WO2009019099A1 - Dérivés de pyrimidine tétrasubstitués permettant de contrôler des champignons phytopathogènes - Google Patents

Dérivés de pyrimidine tétrasubstitués permettant de contrôler des champignons phytopathogènes Download PDF

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WO2009019099A1
WO2009019099A1 PCT/EP2008/058794 EP2008058794W WO2009019099A1 WO 2009019099 A1 WO2009019099 A1 WO 2009019099A1 EP 2008058794 W EP2008058794 W EP 2008058794W WO 2009019099 A1 WO2009019099 A1 WO 2009019099A1
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alkyl
compounds
cycloalkyl
group
alkenyl
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PCT/EP2008/058794
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English (en)
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Bernd Müller
Jens Renner
Sarah Ulmschneider
Marianna Vrettou
Jochen Dietz
Joachim Rheinheimer
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Basf Se
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
    • C07D239/32—One oxygen, sulfur or nitrogen atom
    • C07D239/42—One nitrogen atom
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
    • C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
    • C07D239/47—One nitrogen atom and one oxygen or sulfur atom, e.g. cytosine
    • 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

Definitions

  • R 1 may comprise one, two, three or four identical or different groups selected from P 1 and R a , wherein P 1 is as defined below and wherein 5
  • R a is halogen, cyano, nitro, hydroxy, carboxyl, d-Cs-alkyl, Ci-Cs-haloalkyl, C 2 - Cs-alkenyl, C 2 -C8-haloalkenyl, C 2 -Cs-alkynyl, C 2 -C8-haloalkynyl, C 4 -Ci 0 - alkadienyl, Ci-Cs-alkoxy, Ci-Cs-haloalkoxy, C 2 -C8-alkenyloxy, C 2 -Cs-haloalkenyl- oxy, Cs-Cs-alkynyloxy, C3-Cs-haloalkynyloxy, Cs-Cs-cycloalkyl, C3-C8- 0 halocycloalkyl, Cs-Cs-cycloalkenyl, C3-Cs-cycloalkoxy, Cs-Cs-halo
  • n 0, 1 or 2;
  • aliphatic, alicyclic and/or aromatic groups in R a for their part may carry one, two or three identical or different groups R b ;
  • R b is halogen, cyano, nitro, hydroxy, mercapto, Ci-Cs-alkyl, C2-C8-alkenyl, C2-
  • R 5 is hydrogen, Ci-Ci2-alkyl, Ci-Ci2-haloalkyl, C2-Ci2-alkenyl, C2-Ci2-alkynyl, C3-Cs-cycloalkyl, C3-Cs-halocycloalkyl, Cs-C ⁇ -cycloalkenyl, Cs-C ⁇ -halocycIo- alkenyl, Ci-Cs-alkoxy, C2-Cs-alkenyloxy, C2-Cs-alkynyloxy, Cs-Cs-cycloalkoxy, NH2, Ci-C ⁇ -alkylamino, di-Ci-Cs-alkylamino, phenyl, naphthyl or a five- or six- membered saturated, partially unsaturated or aromatic heterocycle which contains one, two, three or four heteroatoms from the group consisting of O, N and S, wherein R 5 may be substituted by one, two, three or four R a ;
  • R 6 is Z-Y-(CR 11 R 12 )p-(CR 9 R 10 ) q -CR 7 R 8 -# or has the meaning as defined for R 5 except hydrogen; wherein # is the point of attachment to the N atom and wherein
  • R 7 ,R 8 ,R 9 ,R 10 ,R 11 ,R 12 are independently hydrogen, Ci-Cs-alkyl, Ci-Cs-haloalkyl,
  • R 7 together with R 8 , R 9 together with R 10 , R 11 together with R 12 may independently represent oxygen and form a carbonyl group or may represent a C2-C5-alkylene-, alkenylene- or alkynylene chain and form a spiro group, wherein the chains may be interrupted by one, two or three heteroatoms selected from O,
  • R 5 and R 7 may together with the nitrogen atom to which they are attached form a five-, six-, seven-, eight-, nine- or ten-membered saturated or partially saturated heterocyclus, that may contain one, two or three additional heteroatoms from the group O, N and S as ring members in addition to carbon atoms;
  • Y is O or S
  • Z is hydrogen, carboxyl, formyl, d-Cs-alkyl, d-Cs-haloalkyl, C2-C8-alkenyl,
  • R c is Ci-C 8 -alkyl, C 3 -C 8 -alkenyl, C 3 -C 8 -alkynyl, C 3 -C 6 -cycloalkyl, C 3 -C 6 - cycloalkenyl;
  • R A , R B independently of one another are hydrogen, Ci-C 8 -alkyl, C2-C 8 - alkenyl, C2-C 8 -alkynyl, C 3 -C6-cycloalkyl, C 3 -C6-cycloalkenyl; R A and R B together with the nitrogen atom to which they are attached or R A and R c together with the carbon and heteroatoms via which they are attached may also form a five- or six- membered saturated, partially unsaturated or aromatic ring which, in addition to carbon atoms, may contain one, two or three further heteroatoms from the group consisting of O, N and S as ring member and/or may carry one or more substituents R a ; or
  • Z and R 10 or R 12 may also form a five- or six-membered saturated or partially unsaturated ring which, in addition to carbon atoms and Y, may contain one or two further heteroatoms from the group consisting of N and S as ring member and/or may carry one or more substituents R a ;
  • R 5 and R 6 together with the nitrogen atom to which they are attached may also form a five-, six-, seven-, eight-, nine- or ten-membered saturated, partially unsaturated or aromatic heterocycle which, in addition to carbon atoms, may contain one, two or three further heteroatoms from the group consisting of O, N and S as ring member; wherein the heterocycle may be unsubstituted or substituted by one, two or three groups independently selected from Z-Y-#, Z-Y- (CR 9 R 10 ) q -CR 7 R 8 -# and R a , wherein # is the point of attachment to the heterocycle;
  • R 2 cyano, halogen, C2-C3-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, C2-C4- alkenyl, C3-C4-alkenyloxy, C2-C4-alkynyl or C3-C4-alkynyloxy;
  • R 3 five- or six-membered saturated, partially unsaturated or aromatic heterocycle which contains one, two, three or four heteroatoms from the group consisting of O, N and
  • R 3 is not pyrazol-1-yl, wherein R 3 may be partially or fully halogenated and/or may carry one, two, three, four or five identical or different groups R d , wherein
  • R d is halogen, hydroxy, cyano, nitro, d-Cs-alkyl, d-Cs-haloalkyl, C2-C8-alkenyl, C2-
  • R 3 may furthermore be:
  • W is O, S, NR9, NOR9 or N-NR z R g ;
  • R e ,R f ,R9,R h independently of one another are hydrogen, Ci-C ⁇ -alkyl,
  • aliphatic and/or alicyclic groups of the radical definitions of R e , R f , R9, R h , R y and R z for their part may be partially or fully halogenated and/or may carry one, two, three or four identical or different groups R w :
  • R w is halogen, cyano, Ci-Cs-alkyl, C2-Cio-alkenyl, C2-Cio-alkynyl, C3-C6- cycloalkyl, Cs-C ⁇ -cycloalkenyl, Ci-C ⁇ -alkoxy, C2-Cio-alkenyloxy, C2- Cio-alkynyloxy, Cs-C ⁇ -cycloalkoxy, Cs-C ⁇ -cycloalkenyloxy;
  • Y 1 is C k R', C(O)O, C(O)NR', oxygen, sulfur, NR 1 , SO or SO 2 ;
  • Y 2 is Ci-Cs-alkylene, C2-Cs-alkenylene or C2-C8-alkynylene, where Y 2 may be interrupted by one, two, three or four heteroatoms from the group consisting of NR A , oxygen, sulfur, SO and SO2;
  • T is OR 1 , NR k R', C(O)OR 1 , C(O)NR k R', C(NOR k )R' or
  • T 1 -C( T 2 )-T 3 in which T 1 is oxygen or NR 1 ;
  • T 2 is oxygen, sulfur or NR 1 ;
  • T 3 is R 1 , OR 1 , SR 1 or NR k R'; each R 1 and R k is independently hydrogen, Ci-Cs-alkyl, C3-Cs-alkenyl, C3- Cs-alkynyl, Cs-C ⁇ -cycloalkyl or Cs-C ⁇ -cycloalkenyl, wherein the last five radicals may be unsubstituted, partially or fully halogenated and/or may carry one, two or three groups R m ; each R m is independently cyano, nitro, hydroxyl, mercapto, amino, carboxyl, d-C ⁇ -alkyl, C2-C8-alkenyl, Ci-C ⁇ -alkoxy, C2-C8-alkenyloxy, C2-C8- alkynyloxy, C-i-C ⁇ -alkylthio, Ci-C ⁇ -alkylamino, di-(Ci-C
  • the present invention relates to the use thereof for controlling phytopathogenic fungi, to a method for controlling phytopathogenic fungi wherein the fungi and/or the materials, plants, the soil and/or the seed to be protected against fungal attack are treated with an effective amount of at least one pyrimidine of the formula I.
  • the present invention furthermore provides fungicidal compositions comprising at least one of the compounds according to the invention.
  • the pyrimidines I according to the invention may have one or more centers of chirality, in which case they are present as enantiomer or diastereomer mixtures.
  • the invention provides both the pure enantiomers or diastereomers or rotamers and mixtures thereof.
  • Suitable compounds of the formula I also include all possible stereoisomers (cis/trans isomers) and mixtures thereof.
  • the compounds according to the invention can be present in different crystal modifications, which may differ in their biological activity. They also form part of the subject matter of the present invention.
  • WO 01/096314 WO 02/074753, WO 03/043993, WO 04/103978, WO 2005/019207, WO 2007/036477.
  • WO 2007/083692 A1 is directed to aminopyrimidine compounds, which carry a pyrazol-1-yl group in 2-position and for example an alkyl group in 5-position. 93, WO 04/103978).
  • the compounds of the prior art are, however, with a view to their fungicidal activity, sometimes unsatisfactory, or they have unwanted properties, such as low crop plant compatibility.
  • agriculturally acceptable salts include in particular the salts of those cations and the acid addition salts of those acids whose cations and anions, respectively, have no adverse effect on the pesticidal action of the pyrimidines according to the invention.
  • suitable cations are in particular the ions of the alkali metals, preferably sodium and potassium, of the alkaline earth metals, preferably calcium, magnesium and barium, and of the transition metals, preferably manganese, copper, zinc and iron, and also the ammonium ion which, if desired, may bear from one to four (Ci-C4)-alkyl substituents and/or one phenyl or benzyl substituent, preferably diisopropylammonium, tetramethylammonium, tetrabutylammonium, trimethylbenzylammonium, and also phosphonium ions, sulfonium ions, preferably tri(Ci-C4-alkyl)sulfonium, and sulfoxonium ions, preferably tri(Ci-C4-alkyl)sulfoxonium.
  • the alkali metals preferably sodium and potassium
  • the alkaline earth metals preferably calcium, magnesium and barium
  • Anions of useful acid addition salts are for example chloride, bromide, fluoride, hydrogen sulfate, sulfate, dihydrogenphosphate, hydrogenphosphate, phosphate, nitrate, bicarbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate, and also the anions of (Ci-C4)-alkanoic acids, preferably formate, acetate, propionate and butyrate. They can be formed by reacting the compounds according to the invention with an acid of the corresponding anion, preferably hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid or nitric acid.
  • the compounds according to the invention can be obtained by various routes.
  • Hal 1 is halogen, in particular fluorine, chlorine or bromine, preferably chlorine, and R 4 , R 5 and R 6 have the meanings and preferred meanings as defined for formula I.
  • Hal 1 , R 4 , R 5 and R 6 have the meanings as defined herein.
  • the substituted hydroxylamines can be used as free base or, preferably, in the form of their acid addition salts.
  • the halides, such as chlorides, or the sulfates are particularly suitable.
  • the compound of the formula I is prepared by reacting the sulfone of the formula 2 with compounds R 3 -H.
  • the reaction is carried out under basic conditions.
  • the alkali metal, alkaline earth metal or ammonium salt of the compound R 3 -H can be employed directly.
  • bases it is possible to add bases.
  • This reaction is typically carried out under the conditions of a nucleophilic substitution; usually at from 0 to 200 0 C, preferably at from 10 to 150 0 C. If appropriate, it may be advantageous to carry out the reaction in the presence of a phase-transfer catalyst, for example 18-Krone-6.
  • the reaction is usually carried out in the presence of a dipolar aprotic solvent, such as an N,N-dialkylated carboxamide, for example N, N- dimethylformamide, a cyclic ether, for example tetrahydrofuran, or a carbonitrile, such as acetonitrile (cf. DE-A 39 01 084; Chimia, Vol. 50, pp. 525-530 (1996); Khim. Geterotsikl. Soedin, Vol. 12, pp. 1696-1697 (1998)).
  • a dipolar aprotic solvent such as an N,N-dialkylated carboxamide, for example N, N- dimethylformamide, a cyclic ether, for example tetrahydrofuran, or a carbonitrile, such as acetonitrile
  • a heterocyclic radical R 3 the heterocycle can be reacted directly with an alkylsulfonyl compound (compound 2) (such as, for example triazole).
  • an auxiliary base is generally employed.
  • An azole can be introduced, for example, by initially deprotonating this with a suitable base, such as, for example, an alkali metal alkoxide or hydroxide or sodium hydride, and then reacting it in a suitable solvent, such as, for example, tetrahydrofuran, dioxane or dimethylformamide, with the alkylsulfonyl compound.
  • the compounds 2 and R 3 -H are employed in approximately stoichiometric amounts. However, it may be advantageous to use the nucleophile of the formula R 3 -H in excess, for example in excess of up to 10-fold, in particular up to 3-fold, based on the compound 2.
  • a base which may be employed in equimolar amounts or else in excess.
  • bases are alkali metal carbonates and alkali metal bicarbonates, for example sodium carbonate and sodium bicarbonate, nitrogen bases, such as triethylamine, tributylamine and pyridine, alkali metal alkoxides, such as sodium methoxide or potassium tert-butoxide, alkali metal amides, such as sodium amide, or alkali metal hydrides, such as lithium hydride or sodium hydride.
  • Suitable solvents are halogenated hydrocarbons, ethers, such as diethyl ether, diiso- propyl ether, tert-butyl ether, 1 ,2-dimethoxyethane, dioxane, anisole and tetrahydrofuran, and also dimethyl sulfoxide, N,N-dialkylated carboxamides, such as dimethylformamide or dimethylacetamide. Particular preference is given to using ethanol, dichloromethane, acetonitrile or tetrahydrofuran. It is also possible to use mixtures of the solvents mentioned.
  • heterocyclic substituents can also be introduced during the construction of the pyrimidine ring.
  • a corresponding heterocyclic amidine which are known to the person skilled in the art or can be prepared from the corresponding heterocyclic nitriles, is reacted with a malonic ester to give the pyrimidine ring (see also WO 2003/070721 ).
  • Suitable oxidizing agents are in particular hydrogen peroxide or peracids of organic carboxylic acids; advantageously, MCPBA (meta-chloroperbenzoic acid) may be used.
  • MCPBA metal-chloroperbenzoic acid
  • the oxidation may also be carried out using selenium dioxide. The oxidation is preferably carried out at from 10 to 50 0 C in the presence of protic or aprotic solvents (cf. B. Kor. Chem. Soc, Vol. 16, pp. 489-492 (1995); Z. Chem., Vol. 17, p. 63 (1977)).
  • Hal 1 and Hal 2 are each independently of one another halogen, in particular fluorine, chlorine or bromine, preferably chlorine, and R 4 , R 5 and R 6 have the meanings as given above.
  • Compounds 4 are known or obtainable analogously to the known substances.
  • compounds 4 can be prepared from the respective dihydroxy-compounds 5, wherein the dihydroxy-compound 5 is converted with a halogenating agent into the dihalo-compounds of the formula 4.
  • the halogenating agent employed is advantageously a phosphorus oxyhalide or a phosphorus(V) halide, such as phosphorus pentachloride, phosphorus oxybromide or phosphorus oxychloride, or a mixture of phosphorus oxychloride with phosphorus pentachloride.
  • a hydrohalide of a tertiary amine for example triethylamine hydrochloride, may be added as co-catalyst.
  • This reaction of the dihydroxy-compound with the halogenating agent is usually carried out at from 0 0 C to 150 0 C, preferably at from 80°C to 125°C (cf. also EP- A-770615).
  • the reaction can be carried out neat or in an inert solvent, for example a halogenated hydrocarbon, such as dichloromethane, dichloroethane, or an aromatic hydrocarbon, such as, for example, toluene, xylenes and the like, or in a mixture of the solvents mentioned above.
  • a halogenated hydrocarbon such as dichloromethane, dichloroethane, or an aromatic hydrocarbon, such as, for example, toluene, xylenes and the like, or in a mixture of the solvents mentioned above.
  • the dihydroxy-compound 5 can be obtained by reacting thiourea with a malonic ester of formula 6
  • Suitable alkylating agents are, for example, Ci-C ⁇ -alkyl halides, preferably alkyl bromides and alkyl chlorides, di-Ci-C ⁇ -alkyl sulfates or Ci-C ⁇ -alkyl phenyl- sulfonates.
  • the reaction is usually carried out in the presence of a solvent which is inert under the given reaction conditions.
  • R 2 is an alkyl group.
  • An alkyl group (R 2 ) can be introduced using organometallic compounds of the formula (R 2 ) n -M where M is, for example, magnesium, zinc or lithium, for instance at the stage of the compound 2, 3 or Ia.
  • M is, for example, magnesium, zinc or lithium
  • R 2 is a cyano group
  • the radical R 2 can be introduced by reaction with alkali metal cyanides and alkali metal alkoxides, respectively.
  • reaction mixtures are worked up in a customary manner, for example by mixing with water, separating the phases and, if appropriate, chromatographic purification of the crude products.
  • Some of the intermediates and end products are obtained in the form of colorless or slightly brownish viscous oils which are purified or freed from volatile components under reduced pressure and at moderately elevated temperature. If the intermediates and end products are obtained as solids, purification can also be carried out by recrystallization or digestion.
  • halogen fluorine, chlorine, bromine and iodine
  • alkyl and the alkyl moieties of composite groups such as, for example, alkylamino: saturated straight-chain or branched hydrocarbon radicals having 1 to 2, 4, 6, 8, 10 or 12 carbon atoms, for example d-C ⁇ -alkyl, such as methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methyl-propyl, 2-methylpropyl, 1 ,1-dimethylethyl, pentyl, 1-methylbutyl, 2-me- thylbutyl, 3-methylbutyl, 2,2-di-methylpropyl, 1-ethylpropyl, hexyl, 1 ,1-dimethylpropyl, 1 ,2-dimethylpropyl, 1-methylpentyl, 2-methyl pentyl, 3-methylpentyl, 4-methylpentyl, 1 ,1-dimethylbutyl, 1 ,2-dimethylbutyl, 1 ,3-dimethylbuty
  • haloalkyl alkyl as mentioned above, where some or all of the hydrogen atoms in these groups are replaced by halogen atoms as mentioned above.
  • the alkyl groups are substituted at least once or completely by a particular halogen atom, preferably fluorine, chlorine or bromine.
  • the alkyl groups are partially or fully halogenated by different halogen atoms; in the case of mixed halogen substitutions, the combination of chlorine and fluorine is preferred.
  • (Ci-C4)-haloalkyl more preferably (Ci-C2)-haloalkyl, such as chloromethyl, bromomethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoro- methyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-chloroethyl, 1-bromoethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2- trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2- fluoroethyl, 2,2,2-trichloroethyl, pentafluoroethyl or 1 ,1 ,1 -trifl uoroprop-2-yl ;
  • alkenyl and also the alkenyl moieties in composite groups such as alkenyloxy: unsaturated straight-chain or branched hydrocarbon radicals having 2 to 4, 2 to 6, 2 to 8, 2 to 10 or 2 to 12 carbon atoms and one or two, preferably one, double bond in any position.
  • alkenyloxy unsaturated straight-chain or branched hydrocarbon radicals having 2 to 4, 2 to 6, 2 to 8, 2 to 10 or 2 to 12 carbon atoms and one or two, preferably one, double bond in any position.
  • small alkenyl groups such as (C2-C4)-alkenyl
  • larger alkenyl groups such as (C5-C8)-alkenyl.
  • alkenyl groups are, for example, C2-C6-alkenyl, such as ethenyl, 1-propenyl, 2-propenyl, 1-methylethenyl, 1-butenyl, 2- butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl, 2- methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl-1-butenyl, 3-methyl-1-butenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 3- methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, 1 ,1- dimethyl-2-propenyl, 1 ,2-dimethyl-1-propenyl, 1 ,2-dimethyl-2-propenyl, 1-
  • haloalkenyl alkenyl as defined above, where some or all of the hydrogen atoms in these groups are replaced by halogen atoms as described above under haloalkyl, in particular fluorine, chlorine or bromine;
  • alkadienyl unsaturated straight-chain or branched hydrocarbon radicals having 4 to 6, 4 to 8 or 4 to 10 carbon atoms and two double bonds in any position; alkynyl and the alkynyl moieties in composite groups: straight-chain or branched hydrocarbon groups having 2 to 4, 2 to 6, 2 to 8, 2 to 10 or 2 to 12 carbon atoms and one or two triple bonds in any position, for example C2-C6-alkynyl, such as ethynyl, 1- propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-methyl-2-butynyl, 1-methyl-3-butynyl, 2-methyl-3- butynyl, 3-methyl-1-butynyl, 1 ,1-dimethyl-2-prop
  • haloalkynyl alkynyl as defined above, where some or all of the hydrogen atoms in these groups are replaced by halogen atoms as described above under haloalkyl, in particular fluorine, chlorine or bromine;
  • cycloalkyl and also the cycloalkyl moieties in composite groups mono- or bicyclic saturated hydrocarbon groups having 3 to 6, 3 to 8, 3 to 10 or 3 ro 12 carbon ring members, for example Cs-C ⁇ -cycloalkyl, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl;
  • halocycloalkyl cycloalkyl as defined above, where some or all of the hydrogen atoms in these groups are replaced by halogen atoms as described above under haloalkyl, in particular fluorine, chlorine or bromine;
  • cycloalkenyl monocyclic monounsaturated hydrocarbon groups having preferably 3 to 12, 3 to 10, 3 to 8 or 4 to 6, in particular 5 to 6, carbon ring members, such as cyclopenten-1-yl, cyclopenten-3-yl, cyclohexen-1-yl, cyclohexen-3-yl, cyclohexen-4-yl and the like;
  • halocycloalkenyl cycloalkenyl as defined above, where some or all of the hydrogen atoms in these groups are replaced by halogen atoms as described above under haloalkyl, in particular fluorine, chlorine or bromine;
  • alkoxy an alkyl group as defined above which is attached via an oxygen, preferably having 1 to 8, more preferably 2 to 6, carbon atoms. According to the invention it may be preferred to use small alkoxy groups, such as (Ci-C 4 )-alkoxy, on the other hand, it may also be preferred to use larger alkoxy groups, such as (Cs-C8)-alkoxy.
  • alkoxy groups are: methoxy, ethoxy, n-propoxy, 1-methylethoxy, butoxy, 1- methylpropoxy, 2-methylpropoxy or 1 ,1-dimethylethoxy, pentoxy, 1-methylbutoxy, 2- methylbutoxy, 3-methylbutoxy, 1 ,1-dimethylpropoxy, 1 ,2-dimethylpropoxy, 2,2- dimethylpropoxy, 1 -ethyl propoxy, hexoxy, 1-methylpentoxy, 2-methylpentoxy, 3- methylpentoxy, 4-methylpentoxy, 1 ,1-dimethylbutoxy, 1 ,2-dimethylbutoxy, 1 ,3- dimethylbutoxy, 2,2-dimethylbutoxy, 2,3-dimethylbutoxy, 3,3-dimethylbutoxy, 1- ethylbutoxy, 2-ethylbutoxy, 1 ,1 ,2-trimethylpropoxy, 1 ,2,2-trimethylpropoxy, 1-ethyl-1- methylpropoxy or 1-ethyl
  • haloalkoxy alkoxy as defined above, where some or all of the hydrogen atoms in these groups are replaced by halogen atoms as described above under haloalkyl, in particular fluorine, chlorine or bromine.
  • short-chain haloalkoxy groups such as (Ci-C4)-haloalkoxy
  • relatively long-chain haloalkoxy groups such as (Cs-Cs)- haloalkoxy.
  • haloalkoxy radicals are OCH2F, OCHF2, OCF3, OCH2CI, OCHCb, OCCb, chlorofluoromethoxy, dichlorofluoromethoxy, chlorodifluoro- methoxy, 2-fluoroethoxy, 2-chloroethoxy, 2-bromoethoxy, 2-iodoethoxy, 2,2- difluoroethoxy, 2,2,2-trifluoroethoxy, 2-chloro-2-fluoroethoxy, 2-chloro-2,2- difluoroethoxy, 2,2-dichloro-2-fluoroethoxy, 2,2,2-trichloroethoxy, OC2F5, 2- fluoropropoxy, 3-fluoropropoxy, 2,2-difluoropropoxy, 2,3-difluoropropoxy, 2- chloropropoxy, 3-chloropropoxy, 2,3-dichloropropoxy, 2-bromopropoxy, 3- bromopropoxy, 3,3,3
  • alkenyloxy alkenyl as defined above which is attached via an oxygen atom. Preference is given to (C2-C8)-alkenyloxy, more preference to (C3-C6)-alkenyloxy. According to the invention, it may be preferred to use short-chain alkenyloxy radicals, such as (C 2 -C 4 )- alkenyloxy, on the other hand, it may also be preferred to use relatively long-chain alkenyloxy groups, such as (C5-C8)-alkenyloxy;
  • alkylene divalent unbranched chains of CH2 groups. Preference is given to (Ci-C ⁇ )- alkylene, more preference to (C2-C4)-alkylene; furthermore, it may be preferred to use (Ci-Cs)-alkylene groups.
  • preferred alkylene radicals are CH2, CH2CH2, CH 2 CH 2 CH 2 , CH 2 (CH 2 )2CH2, CH 2 (CH 2 )SCH 2 and CH 2 (CH 2 ) 4 CH 2 ;
  • oxyalkylene alkylene as defined above, preferably with 2 to 4 CH 2 groups, where one valency is attached to the skeleton via an oxygen atom.
  • preferred oxyalkylene radicals are OCH 2 , OCH 2 CH 2 , OCH 2 CH 2 CH 2 and OCH 2 (CH 2 ) 2 CH 2 ;
  • oxyalkyleneoxy alkylene as defined above, preferably with 1 to 3 CH 2 groups, where both valencies are attached to the skeleton via an oxygen atom.
  • oxyalkyleneoxy radicals are OCH 2 O, OCH 2 CH 2 O and OCH 2 CH 2 CH 2 O; alkylthio: alkyl as defined above which is attached via an S atom;
  • alkylsulfinyl alkyl as defined above which is attached via an SO group;
  • alkylsulfonyl alkyl as defined above which is attached via an S(O)2 group;
  • the heterocycle in question may be attached via a carbon atom or via a nitrogen atom, if present. According to the invention it may be preferred for the heterocycle in question to be attached via carbon; on the other hand, it may also be preferred for the heterocycle to be attached via nitrogen.
  • the heterocycle is in particular: - 5- or 6-membered saturated or partially unsaturated heterocyclyl which contains one, two or three nitrogen atoms and/or one oxygen or sulfur atom or one or two oxygen and/or sulfur atoms, where the heterocyclyl may be attached via C or N;
  • 5- or 6-membered saturated or partally unsaturated heterocyclyl which contains one, two or three nitrogen atoms and/or one oxygen or sulfur atom or one or two oxygen and/or sulfur atoms, where the heterocyclyl may be attached via C or N, if present: for example 2-tetrahydrofuranyl, 3-tetrahydrofuranyl, 2-tetrahydrothienyl, 3- tetrahydrothienyl, 2-pyrrolidinyl, 3-pyrrolidinyl, 3-isoxazolidinyl, 4-isoxazolidinyl, 5- isoxazolidinyl, 3-isothiazolidinyl, 4-isothiazolidinyl, 5-isothiazolidinyl, 3-pyrazolidinyl, 4- pyrazolidinyl, 5-pyrazolidinyl, 2-oxazolidinyl, 4-oxazolidinyl, 5-oxazolidinyl, 2-thia- zolidinyl, 4-thi
  • 5-membered heteroaryl which contains one, two, three or four nitrogen atoms or one, two or three nitrogen atoms and/or one sulfur- or oxygen atom, where the heteroaryl may be attached via C or N, if present: 5-membered heteroaryl groups which, in addition to carbon atoms, may carry one to four nitrogen atoms or one to three nitrogen atoms and/or one sulfur or oxygen atom as ring members, for example furyl, thienyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl (1 ,2,3-; 1 ,2,4-triazolyl), tetrazolyl, oxazolyl, isoxazolyl, 1 ,3,4-oxadiazolyl, thiazolyl, isothiazolyl and thiadiazolyl, in particular 2-furyl, 3-furyl, 2-thienyl, 3-thienyl, 2-pyrrolyl, 3-pyrrolyl, 3-isoxazo
  • 6-membered heteroaryl which contains one, two, three or four, preferably one, two or three, nitrogen atoms, where the heteroaryl may be attached via C or N, if present: 6- membered heteroaryl groups which, in addition to carbon atoms, may contain one to four or one to three nitrogen atoms as ring members, for example pyridinyl, pyrimidinyl, pyrazinyl, pyridazinyl, 1 ,2,3-triazinyl, 1 ,2,4-triazinyl, 1 ,3,5-triazinyl, in particular 2- pyridinyl, 3-pyridinyl, 4-pyridinyl, 3-pyridazinyl, 4-pyridazinyl, 2-pyrimidinyl, 4- pyrimidinyl, 5-pyrimidinyl, 2-pyrazinyl, 1 ,3,5-triazin-2-yl and 1 ,2,4-triazin-3-yl.
  • the scope of the present invention embraces the (R) and (S) isomers or rotamers and the racemates of compounds according to the invention having chiral centers.
  • the compounds according to the invention may be present in various crystal modifications which may differ in their biological activity. They are likewise provided by the present invention.
  • a heterocyclic ring may be, according to one embodiment of the invention, attached via C to the pyrimidine skeleton of the compounds of the invention.
  • the heterocyclic ring is attached via N (if present) to the pyrimidine skeleton.
  • “partially unsaturated” means that the heterocycle does not form an aromatic system, wherein the heterocycle preferably contains one or two double bonds.
  • R 1 is NR 5 R 6 .
  • R 5 is hydrogen.
  • also preferred compounds are compounds of formula I in which R 5 and R 6 are both different from hydrogen. From among these, preference is given to compounds of the formula I in which R 6 is Ci-C4-alkyl, Ci-C4-haloalkyl or Ci-C4-alkoxy, especially methyl, ethyl or methoxy, in particular methyl or ethyl.
  • R 5 is hydrogen, straight-chain or branched Ci- Cs-alkyl or d-Cs-haloalkyl, Cs-Cs-cycloalkyl, Cs-Cs-halocycloalkyl, C2-C8-alkenyl, C2-C8- haloalkenyl, C4-C8-halocycloalkenyl or phenyl or naphthyl, that may be unsubstituted or substituted by one, two or three R a , preferably independently selected from halogen, Ci-C ⁇ -alkyl, d-C ⁇ -haloalkyl, cyano, hydroxy, Ci-C ⁇ -alkoxy, C-i-C ⁇ -haloalkoxy, C2-C6- alkenyloxy, C2-C6-haloalkenyloxy, Cs-C ⁇ -alkynyloxy, Cs-C ⁇ -haloalkynyloxy, Cs-C ⁇ -
  • R 5 is hydrogen, straight-chain or branched Ci- Cs-alkyl or d-Cs-haloalkyl, Cs-Cs-cycloalkyl or C2-Cs-alkenyl, that may be further substituted by one or two R a as defined herein.
  • R 5 is hydrogen, straight-chain or branched C2- C ⁇ -alkyl, C5-C7-cycloalkyl or C2-C4-alkenyl, that may be further substituted by one or two R a as defined herein.
  • R 5 is hydrogen or straight-chain or branched C2-C6-alkyl.
  • R 6 is hydrogen, methyl, ethyl or propyl.
  • R 6 is straight-chain or branched d-Cs-alkyl or d-Cs-haloalkyl, Cs-Cs-cycloalkyl, Cs-Cs-halocycloalkyl, straight-chain or branched unsubstituted or substituted C2-Cs-alkenyl, d-Cs-haloalkenyl, d-Cs-halocycloalkenyl or unsubstituted or substituted phenyl or naphthyl, that may be each further substituted by one or two R a as defined herein.
  • R 6 is C3-C6-cycloalkyl which may be substituted by Ci-C4-alkyl and/or C 3 -C6-cycloalkyl-(Ci- C4)-alkyl.
  • R 6 is straight-chain or branched Ci-Cs- alkyl, d-Cs-haloalkyl, C 3 -C8-cycloalkyl or C 2 -Cs-alkenyl, that may be further substituted by one or two R a as defined herein.
  • R 6 is straight-chain or branched C 3 - C ⁇ -alkyl, C5-C7-cycloalkyl or C 2 -C4-alkenyl, that may be further substituted by one or two R a as defined herein.
  • R 6 is straight-chain or branched C 3 - C ⁇ -alkyl or Ci-Cs-haloalkyl, in particular methyl, ethyl, propyl, isopropyl, 1 ,2- dimethylpropyl, 1 ,2,2-trimethylpropyl, trifluoroethyl or 2,2,2-trifluoro-1-methylethyl.
  • R 6 is Z-Y-(CR 11 R 12 ) p - (CR 9 R 10 )q-CR 7 R 8 -#; wherein # is the point of attachment to the N atom and wherein R 7 ,R 8 ,R 9 ,R 10 ,R 11 ,R 12 are independently selected from hydrogen, Ci-C 8 -alkyl, Ci-C 8 - haloalkyl, C 2 -Cs-alkenyl, C 2 -Cs-haloalkenyl, C 2 -Cs-alkinyl, C 2 -Cs-haloalkinyl, Cs-C ⁇ - cycloalkyl, C 3 -C6-halocycloalkyl, Cs-C ⁇ -cycloalkenyl, C 3 -C6-halocycloalkenyl, phenyl, naphthyl and a five- or six-membered saturated, partially unsaturated or aromatic heterocycle, containing one
  • R 5 is hydrogen or Ci-C4-alkyl, such as hydrogen or methyl or ethyl, in particular hydrogen.
  • R5 and/or R6 may be further substituted by one, two or three R a as defined herein.
  • substituents independently selected from halogen, Ci-C ⁇ -alkyl, Ci-C ⁇ -haloalkyl, cyano, hydroxy, Ci-C ⁇ -alkoxy, Ci-C ⁇ -hal
  • R 7 is straight-chain or branched Ci- Cs-alkyl, C 3 -Cs-alkenyl or Cs-C ⁇ -cycloalkyl, in particular Ci-C ⁇ -alkyl or C 3 -C6-cycloalkyl, preferably isopropyl, isobutyl, tert-butyl, sec-pentyl, cyclopropyl or cyclopentyl, in particular tert-butyl.
  • a further specification of this embodiment relates to compounds I, wherein R 7 is not hydrogen or methyl.
  • the group R 7 is branched at the ⁇ -carbon.
  • a further specification of this embodiment relates to compounds I in which R 8 is hydrogen, straight-chain or branched Ci-Cs-alkyl or Cs-C ⁇ -cycloalkyl, in particular hydrogen, d-C ⁇ -alkyl or Cs-C ⁇ -cycloalkyl, preferably hydrogen, isopropyl, tert-butyl. If R 8 is an alkyl group, R 8 preferably has the same meaning as R 7 .
  • R 7 and R 8 together form a C3-C6-alkylene group, in particular a C3-C4-alkylene group, where the carbon chains may be substituted by groups attached via heteroatoms, such as halogen, alkoxy, alkylthio, amino, alkylamino, dialkylamino or alkoxycarbonyl.
  • R 7 and R 8 together form a C3-C6-alkylene group, in particular a C3-C4-alkylene group, where the carbon chains are interrupted by one or two heteroatoms from the group consisting of O, N and S and may be substituted by groups attached via heteroatoms, such as halogen, alkoxy, alkylthio, amino, alkylamino, dialkylamino or alkoxycarbonyl.
  • R 8 , R 9 , R 10 , R 11 and R 12 are each hydrogen or Ci-C4-alkyl, preferably hydrogen, methyl or ethyl, in particular hydrogen.
  • R 7 and R 9 together form a C3-C6-alkylene, Cs-C ⁇ -oxyalkylene or C2-Cs-oxyalkyleneoxy group, in particular a C3-C4- alkylene group.
  • R 9 and R 10 and/or R 11 and R 12 in each case together form a Cs-C ⁇ -alkylene, Cs-C ⁇ -oxyalkylene or C2-Cs-oxyalk- yleneoxy group, in particular a C3-C4-alkylene group.
  • the index q has the value zero.
  • a further embodiment relates to compounds I in which the index q is 1.
  • a further embodiment relates to compounds I in which the index p is zero or 1 , in particular zero.
  • R 9 and R 10 are preferably hydrogen if the index p has the value zero.
  • R 11 is not hydrogen and R 12 is hydrogen, if the index p has the value zero.
  • the index p has the value or 1 and the index q has the value 1.
  • R 11 and R 12 are preferably hydrogen. In a further embodiment of the compounds of the formula I, R 11 is not hydrogen and R 12 is hydrogen.
  • Y is oxygen
  • Z is a monovalent group.
  • a further embodiment relates to compound I, in which Z is Ci-C4-alkylcarbonyl, in particular acetyl, n-propan-1 -one, 2-methylpropan-1 -one or butan-1 -one.
  • a further embodiment relates to compound I in which Z is carboxyl or formyl.
  • a further embodiment relates to compound I in which Z is hydrogen.
  • a further embodiment relates to compound I in which Z is carboxyl.
  • a further embodiment relates to compound I in which Z is formyl.
  • a further embodiment relates to compound I in which Z is d-Cs-alkyl.
  • a further embodiment relates to compound I in which Z is Ci-Cs- haloalkyl.
  • a further embodiment relates to compound I in which Z is C2-Ce-alkenyl.
  • a further embodiment relates to compound I in which Z is C2-Ce-haloalkenyl.
  • a further embodiment relates to compound I in which Z is C2-C ⁇ -alkynyl.
  • a further embodiment relates to compound I in which Z is C2-C8-haloalkynyl.
  • a further embodiment relates to compound I in which Z is Cs-C ⁇ -cycloalkyl.
  • a further embodiment relates to compound I in which Z is Cs-Cs-cycloalkenyl.
  • a further embodiment relates to compound I in which Z is C(O)R C .
  • a further embodiment relates to compound I in which Z is C(O)OR C .
  • a further embodiment relates to compound I in which Z is C(S)OR C .
  • a further embodiment relates to compound I in which Z is C(O)SR C .
  • a further embodiment relates to compound I in which Z is C(S)SR C .
  • a further embodiment relates to compound I in which Z is C(NR A )SR C .
  • a further embodiment relates to compound I in which Z is C(S)R C .
  • a further embodiment relates to compound I in which Z is C(NR C )NR A R B .
  • a further embodiment relates to compound I in which Z is C(NR C )R A .
  • a further embodiment relates to compound I in which Z is C(NR C )OR A .
  • a further embodiment relates to compound I in which Z is C(O)NR A R B .
  • a further embodiment relates to compound I in which Z is C(S)NR A R B .
  • a further embodiment relates to compound I in which Z is C i -C ⁇ -a I ky I s u lfi ny I .
  • a further embodiment relates to compound I in which Z is d-Cs-alkylthio.
  • a further embodiment relates to compound I in which Z is d-Cs-alkylsulfonyl.
  • a further embodiment relates to compound I in which Z is (O)-Ci-C 4 -alkylene-NR A C(NR c )NR A R B .
  • a further embodiment relates to compound I in which Z is C(S)-Ci-C 4 -alkylene-NR A C(NR c )NR A R B .
  • a further embodiment relates to compound I in which Z is C(NR c )-Ci-C 4 -alkylene-NR A C(NR c )NR A R B .
  • a further embodiment relates to compound I in which Z is phenyl.
  • the groups Z mentioned above may be substituted by one, two, three or four groups R b as defined herein.
  • a further specific embodiment relates to compounds I in which the group NR 5 R 6 is ethylglycinol, leucinol, tert-leucinol, valinol, norvalinol, methioninol, phenylalaninol, lysinol, argininol, histidinol, asparaginol, glutaminol, serinol, isoleucinol, cysteinol, hydroxymethylpiperidine, cis-2-hydroxymethyl-4-methylpiperidine, trans-2-hydroxy- methyl-4-methyl-piperidine, cyclohexylglycinol, cyclopentylglycinol, butylglycinol, pentylglycinol, cis-2-aminocyclohexanol, trans-2-aminocyclohexanol, cis-2-aminocyclo- pentanol, trans-2-aminocyclopen
  • R 5 and R 6 together with the nitrogen atom to which they are attached form an unsubstituted or substituted saturated or partially unsaturated five- or six-membered ring.
  • heterocyclyl is in particular unsubstituted or substituted by 1 , 2 or 3 substituents R a , preferred substituents R a on heterocyclyl being selected from the group consisting of halogen, Ci-C4-alkyl and Ci-C4-haloalkyl.
  • preferred heterocyclyl rings are pyrrolidinyl, 2-methylpyrrolidinyl, piperidinyl, 4-methylpiperidinyl, 4-trifluoromethylpiperi- dinyl, 3,4-dimethylpiperidinyl, morpholinyl, 5-methylperhydro-(1 ,2)-oxazinyl and 6- methylperhydro-(1 ,2)-oxazinyl. It may be especially preferred, if R 5 and R 6 together form pyrrolidinyl, piperidinyl, 4-methylpiperidinyl or morpholinyl.
  • R 1 is C3-Cio-alkyl, in particular Cs-Cs-alkyl, which is optionally substituted by one, two or three R a .
  • R a is preferably selected from the group consisting of halogen, cyano, d-C ⁇ -alkyl, C2-C6- alkenyl, C2-C6-alkynyl, Ci-C ⁇ -alkoxycarbonyl, Ci-C ⁇ -alkoximino, C2-C6-alkenyloximino, C2-C6-alkynyloximino, Cs-C ⁇ -cycloalkyl and Cs-C ⁇ -cycloalkenyl, where the aliphatic and/or alicyclic groups for their part may be substituted by one, two or three groups R b .
  • R b is preferably independently halogen, cyano, d-C ⁇ -alkyl, C2-C6- alkenyl, C2-C6-alkynyl, Ci-C ⁇ -alkoxy, Ci-C ⁇ -alkylcarbonyl or Ci-C ⁇ -haloalkylcarbonyl.
  • R 1 is Ci-Cio-haloalkyl, in particular Cs-Cs-haloalkyl.
  • R 1 is C2-Cio-alkenyl, in particular C3- Cs-alkenyl, which is optionally substituted by one, two or three R a , as defined herein.
  • the alkenyl group is substituted by one, two or three halogen atoms.
  • R 1 is C2-Cio-alkynyl, in particular Cs-Cs-alkynyl, which is optionally substituted by one, two or three R a , as defined herein.
  • the alkynyl group is substituted by one, two or three halogen atoms.
  • R 1 is Cs-Cs-cycloalkyl, in particular C5-C7-cycloalkyl, especially C5- or C ⁇ -cycloalkyl, wherein the cycloalkyl groups are optionally substituted by one, two or three R a , as defined herein.
  • the cycloalkyl is mono-, di- or trisubstituted by Ci-C4-alkyl, such as, for example, methyl and/or ethyl.
  • the cycloalkyl is mono-, di- or trisubstituted by halogen.
  • R 1 is C3-Cio-alkyl, Ci-
  • Y 1 is C k R', C(O)O, C(O)NR 1 , oxygen, sulfur, NR 1 , SO or SO 2 ;
  • Y 2 is d-Cs-alkylene, C2-Cs-alkenylene or C2-C8-alkynylene, where Y 2 may be interrupted by one, two, three or four heteroatoms from the group consisting of NR A , oxygen, sulfur, SO and SO2;
  • T 1 is oxygen or NR 1 ;
  • T 2 is oxygen, sulfur or NR 1 ;
  • T 3 is R 1 , OR 1 , SR 1 or NR k R'; each R 1 and R k is independently hydrogen, C-i-Cs-alkyl, Cs-Cs-alkenyl, Cs-Cs-alkynyl, C3-C6-cycloalkyl or Cs-C ⁇ -cycloalkenyl, wherein the last five radicals are unsubstituted or are partially or fully halogenated and/or may carry one, two or three groups R m or three groups R m as defined herein.
  • P 1 is -Y 1 -Y 2 -T, wherein Y 1 is C(O)O, C(O)NR 1 , oxygen, NR 1 ;
  • Y 2 is d-Cs-alkylene, C2-C8-alkenylene or C2-C8-alkynylene, where Y 2 may be interrupted by one, two, three or four heteroatoms from the group consisting of NR A , oxygen;
  • T 2 is oxygen or NR 1 ;
  • T 3 is R 1 , OR 1 , or NR k R'; each R 1 and R k is independently hydrogen, Ci-Cs-alkyl, Cs-C ⁇ -cycloalkyl or C3-C6- cycloalkenyl wherein the last three radicals are unsubstituted or are partially or fully halogenated and/or may carry one, two or three groups R m or three groups R m as defined herein.
  • Y 1 is C(O)O. According to another embodiment of the invention, Y 1 is C(O)NR 1 .
  • Y 2 is Ci-C4-alkylene or C2-C6- alkenylene. According to another embodiment of the invention, Y 2 is interrupted by oxygen.
  • T is OR 1 , NR k R ⁇ C(O)OR 1 or C(O)NR k R 1 , in particular OR 1 or NR k R'.
  • R 1 and R k are thereby independently selected from hydrogen, Ci-C ⁇ -alkyl, C-i-C ⁇ -haloalkyl, C3-C6- cycloalkyl and Cs-C ⁇ -halocycloalkyl.
  • R 2 is halogen, in particular Cl or F.
  • R 2 is cyano
  • R 2 is C2-C3-alkyl, in particular ethyl, n-propyl or isopropyl.
  • R 2 is Ci-C4-haloalkyl, such as, for example, fluoromethyl, chloromethyl, bromomethyl, difluoromethyl, dichloromethyl, trifluoromethyl, trichloromethyl, chlorofluoromethyl, dichlorofluoromethyl or chlorodifluoromethyl, in particular trifluoromethyl.
  • R 3 is a cyano group.
  • R 3 is a five-membered saturated heterocycle, which contains one, two or three heteroatoms from the group consisting of O, N and S.
  • R 3 is tetrahydrofuran, pyrrolidine, pyrrolidinone, sulfolane, thiazolidine, oxathiolane, dithiolane, dioxolane or oxazolidine.
  • R 3 is pyrrolidinone, in particular 1-pyrrolidin-2-one.
  • R 3 is a six-membered saturated heterocycle, which contains one, two or three heteroatoms from the group consisting of O, N and S.
  • R 3 is piperidine, tetrahydropyran, dioxane, morpholine or triazinone.
  • R 3 is piperidine, morpholine or triazinone, in particular piperidine or morpholine.
  • R 3 is piperazine.
  • R 3 is optionally substituted 1-pyrrolidin-2-one.
  • R 3 is a five-membered partially unsaturated heterocycle which contains one, two or three heteroatoms from the group consisting of O, N and S. According to one specification of this embodiment, R 3 is 3,4-dihydro-2H-pyrrole or 2,3-dihydrofuran.
  • R 3 is a six-membered partially unsaturated heterocycle which contains one, two or three heteroatoms from the group consisting of O, N and S. According to one specification of this embodiment, R 3 is 1 ,2-dihydropyridine, 1 ,4- dihydropyridine, 2,3,4,5-tetrahydropyridine, 2H-pyran or 4H-pyran.
  • R 3 is a five-membered aromatic heterocycle which contains one, two, three or four heteroatoms from the group consisting of O, N and S, with the proviso that the heterocycle is not pyrazol-1-yl.
  • R 3 is not pyrazolyl.
  • R 3 is a five-membered aromatic heterocycle selected from furan, pyrrole, thiophene, imidazole, oxazole, thiazole, isoxazole, isothiazole, triazole, oxadiazole, thiadiazole, thiatriazole and tetrazole.
  • R 3 is selected from thiophene, imidazole, oxazole, thiazole, isoxazole, isothiazole, triazole, oxadiazole, thiadiazole, thiatriazole and tetrazole.
  • R 3 is selected from thiophene, imidazole, thiazole, triazole and tetrazole, in particular 2- thiazolyl, 1-[1 ,2,3]-triazolyl, 2-[1 ,2,3]-triazolyl, 1-[1 ,2,4]-triazolyl and 4-[1 ,2,4]-triazolyl.
  • R 3 is a six-membered aromatic heterocycle which contains one, two, three or four heteroatoms from the group consisting of O, N and S. According to one embodiment, said six-membered heterocycle is not pyridin-2-yl. According to another embodiment, said six-membered heterocycle is not pyridinyl. According to still another embodiment, said six-membered heterocycle is pyridinyl, in particular pyridin-2-yl. According to another embodiment of the invention, R 3 is selected from pyrimidine, pyrazine, pyridazine, triazine and tetrazine.
  • the aromatic heterocycle is preferably selected from pyrimidine, pyrazine, pyridazine and triazine.
  • R 3 is selected from pyrazine and pyrimidine.
  • R 3 is selected from 4-pyrimidyl, 5-pyrimidyl, pyrazine, 3- pyridazinyl and 4-pyridazinyl.
  • R 3 is morpholinyl, piperazinyl, 1 ,2,4-triazolyl, tetrazolyl, imidazolyl, thiazolyl, oxazolyl, isoxazolyl, oxadiazolyl, pyrazinyl, pyrimidinyl or pyrrolidonyl.
  • R 3 is a heterocycle as defined above which carries at least one substituent, wherein this at least one substituent is ortho to the attachment site to the pyrimidine ring of compound I.
  • R e ,R9,R y are independently hydrogen, d-C ⁇ -alkyl or Cs-C ⁇ -cycloalkyl, more specifically hydrogen, Ci-C4-alkyl or Cs-C ⁇ -cycloalkyl, in particular may be preferred that R e ,R9,R y are independently selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, cyclopentyl and cyclohexyl. According to one specific example of this embodiment, R e ,R9,R y are independently selected from hydrogen and methyl.
  • R 3 is a group
  • R 3 is a group
  • R 3 is a group
  • Y 3 and Y 4 are independently CH-R e , C(R f )-R e , N- NH-R e or N-R e and R x is independently defined like R d .
  • each of the heterocycles for R 3 listed herein may be unsubstituted or may be independently substituted by one, two, three or four, more specifically one, two or three R d as defined herein.
  • R d is/are independently selected from halogen, cyano, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, Oxo
  • R d is/are independently selected from halogen, C-i-C ⁇ - alkyl, C-i-C ⁇ -haloalkyl, cyano, hydroxy, d-C ⁇ -alkoxy, Ci-C6-haloalkoxy, C 2 -C 8 - alkenyloxy, C 2 -C 8 -alkynyloxy, Cs-C ⁇ -cycloalkyloxy, C4-C6-cycloalkenyloxy, N(A)A, CO 2 H, CO 2 A and CON(A)A.
  • R d is/are independently selected from halogen, C-i-C ⁇ -alkyl, C-i-C ⁇ -haloalkyl, cyano, C-i-C ⁇ -alkoxy, d-C ⁇ -haloalkoxy, C 2 - C 8 -alkenyloxy, C 2 -C 8 -alkynyloxy, Cs-C ⁇ -cycloalkyloxy, C4-C6-cycloalkenyloxy, CO 2 A and CON(A)A.
  • R d is/are independently selected from fluoro, chloro, methyl, trifluoromethyl, cyano, methoxy, CO 2 CHs, CO 2 CH 2 CHs, CONH 2 , CONHCH 3 and CON(CHs) 2 .
  • R 4 according to a preferred embodiment of the present invention is Cs-C ⁇ -alkyl, C-i-C ⁇ - haloalkyl, C4-C7-cycloalkyl or C4-C7-cycloalkenyl. Also preferred are compounds, wherein R 4 is Cs-C ⁇ -alkyl, C-i-C ⁇ -haloalkyl, Cs-Cz-cycloalkyl or Cs-Cz-cycloalkenyl. Also preferred are compounds, wherein R 4 is Cs-C ⁇ -alkyl, Cs-C ⁇ -haloalkyl or C3-C6- cycloalkyl.
  • R 4 is ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, cyclopentyl, cyclohexyl, cyclopententyl or cyclohexenyl.
  • R 4 is isopropyl, tert-butyl or cyclopentyl.
  • R 4 contains as substituents at least one substituent P 1 or preferred embodiment of P 1 as defined above.
  • particularly preferred compounds are the compounds I compiled in the tables below.
  • the groups mentioned in the tables for a substituent are furthermore per se, independently of the combination in which they are mentioned, a particularly preferred embodiment of the substituent in question.
  • Table 1 is a particularly preferred embodiment of the substituent in question.
  • R 2 for a particular compound correspond in each case to one row of table A
  • R 2 for a particular compound correspond in each case to one row of table A
  • R 1 and R 2 for a particular compound correspond in each case to one row of table A
  • R 1 and R 2 for a particular compound correspond in each case to one row of table A
  • R 2 for a particular compound correspond in each case to one row of table A
  • R 2 for a particular compound correspond in each case to one row of table A
  • R 1 and R 2 for a particular compound correspond in each case to one row of table A Table 87
  • R 2 for a particular compound correspond in each case to one row of table A
  • the compounds I are suitable as fungicides. They are distinguished by an excellent activity against a broad spectrum of phytopathogenic fungi from the class of the Ascomycetes, Deuteromycetes, Oomycetes and Basidiomycetes, in particular from the class of the Oomycetes. Some of them are systemically effective and can be used in crop protection as foliar fungicides, as fungicides for seed dressing and as soil fungicides.
  • Drechslera species Pyrenophora species on corn, cereals, rice and lawns, such as, for example, D. teres on barley or D. tritici-repentis on wheat; • Esca on grapevines, caused by Phaeoacremonium chlamydosporium,
  • Mycosphaerella species on cereals, bananas and groundnuts such as, for example, M. graminicola on wheat or M.fijiensis on bananas;
  • Peronospora species on cabbage and bulbous plants such as, for example, P. brassicae on cabbage or P. destructor on onion;
  • Puccinia species on various plants such as, for example, P. triticina,
  • Rhizoctonia species on cotton, rice, potatoes, lawns, corn, oilseed rape, potatoes, sugar beet, vegetables and on various plants such as, for example,
  • Venturia species (scab) on apples and pears such as, for example, V. inaequalis on apple.
  • Peronosporomycetes such as Peronospora species, Phytophthora species, Plasmopara viticola , Pseudoperonospora species and Pythium species.
  • the compounds I are also suitable for controlling harmful fungi in the protection of materials (for example wood, paper, paint dispersions, fibers or fabrics) and in the protection of stored products.
  • harmful fungi Ascomycetes, such as Ophiostoma spp., Ceratocystis spp., Aureobasidium pullulans, Sclerophoma spp., Chaetomium spp., Humicola spp., Petriella spp., Trichurus spp.; Basidiomycetes, such as Coniophora spp., Coriolus spp., Gloeophyllum spp., Lentinus spp., Pleurotus spp., Poria spp., Serpula spp.
  • Tyromyces spp. Deuteromycetes, such as Aspergillus spp., Cladosporium spp., Penicillium spp., Trichoderma spp., Alternaria spp., Paecilomyces spp. and Zygomycetes, such as Mucor spp., additionally in the protection of materials the following yeasts: Candida spp. and Saccharomyces cerevisae.
  • the compounds I are employed by treating the fungi or the plants, seeds or materials to be protected against fungal attack or the soil with a fungicidally effective amount of the active compounds.
  • Application can be both before and after the infection of the materials, plants or seeds by the fungi.
  • the fungicidal compositions generally comprise between 0.1 and 95% by weight, preferably between 0.5 and 90% by weight, of active compound.
  • the application rates are, depending on the kind of effect desired, between 0.01 and 2.0 kg of active compound per ha.
  • the amounts of active compound required are generally from 1 to 1000 g/100 kg of seed, preferably from 5 to 100 g/100 kg of seed.
  • the active compound application rates depend on the kind of application area and on the desired effect. Amounts typically applied in the protection of materials are, for example, from 0.001 g to 2 kg, preferably from 0.005 g to 1 kg, of active compound per cubic meter of treated material.
  • the compounds of the formula I can be present in different crystal modifications which may differ in their biological activity. They are likewise subject matter of the present invention.
  • the compounds I can be converted into the customary formulations, for example solutions, emulsions, suspensions, dusts, powders, pastes and granules.
  • the application form depends on the particular purpose; in each case, it should ensure a fine and uniform distribution of the compound according to the invention.
  • the formulations are prepared in a known manner, for example by extending the active compound with solvents and/or carriers, if desired using emulsifiers and dispersants.
  • Solvents/auxiliaries suitable for this purpose are essentially: water, aromatic solvents (for example Solvesso products, xylene), paraffins (for example mineral oil fractions), alcohols (for example methanol, butanol, pentanol, benzyl alcohol), ketones (for example cyclohexanone, gamma-butyrolactone), pyrrolidones (NMP, NOP), acetates (glycol diacetate), glycols, fatty acid dimethylamides, fatty acids and fatty acid esters.
  • aromatic solvents for example Solvesso products, xylene
  • paraffins for example mineral oil fractions
  • alcohols for example methanol, butanol, pentanol, benzyl alcohol
  • ketones for example cyclohexanone
  • solvent mixtures may also be used, carriers such as ground natural minerals (for example kaolins, clays, talc, chalk) and ground synthetic minerals (for example finely divided silica, silicates); emulsifiers such as nonionogenic and anionic emulsifiers (for example polyoxyethylene fatty alcohol ethers, alkylsulfonates and arylsulfonates) and dispersants such as lignosulfite waste liquors and methylcellulose.
  • ground natural minerals for example kaolins, clays, talc, chalk
  • ground synthetic minerals for example finely divided silica, silicates
  • emulsifiers such as nonionogenic and anionic emulsifiers (for example polyoxyethylene fatty alcohol ethers, alkylsulfonates and arylsulfonates) and dispersants such as lignosulfite waste liquors and methylcellulose.
  • Suitable for use as surfactants are alkali metal, alkaline earth metal and ammonium salts of lignosulfonic acid, naphthalenesulfonic acid, phenolsulfonic acid, dibutylnaphthalenesulfonic acid, alkylarylsulfonates, alkyl sulfates, alkylsulfonates, fatty alcohol sulfates, fatty acids and sulfated fatty alcohol glycol ethers, furthermore condensates of sulfonated naphthalene and naphthalene derivatives with formaldehyde, condensates of naphthalene or of naphthalenesulfonic acid with phenol and formaldehyde, polyoxyethylene octylphenyl ether, ethoxylated isooctylphenol, octylphenol, nonylphenol, alkylphenyl polyglycol ethers, tributy
  • mineral oil fractions of medium to high boiling point such as kerosene or diesel oil, furthermore coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, for example toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, methanol, ethanol, propanol, butanol, cyclohexanol, cyclohexanone, isophorone, strongly polar solvents, for example dimethyl sulfoxide, N-methylpyrrolidone and water.
  • mineral oil fractions of medium to high boiling point such as kerosene or diesel oil, furthermore coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, for example toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, m
  • Powders, materials for spreading and dustable products can be prepared by mixing or concomitantly grinding the active substances with a solid carrier.
  • Granules for example coated granules, impregnated granules and homogeneous granules, can be prepared by binding the active compounds to solid carriers.
  • solid carriers are mineral earths such as silica gels, silicates, talc, kaolin, attaclay, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground synthetic materials, fertilizers, such as, for example, ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas, and products of vegetable origin, such as cereal meal, tree bark meal, wood meal and nutshell meal, cellulose powders and other solid carriers.
  • mineral earths such as silica gels, silicates, talc, kaolin, attaclay, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth
  • the formulations comprise from 0.01 to 95% by weight, preferably from 0.1 to 90% by weight, of the active compound.
  • the active compounds are employed in a purity of from 90% to 100%, preferably 95% to 100% (according to NMR spectrum).
  • a Water-soluble concentrates (SL, LS)
  • the active compounds 20 parts by weight of the active compounds are dissolved in 70 parts by weight of cyclohexanone with addition of 10 parts by weight of a dispersant, for example polyvinylpyrrolidone. Dilution with water gives a dispersion.
  • the active compound content is 20% by weight.
  • the active compounds 15 parts by weight of the active compounds are dissolved in 75 parts by weight of xylene with addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5 parts by weight). Dilution with water gives an emulsion.
  • the formulation has an active compound content of 15% by weight.
  • the active compounds 25 parts by weight of the active compounds are dissolved in 35 parts by weight of xylene with addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5 parts by weight).
  • This mixture is added to 30 parts by weight of water by means of an emulsifying machine (e.g. Ultraturrax) and made into a homogeneous emulsion. Dilution with water gives an emulsion.
  • the formulation has an active compound content of 25% by weight.
  • E Suspensions SC, OD, FS
  • 20 parts by weight of the active compounds are comminuted with addition of 10 parts by weight of dispersants and wetters and 70 parts by weight of water or an organic solvent to give a fine active compound suspension.
  • Dilution with water gives a stable suspension of the active compound.
  • the active compound content in the formulation is 20% by weight.
  • Water-dispersible granules and water-soluble granules 50 parts by weight of the active compounds are ground finely with addition of 50 parts by weight of dispersants and wetters and made into water-dispersible or water-soluble granules by means of technical appliances (for example extrusion, spray tower, fluidized bed). Dilution with water gives a stable dispersion or solution of the active compound.
  • the formulation has an active compound content of 50% by weight.
  • Water-dispersible powders and water-soluble powders 75 parts by weight of the active compounds are ground in a rotor-stator mill with addition of 25 parts by weight of dispersants, wetters and silica gel. Dilution with water gives a stable dispersion or solution of the active compound.
  • the active compound content of the formulation is 75% by weight.
  • 0.5 part by weight of the active compounds is ground finely and associated with 99.5 parts by weight of carriers.
  • Current methods are extrusion, spray-drying or the fluidized bed. This gives granules with an active compound content of 0.5% by weight to be applied undiluted.
  • LS Water-soluble concentrates
  • FS suspensions
  • DS dusts
  • WS water-dispersible and water-soluble powders
  • ES emulsions
  • EC emulsifiable concentrates
  • gel formulations GF
  • the active compounds can be used as such, in the form of their formulations or the use forms prepared therefrom, for example in the form of directly sprayable solutions, powders, suspensions or dispersions, emulsions, oil dispersions, pastes, dustable products, materials for spreading, or granules, by means of spraying, atomizing, dusting, spreading or pouring.
  • the use forms depend entirely on the intended purposes; the intention is to ensure in each case the finest possible distribution of the active compounds according to the invention.
  • Aqueous use forms can be prepared from emulsion concentrates, pastes or wettable powders (sprayable powders, oil dispersions) by adding water.
  • the substances as such or dissolved in an oil or solvent, can be homogenized in water by means of a wetter, tackifier, dispersant or emulsifier.
  • concentrates composed of active substance, wetter, tackifier, dispersant or emulsifier and, if appropriate, solvent or oil, and such concentrates are suitable for dilution with water.
  • the active compound concentrations in the ready-to-use preparations can be varied within relatively wide ranges. In general, they are from 0.0001 to 10%, preferably from 0.01 to 1 %.
  • the active compounds may also be used successfully in the ultra-low-volume process (ULV), by which it is possible to apply formulations comprising over 95% by weight of active compound, or even to apply the active compound without additives.
  • UUV ultra-low-volume process
  • compositions can be admixed with the compositions according to the invention in a weight ratio of from 1 :100 to 100:1 , preferably from 1 :10 to 10:1.
  • organically modified polysiloxanes for example Break Thru S 240 ®
  • alcohol alkoxylates for example Atplus 245 ® , Atplus MBA 1303 ®
  • Plurafac LF 300 ® and Lutensol ON 30 ® EO-PO block polymers
  • Pluronic RPE 2035 ® and Genapol B ® alcohol ethoxylates
  • Lutensol XP 80 ® sodium dioctylsulfosuccinate
  • Leophen RA ® sodium dioctylsulfosuccinate
  • compositions according to the invention in the application form as fungicides can also be present together with other active compounds, for example with herbicides, insecticides, growth regulators, fungicides or else with fertilizers.
  • active compounds for example with herbicides, insecticides, growth regulators, fungicides or else with fertilizers.
  • the present invention furthermore provides a combination of at least one azolylmethyloxirane of the formula I, in particular an azolylmethyloxirane disclosed in the present description as being preferred, and/or an agriculturally acceptable salt thereof and at least one further fungicidal, insecticidal, herbicidal and/or growth- regulating active compound, it being possible for a synergistic effect to occur.
  • the present invention also provides a pesticidal composition which comprises at least one compound of the formula I, in particular a compound of the formula I described in the present description as being preferred, and/or an agriculturally acceptable acid addition salt or metal salt thereof and at least one solid or liquid carrier.
  • a pesticidal composition may comprise at least one further fungicidally, insecticidally and/or herbicidally active compound, it also being possible for a synergistic effect to occur.
  • List L strobilurins azoxystrobin, dimoxystrobin, enestroburin, fluoxastrobin, kresoxim-methyl, methominostrobin, orysastrobin, picoxystrobin, pyraclostrobin, pyribencarb, trifloxystrobin, 2-(2-(6-(3-chloro-2-methylphenoxy)-5-fluoropyrimidin-4-yloxy)phenyl)-2- methoxyimino-N-methylacetamide, methyl 2-(ortho-((2,5-dimethylphenyl- oxymethylene)phenyl)-3-methoxyacrylate, methyl 3-methoxy-2-(2-(N-(4-methoxy- phenyl)cyclopropanecarboximidoylsulfanylmethyl)phenyl)acrylate;
  • carpropamid carpropamid, diclocymet, mandipropamid, oxytetracyclin, silthiofam, N-(6-methoxypyridin-3-yl)cyclopropanecarboxamide;
  • azoles - triazoles azaconazole, bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole, diniconazole-M, epoxiconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imibenconazole, ipconazole, metconazole, myclobutanil, oxpoconazole, paclobutrazole, penconazole, propiconazole, prothioconazole, simeconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triticonazole, uniconazole, 1-(4-chlorophenyl)-2-([1 ,2,4]triazol-1-yl)- cycloheptanol; - imidazoles
  • - pyridines fluazinam, pyrifenox, 3-[5-(4-chlorophenyl)-2,3-dimethylisoxazolidin-3-yl]- pyridine, 2,3,5,6-tetrachloro-4-methanesulfonylpyridine, 3,4,5-trichloropyridine-2,6- dicarbonitrile, N-(1-(5-bromo-3-chloropyridin-2-yl)ethyl)-2,4-dichloronicotinamide, N-((5-bromo-3-chloropyridin-2-yl)methyl)-2,4-dichloronicotinamide;
  • - pyrimidines bupirimate, cyprodinil, diflumetorim, fenarimol, ferimzone, mepanipyrim, nitrapyrin, nuarimol, pyrimethanil;
  • dicarboximides fluoroimide, iprodione, procymidone, vinclozolin;
  • acibenzolar-S-methyl acibenzolar-S-methyl, amisulbrom, anilazine, blasticidin-S, captafol, captan, quinomethionate, dazomet, debacarb, diclomezine, difenzoquat, difenzoquat-methyl sulfate, famoxadone, fenamidone, fenoxanil, fenpropidin, folpet, octhilinone, oxolinic acid, piperalin, probenazole, proquinazid, pyroquilon, quinoxyfen, triazoxide, tricyclazole, triforine, 5-chloro-7-(4-methylpiperidin-1 -yl)-6-(2,4,6-trifluorophenyl)- [1 ,2,4]triazolo[1 ,5-a]pyrimidine, 2-butoxy-6-iodo-3-prop
  • carbamates and dithiocarbamates - thio- and dithiocarbamates ferbam, mancozeb, maneb, metam, methasulfocarb, metiram, propineb, thiram, zineb, ziram;
  • guanidines dodine, dodine-free base, guazatine, guazatine-acetate, iminoctadine, iminoctadine-triacetate, iminoctadine-tris(albesilate);
  • antibiotics kasugamycin, kasugamycin-hydrochloride-hydrate, polyoxins, streptomycin, validamycin A;
  • - nitrophenyl derivatives binapacryl, dicloran, dinobuton, dinocap, nitrothal-isopropyl, tecnazen; - organometallic compounds: fentin salts such as, for example, fentin-acetate, fentin- chloride, fentin-hydroxide;
  • organophosphorus compounds edifenphos, fosetyl, fosetyl-aluminum, iprobenfos, pyrazophos, tolclofos-methyl;
  • organochlorine compounds chlorothalonil, dichlofluanid, dichlorophen, flusulfamide, hexachlorobenzene, pencycuron, pentachlorophenol and salts thereof, phthalide, quintozene, thiophanate-methyl, tolylfluanid, N-(4-chloro-2-nitrophenyl)-N-ethyl-4- methylbenzenesulfonamide;
  • - inorganic active compounds phosphorous acid and salts thereof, sulfur, Bordeaux mixture, copper salts such as, for example, copper acetate, copper hydroxide, copper oxychloride, basic copper sulfate;
  • each line of table B corresponding to a fungicidal composition
  • a compound of the formula I component 1
  • component 1 in each line of table B is in each case one of the compounds of the formula I that are specifically individualized in tables 1 to 90.
  • the active compounds Il specified above as component 2 are widely known (cf.: http://www.hclrss.demon.co.uk/index.html); they are available commercially.
  • the compounds with IUPAC nomenclature, their preparation, and their fungicidal activity are likewise known [cf. EP-A 226 917; EP-A 10 28 125; EP-A 10 35 122; EP-A 12 01 648; WO 98/46608; WO 99/24413; WO 03/14103; WO 03/053145; WO 03/066609; WO 04/049804].
  • the present invention furthermore relates to the pharmaceutical use of the compounds according to the invention, in particular the compounds according to the invention described as being preferred, and/or the pharmaceutically acceptable salts thereof, in particular their use for the treatment of tumors in mammals, such as, for example, in humans.
  • Step 1 Synthesis of 2-methylthio-4,6-dihydroxy-5-isopropyl-pyrimidine
  • Step 3 Synthesis of 2-methylthio-4-chloro-6-(4-methyl-piperidin-1-yl)-5-isopropyl- pyrimidine
  • step 2 To the dichloride of step 2 (12.0 g, 50 mmol) in THF (100 ml) was successively added triethylamine (13.4 ml, 1000 mmol), followed by 4-methylpiperidine (9.5 ml, 100 mmol) and the mixture was stirred at ambient temperature overnight. The solvent was removed under reduced pressure and the residue was dissolved in CH2CI2 (250 ml). The latter solution was washed with water (2x100 ml), dried over Na2SO4 and concentrated in vacuo to furnish the desired compound (13.8 g, 40 mmol, 91 %) as off- white solid.
  • Step 4 Synthesis of 2-methylsulfonyl-4-chloro-6-(4-methylpiperidin-1-yl)-5- isopropyl-pyrimidine
  • step 3 To a solution of the compound of step 3 (10.0 g, 30 mmol) in CH 2 CI 2 (100 ml) at -10 0 C under an inert atmosphere was added portion wise m-CPBA (15.6 g, 60 mmol) over a period of 30 min. A precipitate soon formed and stirring was continued overnight. Sat. Na 2 S 2 O 3 (3 ml) was added and the volatiles were removed in vacuo, before adding
  • Step 5 Synthesis of 2-cyano-4-chloro-6-(4-methylpiperidin-1-yl)-5-isopropyl- pyrimidine (compound No. 3)
  • O-methylhydroxylamine hydrochloride (92 mg, 1.08 mmol) was added and stirring was continued overnight. The solvent was removed in vacuo and the residue was dissolved in MTBE (10 ml). The latter was washed with water (2x5 ml) and dried over Na 2 SO 4 .
  • Step 1 Synthesis of 5-lsopropyl-2-methyl-pyrimidine-4,6-diol To a solution of thiourea (9.3 g, 121 mmol) in MeOH (100 mL) was slowly added NaOMe (21.8 g, 121 mmol) and the mixture was stirred for 10 min. Subsequently, a solution of diethyl isopropylmalonate (25.0 g, 121 mmol) in MeOH (100 mL) was added drop wise and stirring continued overnight. Additional NaOMe (43.6 g, 242 mmol) was added and the reaction mixture was heated at reflux for about 6 h. Upon cooling down to room temperature, iodomethane was added and stirring was continued overnight.
  • Step 3 Synthesis of 4-Chloro-5-isopropyl-6-(4-methyl-piperidin-1-yl)-2-methyl- sulfanyl-pyrimidine
  • step 2 To the dichloride of step 2 (12.0 g, 50 mmol) in THF (100 mL) was successively added triethylamine (13.4 mL, 1000 mmol), followed by 4-methylpiperidine (9.5 mL, 100 mmol) and the mixture was stirred at ambient temperature overnight. The solvent was removed under reduced pressure and the residue was dissolved in CH2CI2 (250 mL).
  • Step 4 Synthesis of 4-Chloro-5-isopropyl-2-methanesulfonyl-6-(4-methyl-piperidin- 1-yl)-pyrimidine
  • Step 5 Synthesis of 4-Chloro-5-isopropyl-6-(4-methyl-piperidin-1-yl)-pyrimidine-2- carbonitrile
  • the aqueous phase was extracted with MTBE (2 x 10 ml_), the organic phase was dried over Na2SO4 and the solvent was removed under reduced pressure.
  • the crude yellow oil was purified using flash chromatography (silica, cyclohexane: EtOAc, 70: 30 followed by 50: 50 followed by 0: 100) to yield the desired product (1 10 mg, 0.32 mmol,
  • the aqueous phase was extracted with MTBE (2 x 10 ml_), the organic phase was dried over Na2SO4 and the solvent was removed under reduced pressure.
  • the crude yellow oil was purified using flash chromatography (silica, cyclohexane: EtOAc, 70:30 followed by 50:50 followed by 0:100) to yield the desired product (150 mg, 0.44 mmol, 40%) as a colourless oil.
  • DMSO dimethyl sulfoxide
  • the stock solution was pipetted into a microtiter plate (MTP) and diluted to the stated active substance concentration using a malt-based aqueous nutrient medium for fungi.
  • An aqueous spore suspension of Pyricularia oryzae was then added.
  • the plates were placed in a water vapor-saturated chamber at temperatures of 18°C.
  • the stock solution was pipetted into a microtiter plate (MTP) and diluted to the stated active substance concentration using a malt-based aqueous nutrient medium for fungi. An aqueous spore suspension of Septoria tritici was then added.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Dentistry (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
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  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
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  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
  • Plural Heterocyclic Compounds (AREA)

Abstract

La présente invention concerne des composés de pyrimidine de formule (I) dans laquelle les substituants sont tels que définis dans les revendications et la description, et elle concerne également l'utilisation desdits composés pour contrôler des champignons phytopathogènes.
PCT/EP2008/058794 2007-08-09 2008-07-07 Dérivés de pyrimidine tétrasubstitués permettant de contrôler des champignons phytopathogènes WO2009019099A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8389718B2 (en) 2010-07-20 2013-03-05 Vestaron Corporation Insecticidal triazines and pyrimidines
JP2022504352A (ja) * 2018-10-10 2022-01-13 ジエンス ハンセン ファーマセウティカル グループ カンパニー リミテッド 窒素を含有するヘテロ芳香族誘導体の制御因子、その製造方法及び使用

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Publication number Priority date Publication date Assignee Title
DE1545660A1 (de) * 1964-03-25 1969-08-07 Ciba Geigy Neue Halogenpyrimidine
EP0407899A2 (fr) * 1989-07-11 1991-01-16 Hoechst Schering AgrEvo GmbH Dérivés d'aminopyromidine, leur procédé de préparation, agent les contenant et leur utilisation comme fongicides
WO2005019207A1 (fr) * 2003-08-15 2005-03-03 Nippon Soda Co. Ltd. Derives de pyrimidine fongicides
WO2005079798A1 (fr) * 2004-02-19 2005-09-01 Bayer Cropscience Ag Derives de pyrimidine et utilisation de ceux-ci comme fongicides agricoles et horticoles
WO2006029867A1 (fr) * 2004-09-16 2006-03-23 Bayer Cropscience Aktiengesellschaft 5-heterocyclyl-pyrimidines
DE102005046592A1 (de) * 2005-09-28 2007-03-29 Basf Ag 2-Substituierte Hydroxylaminopyrimidine, Verfahren zu ihrer Herstellung und ihre Verwendung als Pestizid
WO2007083692A1 (fr) * 2006-01-23 2007-07-26 Kumiai Chemical Industry Co., Ltd. Derive d’aminopyridine et agent de lutte contre une maladie de plantes destine a un usage agricole ou horticole

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1545660A1 (de) * 1964-03-25 1969-08-07 Ciba Geigy Neue Halogenpyrimidine
EP0407899A2 (fr) * 1989-07-11 1991-01-16 Hoechst Schering AgrEvo GmbH Dérivés d'aminopyromidine, leur procédé de préparation, agent les contenant et leur utilisation comme fongicides
WO2005019207A1 (fr) * 2003-08-15 2005-03-03 Nippon Soda Co. Ltd. Derives de pyrimidine fongicides
WO2005079798A1 (fr) * 2004-02-19 2005-09-01 Bayer Cropscience Ag Derives de pyrimidine et utilisation de ceux-ci comme fongicides agricoles et horticoles
WO2006029867A1 (fr) * 2004-09-16 2006-03-23 Bayer Cropscience Aktiengesellschaft 5-heterocyclyl-pyrimidines
DE102005046592A1 (de) * 2005-09-28 2007-03-29 Basf Ag 2-Substituierte Hydroxylaminopyrimidine, Verfahren zu ihrer Herstellung und ihre Verwendung als Pestizid
WO2007083692A1 (fr) * 2006-01-23 2007-07-26 Kumiai Chemical Industry Co., Ltd. Derive d’aminopyridine et agent de lutte contre une maladie de plantes destine a un usage agricole ou horticole

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8389718B2 (en) 2010-07-20 2013-03-05 Vestaron Corporation Insecticidal triazines and pyrimidines
US8785630B2 (en) 2010-07-20 2014-07-22 Vestaron Corporation Insecticidal triazines and pyrimidines
JP2022504352A (ja) * 2018-10-10 2022-01-13 ジエンス ハンセン ファーマセウティカル グループ カンパニー リミテッド 窒素を含有するヘテロ芳香族誘導体の制御因子、その製造方法及び使用
EP3868742A4 (fr) * 2018-10-10 2022-11-23 Jiangsu Hansoh Pharmaceutical Group Co., Ltd. Régulateur de dérivés hétéroaromatiques contenant de l'azote, procédé de préparation associé et utilisation correspondante

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