, d-dalkoxy, tri(d-C6alkyl)silyl or by formyl;
A is d-dalkylene; d-dalkylene substituted by halogen, amino, d-dalkylamino, CrCedialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; C C oxyalkylene; d-doxyalkyiene substituted by halogen, amino, d-dalkylamino, d-ddialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; d-dalkyleneoxy; d-dalkyleneoxy substituted by halogen, amino, d-dalkylamino, d-Cedialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; C C4oxy- alkyleneoxy; d-doxyalkyleneoxy substituted by halogen, amino, Crdalkylamino, d-Cedialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; d-daminoalkylene; d-damino- alkylene substituted by halogen, amino, d-dalkylamino, d-Cedialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; d-dalkyleneamino; d-dalkyleneamino substituted by halogen, amino, d-dalkylamino, d-Cedialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; d-C4- aminoalkyleneamino; d-daminoaikyleneamino substituted by halogen, amino, CrCealkylamino, CrCedialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; d-dthioalkylene; d-dthioalkylene substituted by halogen, amino, Crdalkylamino, d-ddialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; C3-C6cycloalkylene; C3-C6cycIoalkylene substituted by halogen, amino, d-dalkylamino, CrCedialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; C2-C4alkenylene; C2-C4alkenylene substituted by halogen, amino, Crdalkylamino, d-ddialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; C2-C4alkynylene; C2-C4alkynyl- ene substituted by halogen, amino, CrGealkylamino, d-Cedialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; O, S, NH, formylamino, d-dalkylamino, S(O)m, oxysulfonyl, sulfonyloxy, aminosulfonyl, sulfonylamino, carbonyl, oxycarbonyl, carbonyloxy, oxycarbonyloxy, carbonylamino, aminocarbonyl, aminocarbonyloxy, oxycarbonylamino or aminocarbonylamino;
Q is aryl, aryl substituted one or more times by halogen, cyano, hydroxy, amino, nitro, formyl, -COOH, -CONH2, -CSNH2, C C6alkyl, halo-d-C6alkyl, d-dalkoxy, halo-d-dalkoxy, d-Cealkylamino, halo-d-dalkylamino, d-ddialkylamino wherein the alkyl groups are the same or different or together with the nitrogen atom to which they are bonded form a 4- to 7- membered ring, halo-d-ddialkylamino wherein the alkyl groups are the same or different, (CrC6alkyl)S(O)m, (halo-CrC6alkyl)S(O)m, (CrC6alkylamino)S(O)m, (C C6dialkyl- amino)S(O)m wherein the alkyl groups are the same or different, (halo-d-ddialkylamino)- S(O)m wherein the alkyl groups are the same or different, d-dalkylsulfonyloxy, halo-d-d- alkylsulfonyloxy, CrC6aIkylS(O)mamino; CrC6alkylS(O)mamino substituted by halogen, amino, d-dalkylamino, d-Cedialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; d-dalkoxy-Crdalkyl, haio-d-dalkoxy-Crdalkyl, d-dalkoxy-Crdalkyloxy, halo- CrC6alkoxy-CrC6alkyloxy, CrC6alkoxy-CrCealkylamino, halo-CrC6alkoxy-CrC6alkylamino, CrC6alkylS(O)m-CrC6alkyl, halo-Cι-C6alkylS(O)m-CrC6alkyl, Cι-C6alkylS(O)m-CrC6alkyloxy, halo-CrC6alkylS(O)m-CrC6alkyloxy, CrC6alkylS(O)m-CrC6alkylamino, halo-d-C6alkylS(O)m- d-C6alkylamino, d-C6alkylcarbonyl; d-C6alkylcarbonyl substituted by halogen, amino, Crdalkylamino, d-ddialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; d-dalkoxycarbonyl; d-dalkoxycarbonyl substituted by halogen, amino, d-dalkylamino, CrCedialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; d-dalkylcarbonyloxy; d-dalkylcarbonyloxy substituted by halogen, amino, d-dalkylamino, d-ddialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; formylamino, CrCealkylcarbonylamino; CrCealkylcarbonylamino substituted by halogen, amino, d-dalkylamino, CrCedialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; Crdalkylaminocarbonyl; CrCealkylaminocarbonyl substituted by halogen, amino, d-dalkylamino, d-ddialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; Crddialkylaminocarbonyl wherein the alkyl groups are the same or different; Crddialkylaminocarbonyl substituted by halogen, amino, d-dalkylamino, CrCedialkylamino, hydroxy, cyano, d-dalkoxy or by formyl, wherein the alkyl groups are the same or different; C2-C6alkenyl, halo-C2-C6alkenyl, C3-C6alkenyloxy, halo-C3-C6alkenyloxy, (C2-C6- alkenyl)S(O)m, (halo-C2-C6alkenyl)S(O)m, C3-C6alkenylamino, halo-C3-C6alkenylamino, C3-C6- dialkenylamino wherein the alkenyl radicals are the same or different, halo-C3-C6dialkenyl- amino wherein the alkenyl radicals are the same or different, C3-C6cycloalkyl; C3-C6cycloalkyl substituted by halogen, amino, d-dalkylamino, d-ddialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; tri(CrC6alkyl)silyl; tri(CrC6alkyl)silyl substituted by halogen, amino, CrC6alkylamino, d-Cedialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; pentafluoro- thio; C2-C6alkynyl, or C2-C6alkynyl substituted by halogen, amino, CrC6alkylamino, CrCedialkylamino, hydroxy, cyano, d-C4alkoxy, tri(d-C6alkyI)silyl or by formyl; C3-C6alkynyloxy, halo-C3-C6alkynyloxy, (C3-C6alkynyl)S(O)m, (halo-C3-C6alkynyl)S(O)m, C3-C6alkynylamino, halo-C3-C6alkynylamino, C3-C6dialkynylamino wherein the alkynyl radicals are the same or different, halo-C3-C6dialkynylamino wherein the alkynyl radicals are the same or different, or Q is a monocyclic heterocycle, or a monocyclic heterocycle substituted one or more times by halogen, cyano, hydroxy, amino, nitro, formyl, -COOH, -CONH2, -CSNH2, d-dalkyl, halo-Crdalkyl, d-dalkoxy, halo-d-C6alkoxy, CrC6alkylamino, halo-CrC6alkylamino, CrCedialkylamino wherein the alkyl groups are the same or different or together with the nitrogen atom to which they are bonded form a 4- to 7-membered ring, halo-d-ddialkyl- amino wherein the alkyl groups are the same or different, (Crdalkyl)S(O)m, (halo-d-d- alkyl)S(O)m, (CrC6alkylamino)S(O)m, (CrC6dialkylamino)S(O)m wherein the alkyl groups are the same or different, (halo-CrC6dialkylamino)S(O)m wherein the alkyl groups are the same or different, d-dalkylsulfonyloxy, halo-d-dalkylsulfonyloxy, CrC6alkylS(O)mamino; CrC6alkylS(O)mamino substituted by halogen, amino, d-da'kylamino, d-ddialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; Crdalkoxy-d-dalkyl, halo-Crdalkoxy-Crd- alkyl, d-dalkoxy-d-dalkyloxy, halo-d-dalkoxy-d-dalkyloxy, CrCealkoxy-Crdalkyl- amino, halo-CrC6alkoxy-CrC6alkylamino, CrC6alkylS(O)m-CrC6alkyl, halo-CrdaIkylS(O)m- CrC6alkyl, CrC6alkylS(O)m-CrC6alkyloxy, halo-CrC6alkylS(O)m-CrC6alkyloxy, C C6alkyl- S(O)m-CrC6alkylamino, halo-CrCealkylS(O)m-CrC6alkylamino, CrC6alkylcarbonyl; CrC6alkylcarbonyl substituted by halogen, amino, d-dalkylamino, CrCedialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; d-dalkoxycarbonyl; d-dalkoxycarbonyl substituted by halogen, amino, d-dalkylamino, d-ddialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; d-dalkylcarbonyloxy; d-C6alkylcarbonyloxy substituted by halogen, amino, d-dalkylamino, d-Cedialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; formylamino, CrCealkylcarbonylamino; CrCealkylcarbonylamino substituted by halogen, amino, Crdalkylamino, d-Cedialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; d-dalkylaminocarbonyl; CrCealkylaminocarbonyl substituted by halogen, amino, CrC6alkylamino, d-Cedialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; d-ddialkylaminocarbonyl wherein the alkyl groups are the same or different; d-Cedialkylaminocarbonyl substituted by halogen, amino, d-dalkylamino, d-ddialkylamino, hydroxy, cyano, d-dalkoxy or by formyl, wherein the alkyl groups are the same or different; C2-C6alkenyl, halo-C2-C6alkenyl, C3-C6alkenyloxy, halo-Cg-dalkenyloxy, (C2-C6alkenyl)- S(O)m, (halo-C2-C6alkenyl)S(O)m, C3-C6alkenylamino, halo-C3-C6alkenylamino, d-ddialkenylamino wherein the alkenyl radicals are the same or different, halo- C3-C6dialkenylamino wherein the alkenyl radicals are the same or different, C3-C6cycloalkyl; C3-C6cycloalkyl substituted by halogen, amino, d-dalkylamino, d-Cedialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; tri(C1-C6alkyl)silyl; tri(CrC6alkyl)sily| substituted by halogen, amino, d-dalkylamino, CrCedialkylamino, hydroxy, cyano, d-dalkoxy or by formyl; pentafluorothio; C2-C6alkynyl, or C2-C6alkynyl substituted by halogen, amino, CrGealkylamino, CrCedialkylamino, hydroxy, cyano, d-dalkoxy, tri(CrC6alkyl)silyl or by formyl; C3-C6alkynyloxy, halo-C3-C6alkynyloxy, (C3-C6alkynyl)S(O)m, (halo-C3-C6alkynyl)S(O)m, C3-C6alkynylamino, halo-C3-C6alkynylamino, C3-C6dialkynylamino wherein the alkynyl radicals are the same or different, halo-C3-C6dialkynylamino wherein the alkynyl radicals are the same or different, and m is 0, 1 or 2, or an enantiomer, a mixture of enantiomers, a tautomer, a mixture of tautomers, or an agrochemically acceptable salt of a compound of formula I, an N-oxide of such a compound or an enantiomer, a mixture of enantiomers, a tautomer, a mixture of tautomers or an agrochemically acceptable salt thereof.
5. A method of controlling undesired plant growth, which comprises applying a herbicidally effective amount of a composition according to claim 4 to the plants or to the locus thereof.
6. A method of inhibiting plant growth, which comprises applying a herbicidally effective amount of a composition according to claim 4 to the plants or to the locus thereof.
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