Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
  • C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more hetero rings
• • 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
  • C07D403/14—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 three or more hetero rings

Definitions

• the present invention relates to novel 5-heterocyclyl-pyrimidines, and to processes for their preparation and their use for controlling unwanted microorganisms.
• the invention also relates to novel intermediates and to processes for their preparation.
• R 1 is hydrogen, C 1 -C 8 -alkyl, C 2 -C 8 -alkenyl, C 3 -C 8 -alkynyl, C 3 -C 8 -cycloalkyl or C 3 -C 8 -cycloalkenyl, wherein R 1 is replaced by one to three identical or different groups R a may be substituted and
• R a is halogen, hydroxy, cyano, C 1 -C 4 -alkoxy and / or C 3 -C 6 -cycloalkyl, or
• R 1 is a five to ten membered saturated, unsaturated or aromatic mono- or bicyclic heterocycle containing one to four heteroatoms from the group O, N or S, wherein R 1 may be substituted by one to two identical or different groups R b , and
• R b Ci-C 6 alkyl, cyano, nitro, and / or C 3 -C 6 cycloalkyl halo;
• R 2 is hydrogen or C, -C 6 alkyl, or
• R 1 and R 2 together with the nitrogen atom to which they are attached, represent a three- to six-membered saturated, unsaturated or aromatic mono- or bicyclic
• Heterocycle is, wherein the heterocycle may contain another heteroatom from the group O, N or S and may be substituted by one to three identical or different groups R c , and
• R c is halogen, C r C 6 alkyl, and / or C, -C 6 -haloalkyl,
• R 3 is a three- to ten-membered saturated, partially unsaturated or aromatic mono- or bicyclic heterocycle containing one to four heteroatoms from the group O, N or S, where R 3 is substituted by one to four identical or different groups R d can, and
• R d is halogen, hydroxy, cyano, oxo, nitro, amino, mercapto, C r C 6 alkyl, C r C 6 - halogenoalkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 - C 6 cycloalkyl, C, -C 6 alkoxy, C 1 - C ö haloalkoxy, carboxyl, Ci-C 7 alkoxycarbonyl, carbamoyl, C1 -C7- alkylaminocarbonyl, Ci-C 6 alkyl-C 6 alkylamino carbonyl, morpholinocarbonyl,
• Pyrrolidinocarbonyl CPCV-alkylcarbonylamino, Ci-C 6 -alkylamino, di- (Ci-C 6 - alkyl) amino, C r C 6 alkylthio, C, -C 6 alkylsulfinyl, Ci-C 6 alkylsulfonyl, hydroxy sulfonyl , aminosulfonyl, Ci-C ö alkylaminosulfonyl, and / or di- (Ci-C 6 alkyl) - aminosulfonyl group;
• R 4 represents halogen or C r C 8 alkyl, C r C 8 alkoxy, C, -C 8 haloalkyl, C r C 8 alkylthio, C 1 -C 8 - alkylsulphinyl, C 8 alkylsulfonyl or cyano stands,
• R 5 is a five- or six-membered saturated, unsaturated or aromatic mono- or bicyclic heterocycle containing one to four heteroatoms from the group O, N or S, wherein R 5 may be substituted by one to four identical or different groups R e , and
• R e is halogen, hydroxy, cyano, nitro, C r C 6 alkyl, Ci-C 6 haloalkyl, C 2 -C 6 - alkenyl, C 2 -C 6 alkynyl, C 3 -C 6 cycloalkyl, C r C 6 alkoxy, C, -C 6 haloalkoxy, carboxyl, Ci-C 7 alkoxycarbonyl, carbamoyl, CPCV-alkylaminocarbonyl, CpC 6 - alkyl CpC 6 -alkylamincarbonyl, C r C 6 alkylthio, Ci-C 6 Alkylsulfinyl, C r C 6 - alkylsulfonyl, hydroxyimino-C 1 -C 6 -alkyl and / or C 1 -C 6 -alkyl alkoxyimino-C r
• the compounds of formula I have a good activity against undesirable microorganisms.
• Scheme 1 shows the synthesis of compounds I 'in which R 3 is an N-linked heterocycle.
• thiourea is obtained by cyclization with malonates of type XVII pyrimidines of type XVI (process I)) or by cyclization with acetoacetic esters of type X ⁇ i pyrimidines of type XI (process i)). Alkylation of the thio group gives compounds of the type XV (process k)) or of the type X (process h)). After halogenation to pyrimidines of the type IX (process j) or g)), a conversion to the amines of type II (process f)). Oxidation yields compounds of type III (process a)) and reaction with N-containing heterocycles finally gives the novel compounds of the formula P (process b)).
• the hydrazine compound XXI is condensed with a dicarbonyl compound XXII, where the substituents R 1 , R 2 , R 4 , R 5 , R 6 and R d have the abovementioned meaning and R 'is an alkyl, aryl or benzyl group (s. Scheme 3) and thus the compounds of formula XXIII.
• the dicarbonyl compounds of the formula XXII are known from Angew. Chem. Int. Ed. Engl. 1989, 28, p. 500. The condensation is carried out as described in DE 19627002 in more detail.
• R 4 halogen, C 1 -C 4 -alkyl or C 1 -C 4 -haloalkyl
• pyrimidines of the type F "according to the invention substituted in 6-position R 4 are obtained by reacting the halopyrimidines (I'a or I" a) with metal compounds of the type R 4 M 1 or Grignard compounds VIII (see Scheme 5).
• R 1 , R 2 and R 5 have the meanings given above, R 3 is an N-bonded heterocycle and R 4 is halogen, C] -C 4 alkyl or Ci-Q-haloalkyl, can be prepared by according to method a)
• R, R and R have the meanings given above, R 4 is halogen, C 1 -C 4 -alkyl or Cp C 4 haloalkyl, and R 6 6 alkyl for C r C, with an oxidizing agent optionally in the presence of a diluent oxidized
• R 1 , R 2 , R 5 and R 6 have the meanings given above, R 4 is halogen, C 1 -C 4 -alkyl
• n 1 or 2
• R 3 has the meanings given above with the proviso that R 3 must have at least one nitrogen atom, via which the connection to the pyrimidine ring in compounds of formula (V), optionally in the presence of a diluent and optionally in the presence of a base.
• R 1, R 2, and R 5 have the meanings given above
• R 3 4 -alkyl or Ci-C stands for a C- g over geebbuunnddeenneenn Heetteerrooccyycclluuss H and R 4 is halogen
• C] -C 4 haloalkyl can be made by according to process c) compounds of the formula (V),
• R 3 have the meanings given above with the proviso that R 3 is a heterocycle which is attached via a C atom to the pyrimidine ring in compounds of the type (V), and R 4 is halogen, C r C 4 alkyl or C is 4 haloalkyl,
• R 1 and R 2 have the meanings given above,
• R 1 , R 2 and R 5 have the meanings given above
• R ⁇ is a heterocycle bonded via N- or C- and R 4 is Ci-Cg-alkyl, Cj-Cg-alkoxy, Cj-Cg-alkylthio , C 1 "is C 8 alkylsulfonyl or cyano, can be prepared by reacting compounds of the formula (I'a) or (I" a)
• R 1 , R 2 , R 3 and R 5 have the meanings given above and Hal is halogen
• R 4 is Ci-C 8 alkoxy, Ci-Cg-alkylthio, Ci-Cg-alkylsulfinyl, Ci-Cg-alkylsulfonyl, or cyano, and
• Ml stands for sodium or potassium
• R 4 is C i -C 8 alkyl
• Hal is chlorine or bromine
• the 5-heterocyclylpyrimidines of the formula (I) are very suitable for controlling unwanted microorganisms. Above all, they show a strong fungicidal activity and can be used both in crop protection and in the protection of materials.
• the inventive 5-heterocyclyl-pyrimidineder of formula (I) have a much better microbicidal activity than the constitutionally similar, previously known substances same direction of action.
• the compounds of the formula (I) according to the invention can be used as mixtures of various possible isomeric forms, in particular stereoisomers, such as E and Z, threo and erythro, and optical isomers, such as R and S isomers or atropisomers, but if appropriate also of tautomers.
• Halogen fluorine, chlorine, bromine and iodine; Halogen is preferably chlorine or bromine, particularly preferably chlorine;
• Alkyl saturated, straight-chain or branched hydrocarbon radicals having 1 to 4, 6 or 8 carbon atoms, for example C 1 -C 6 -alkyl, such as methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methyl-propyl, 2-methylpropyl, 1 , 1-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl,
• Haloalkyl straight-chain or branched alkyl groups having 1 to 8 carbon atoms (as mentioned above), wherein in these groups partially or completely the hydrogen atoms may be replaced by halogen atoms as mentioned above, for example Ci-C ß -haloalkyl such as chloromethyl, bromomethyl, dichloromethyl, trichloromethyl , Fluoromethyl, difluoromethyl, 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-di-fluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl,
• Alkenyl unsaturated, straight-chain or branched hydrocarbon radicals having 2 to 4, 6 or 8 carbon atoms and a double bond in any position, for example C 2 -C 6 -alkenyl, such as ethenyl, 1-propenyl, 2-propenyl, 1-methylethenyl, 1 Butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-one 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-propen
• Alkynyl straight-chain or branched hydrocarbon groups having 2 to 4, 6 or 8 carbon atoms and a triple bond in any position, for example C 2 -C 6 -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 butinyl, 3-methyl-1-butynyl, 1, 1-dimethyl-2-propynyl, 1-ethyl-1-propynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, 1 Methyl 2-pentynyl
• Cycloalkyl monocyclic, saturated hydrocarbon groups having 3 to 8 carbon ring members, such as cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl;
• Cylcoalkenyl monocyclic, non-aromatic hydrocarbon groups having 3 to 8 carbon ring members having at least one double bond, such as cyclopenten-1-yl, cyclohexene-1-yl, cyclohepta-1,3-dien-1-yl;
• Alkoxycarbonyl an alkoxy group having 1 to 6 carbon atoms (as mentioned above), which is bonded to the skeleton via a carbonyl group (-CO-);
• Oxyalkylene oxide divalent unbranched chains of 1 to 3 CH 2 groups, both valences being bonded to the skeleton via an oxygen atom, eg OCH 2 O, OCH 2 CH 2 O and OCH 2 CH 2 CH 2 O;
• Hexahydropyrimidinyl 5-hexahydropyrimidinyl, 2-piperazinyl, 1, 3,5-hexahydro-triazin-2-yl, and 1, 2,4-hexahydrotriazin-3-yl;
• 5- to 10-membered aromatic heterocycle containing one to four heteroatoms from the group oxygen, nitrogen or sulfur mononuclear or binuclear heteroaryl, for example 5-membered heteroaryl. containing one to four nitrogen atoms or one to three nitrogen atoms and one sulfur or oxygen atom: 5-membered ring heteroaryl groups which, in addition to carbon atoms, may contain one to four nitrogen atoms or one to three nitrogen atoms and one sulfur or oxygen atom as ring members, eg. Furyl, 3-furyl, 2-thienyl, 3-thienyl, 2-pyrrolyl, 3-pyrrolyl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 3
• benzo-fused 5-membered heteroaryl containing one to three nitrogen atoms or one nitrogen atom and one oxygen or sulfur atom: 5-membered heteroaryl groups which may contain, in addition to carbon atoms, one to four nitrogen atoms or one to three nitrogen atoms and one sulfur or oxygen atom as ring members and in which two adjacent carbon ring members or a nitrogen and a neighboring carbon ring member can be bridged by a buta-1,3-diene-1,4-diyl group in which one or two C atoms have been replaced by N atoms can;
• 5-membered heteroaryl bonded via nitrogen containing one to four nitrogen atoms, or benzo-fused 5-membered heteroaryl bonded via nitrogen.
• 5-membered ring heteroaryl groups which in addition to carbon atoms may contain one to four nitrogen atoms or one to three nitrogen atoms as ring members, and in which two adjacent carbon ring members or a nitrogen and an adjacent carbon ring member by a Buta-l, 3rd in which one or two C atoms may be replaced by N atoms in which one or two C atoms may be replaced by N atoms, these rings being bonded via one of the N-atoms
• Nitrogen ring members are bonded to the framework, eg 1-pyrrolyl, 1-pyrazolyl, 1, 2,4-triazol-1-yl, 1-imidazolyl, 1,2,3-triazol-1-yl, 1,3,4-triazol-1-yl;
• 6-membered heteroaryl containing one to three or one to four nitrogen atoms 6-membered ring heteroaryl groups which, besides carbon atoms, may contain one to three or one to four nitrogen atoms as ring members, for example 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 particularly preferred embodiments of the intermediates with respect to the variables correspond to those of the radicals R 1 to R 5 of the formula (I).
• R 2 is hydrogen, methyl, ethyl or propyl.
• R 1 and R 1 together with the nitrogen atom to which they are bonded are pyrrolidinyl, piperidinyl, morpholinyl, thiomorpholinyl, piperazinyl, 3,6-dihydro-1 (2H) are piperidinyl or tetrahydro-l (2H) -pyridazinyl, where these radicals can be substituted by 1 to 3 fluorine atoms, 1 to 3 methyl groups and / or trifluoromethyl,
• R 7 is hydrogen or methyl
• R 8 is methyl, ethyl, fluorine, chlorine or trifluoromethyl
• n is the numbers 0, 1, 2 or 3, where R 8 is identical or different radicals, when m is 2 or 3,
• R 9 is methyl, ethyl, fluorine, chlorine or trifluoromethyl
• o is the numbers 0, 1, 2 or 3, where R 9 is identical or different radicals, when n is 2 or 3,
• R 3 is a three-, five- or six-membered heterocycle, in particular a five-membered heterocycle.
• R 3 is a heterocycle which is bonded to the pyrimidine ring via nitrogen. It is preferred to use compounds of the formula (I) in which R 3 represents the following groups: pyrrole, pyrazole, imidazole, 1, 2,4-triazole, 1,2,3-triazole, tetrazole, 1,2,3 Triazine, 1,2,4-triazine, oxazole, isoxazole, 1,3,4-oxadiazole, 1, 3,4-thiadiazole, furan, thiophene, thiazole, isothiazole, the heterocycle being bonded to the pyrimidine ring via C or N can be.
• R 3 is pyrazole optionally substituted by up to four R d groups, pyrrole, imidazole, 1,2,3-triazole, 1,2,4-triazole, 1,3, 4- oxadiazole, 1,3,4-thiadiazole, tetrazole, 2-pyridine, 2-pyrimidine, pyrazine or 3-pyridazine.
• R 3 is pyrazole optionally substituted by up to three R d groups, pyrrole, imidazole, 1,2,3-triazole, 1,2,4-triazole, 1,3, 4- oxadiazole, 1,3,4-thiadiazole, tetrazole, 2-pyridine, 2-pyrimidine, pyrazine or 3-pyridazine.
• R 3 is pyrazole, 1,2,3-triazole, 1, 2,4-triazole or pyridazine.
• R 3 is unsubstituted or monosubstituted by halogen, cyano, nitro, methyl, hydroxyl, oxo or methoxy.
• R 4 is halogen, C r C 6 alkyl, Ci-C 6 haloalkyl or C r C 6 -alkoxy, in particular represents halogen.
• pyrimidines of the formula (I) are preferred in which R 5 is pyridyl which is linked in the 2- or 4-position and may be monosubstituted, monosubstituted or differently substituted by fluorine, chlorine, bromine, cyano, nitro, Methyl, ethyl, methoxy, methylthio, hydroximinomethyl, hydroximinoethyl, methoximinomethyl, methoximinoethyl and / or trifluoromethyl.
• pyrimidines of the formula (I) are preferred in which R 5 is pyrimidyl which is linked in the 2- or 4-position and may be monosubstituted to trisubstituted, identically or differently substituted by fluorine, chlorine, bromine, cyano, nitro , Methyl, ethyl, methoxy, methylthio, hydroximinomethyl, hydroximinoethyl, methoximinomethyl, methoximinoethyl and / or trifluoromethyl.
• R 5 is thienyl which is linked in the 2- or 3-position and may be monosubstituted to trisubstituted, identically or differently substituted by fluorine, chlorine, bromine, cyano, nitro, Methyl, ethyl, methoxy, methylthio, Hydrox ⁇ iminomethyl, hydroximinoethyl, Methoximinimethyl, methoximinoethyl and / or trifluoromethyl.
• R 5 is thiazolyl which is linked in the 2-, 4- or 5-position and may be monosubstituted, disubstituted or differently substituted by fluorine, chlorine, bromine, Cyano, nitro, methyl, ethyl, methoxy, methylthio, hydroximinomethyl, hydroximinoethyl, methoximinimethyl, methoximinoethyl and / or trifluoromethyl.
• Radicals R and R for a compound corresponds in each case to one row of Table A.
• Radicals R 1 and R 2 for a compound corresponds in each case to one row of Table A.
• Radicals R 1 and R 2 for a compound corresponds in each case to one row of Table A.
• R 1 and R 2 for a compound corresponds in each case to one row of Table A.
• Radicals R 1 and R 2 for a compound corresponds in each case to one row of Table A.
• Radicals R 1 and R 2 for a compound corresponds in each case to one row of Table A.
• Radicals R 1 and R 2 for a compound corresponds in each case to one row of Table A.
• R 1 and R 2 for a compound corresponds in each case to one row of Table A.
• Radicals R 1 and R 2 for a compound corresponds in each case to one row of Table A.
• Radicals R 1 and R 2 for a compound corresponds in each case to one of the rows of Table A.
• Radicals R 1 and R 2 for a compound corresponds in each case to one row of Table A.
• Radicals R and R for a compound corresponds in each case to one row of Table A.
• Radicals R 1 and R 2 for a compound corresponds in each case to one row of Table A.
• R 1 and R 2 for a compound corresponds in each case to one row of Table A.
• Radicals R 1 and R 2 for a compound corresponds in each case to one row of Table A.
• Radicals R 1 and R 2 for a compound corresponds in each case to one row of Table A.
• Radicals R 1 and R 2 for a compound corresponds in each case to one of the rows of Table A.
• Radicals R 1 and R 2 for a compound corresponds in each case to one row of Table A.
• Radicals R 1 and R 2 for a compound corresponds in each case to one row of Table A.
• Radicals R 1 and R 2 for a compound corresponds in each case to one row of Table A.
• Radicals R and R for a compound corresponds in each case to one row of Table A.
• R 1 and R 2 for a compound corresponds in each case to one row for Table A.
• R 1 and R 2 for a compound corresponds in each case to one row of Table A.
• Radicals R 1 and R 2 for a compound corresponds in each case to one row of Table A.
• Radicals R 1 and R 2 for a compound corresponds in each case to one row of Table A.
• Radicals R 1 and R 2 for a compound corresponds in each case to one of the rows of Table A.
• Radicals R 1 and R 2 for a compound corresponds in each case to one row of Table A.
• Radicals R 1 and R 2 for a compound corresponds in each case to one row of Table A.
• Radicals R 1 and R 2 for a compound corresponds in each case to one row of Table A.
• Radicals R 1 and R 2 for a compound corresponds in each case to one row of Table A.
• HR 1 and R 2 for a compound corresponds in each case to one row for Table A.
• R 1 and R 2 for a compound corresponds in each case to one row of Table A.
• Radicals R 1 and R 2 for a compound corresponds in each case to one row of Table A.
• Radicals R 1 and R 2 for a compound corresponds in each case to one row of Table A.
• Radicals R 1 and R 2 for a compound corresponds in each case to one row of Table A.
• Radicals R 1 and R 2 for a compound corresponds in each case to one row of Table A.
• Radicals R 1 and R 2 for a compound corresponds in each case to one row of Table A.
• Radicals R 1 and R 2 for a compound corresponds in each case to one row of Table A.
• Radicals R and R for a compound corresponds in each case to one of the rows of Table A.
• Radicals R 1 and R 2 for a compound corresponds in each case to one row of Table A.
• Radicals R 1 and R 2 for a compound corresponds in each case to one row of Table A.
• Radicals R 1 and R 2 for a compound corresponds in each case to one row of Table A.
• HR 1 and R 2 for a compound corresponds in each case to one row for Table A.
• ADR 2 for a compound corresponds in each case to one row of Table A.
• Radicals R 1 and R 2 for a compound corresponds in each case to one row of Table A.
• Radicals R 1 and R 2 for a compound corresponds in each case to one row of Table A.
• Radicals R 1 and R 2 for a compound corresponds in each case to one row of Table A.
• Radicals R 1 and R 2 for a compound corresponds in each case to one row of Table A.
• Radicals R 1 and R 2 for a compound corresponds in each case to one row of Table A.
• Radicals R 1 and R 2 for a compound corresponds in each case to one row of Table A.
• Radicals R and R for a compound corresponds in each case to one of the rows of Table A.
• Radicals R and R for a compound corresponds in each case to one row of Table A.
• Radicals R 1 and R 2 for a compound corresponds in each case to one row of Table A.
• HR 1 and R 2 for a compound corresponds in each case to one row for Table A.
• R 1 and R 2 for a compound corresponds in each case to one row of Table A.
• Radicals R 1 and R for a compound corresponds in each case to one row of Table A.
• Radicals R 1 and R 2 for a compound corresponds in each case to one row of Table A.
• Radicals R 1 and R 2 for a compound corresponds in each case to one row of Table A.
• Radicals R 1 and R 2 for a compound corresponds in each case to one row of Table A.
• Radicals R 1 and R 2 for a compound corresponds in each case to one row of Table A.
• Radicals R 1 and R 2 for a compound corresponds in each case to one of the rows of Table A.
• Radicals R 1 and R 2 for a compound corresponds in each case to one row of Table A.
• Radicals R 1 and R 2 for a compound corresponds in each case to one row of Table A.
• Radicals R 1 and R 2 for a compound corresponds in each case to one row of Table A.
• R 1 and R 2 for a compound corresponds in each case to one row of Table A.
• Radicals R 1 and R 2 for a compound corresponds in each case to one row of Table A.
• Radicals R 1 and R 2 for a compound corresponds in each case to one row of Table A.
• Radicals R 1 and R 2 for a compound corresponds in each case to one row of Table A.
• Radicals R 1 and R 2 for a compound corresponds in each case to one row of Table A.
• Radicals R 1 and R 2 for a compound corresponds in each case to one row of Table A.
• Radicals R 1 and R 2 for a compound corresponds in each case to one row of Table A.
• Radicals R 1 and R 2 for a compound corresponds in each case to one of the rows of Table A.
• Radicals R 1 and R 2 for a compound corresponds in each case to one row of Table A.
• Radicals R 1 and R 2 for a compound corresponds in each case to one row of Table A.
• R 1 and R 2 for a compound corresponds in each case to one row of Table A.
• Radicals R 1 and R 2 for a compound corresponds in each case to one row of Table A.
• Radicals R 1 and R 2 for a compound corresponds in each case to one row of Table A.
• Radicals R 1 and R 2 for a compound corresponds in each case to one row of Table A.
• Radicals R 1 and R 2 for a compound corresponds in each case to one row of Table A.
• Radicals R 1 and R 2 for a compound corresponds in each case to one row of Table A.
• Radicals R 1 and R 2 for a compound corresponds in each case to one row of Table A.
• Radicals R 1 and R 2 for a compound corresponds in each case to one of the rows of Table A.
• Radicals R and R for a compound corresponds in each case to one row of Table A.
• HR 1 and R 2 for a compound corresponds in each case to one row for Table A.
• Radicals R 1 and R 2 for a compound corresponds in each case to one row of Table A.
• Radicals R 1 and R 2 for a compound corresponds in each case to one row of Table A.
• Radicals R 1 and R 2 for a compound corresponds in each case to one row of Table A.
• Radicals R 1 and R 2 for a compound corresponds in each case to one row of Table A.
• Radicals R 1 and R 2 for a compound corresponds in each case to one row of Table A.
• Radicals R 1 and R 2 for a compound corresponds in each case to one row of Table A.
• Radicals R 1 and R 2 for a compound corresponds in each case to one of the rows of Table A.
• Radicals R 1 and R 2 for a compound corresponds in each case to one row of Table A.
• HR 1 and R 2 for a compound corresponds in each case to one row for Table A.
• Radicals R 1 and R 2 for a compound corresponds in each case to one row of Table A.
• Radicals R 1 and R 2 for a compound corresponds in each case to one row of Table A.
• Radicals R 1 and R 2 for a compound corresponds in each case to one row of Table A.
• Radicals R 1 and R 2 for a compound corresponds in each case to one row of Table A.
• Radicals R 1 and R 2 for a compound corresponds in each case to one row of Table A.
• Radicals R 1 and R 2 for a compound corresponds in each case to one row of Table A.
• radicals R 1 and R 2 for a compound corresponds in each case to one line of Table A.
• Radicals R 1 and R 2 for a compound corresponds in each case to one of the rows of Table A.
• Radicals R 1 and R 2 for a compound corresponds in each case to one row of Table A.
• Radicals R 1 and R 2 for a compound corresponds in each case to one row of Table A.
• Radicals R 1 and R 2 for a compound corresponds in each case to one row of Table A.
• HR 1 and R 2 for a compound corresponds in each case to one row for Table A.
• Radicals R 1 and R 2 for a compound corresponds in each case to one row of Table A.
• Radicals R 1 and R 2 for a compound corresponds in each case to one row of Table A.
• Radicals R 1 and R 2 for a compound corresponds in each case to one row of Table A.
• Radicals R 1 and R 2 for a compound corresponds in each case to one row of Table A.
• Radicals R and R for a compound corresponds in each case to one row of Table A.
• Radicals R 1 and R 2 for a compound corresponds in each case to one row of Table A.
• Radicals R and R for a compound corresponds in each case to one of the rows of Table A.
• Radicals R 1 and R 2 for a compound corresponds in each case to one row of Table A.
• Radicals R 1 and R 2 for a compound corresponds in each case to one row of Table A.
• HR 1 and R 2 for a compound corresponds in each case to one row for Table A.
• Radicals R 1 and R 2 for a compound corresponds in each case to one row of Table A.
• Radicals R 1 and R 2 for a compound corresponds in each case to one row of Table A.
• Radicals R 1 and R 2 for a compound corresponds in each case to one row of Table A.
• Radicals R 1 and R 2 for a compound corresponds in each case to one row of Table A.
• Radicals R 1 and R 2 for a compound corresponds in each case to one row of Table A.
• Radicals R 1 and R 2 for a compound corresponds in each case to one row of Table A.
• Radicals R 1 and R 2 for a compound corresponds in each case to one of the rows of Table A.
• Radicals R 1 and R 2 for a compound corresponds in each case to one row of Table A.
• Radicals R 1 and R 2 for a compound corresponds in each case to one row of Table A.
• Radicals R 1 and R 2 for a compound corresponds in each case to one row of Table A.
• Radicals R 1 and R 2 for a compound corresponds in each case to one row of Table A.
• Radicals R 1 and R 2 for a compound corresponds in each case to one row of Table A.
• Radicals R 1 and R 2 for a compound corresponds in each case to one row of Table A.
• Radicals R 1 and R 2 for a compound corresponds in each case to one row of Table A.
• Radicals R 1 and R 2 for a compound corresponds in each case to one row of Table A.
• Radicals R and R for a compound corresponds in each case to one of the rows of Table A.
• Radicals R 1 and R 2 for a compound corresponds in each case to one row of Table A.
• HR 1 and R 2 for a compound corresponds in each case to one row for Table A.
• Radicals R 1 and R 2 for a compound corresponds in each case to one row of Table A.
• Radicals R 1 and R 2 for a compound corresponds in each case to one row of Table A.
• Radicals R 1 and R 2 for a compound corresponds in each case to one row of Table A.
• Radicals R 1 and R 2 for a compound corresponds in each case to one row of Table A.
• Radicals R 1 and R 2 for a compound corresponds in each case to one row of Table A.
• Radicals R 1 and R 2 for a compound corresponds in each case to one row of Table A.
• Radicals R 1 and R 2 for a compound corresponds in each case to one of the rows of Table A.
• Radicals R 1 and R 2 for a compound corresponds in each case to one row of Table A.
• Radicals R and R for a compound corresponds in each case to one row of Table A.
• R and R for each compound corresponds to one row for Table A.
• Radicals R 1 and R 2 for a compound corresponds in each case to one row of Table A.
• Radicals R 1 and R 2 for a compound corresponds in each case to one row of Table A.
• Radicals R 1 and R 2 for a compound corresponds in each case to one row of Table A.
• Radicals R 1 and R 2 for a compound corresponds in each case to one row of Table A.
• Radicals R 1 and R 2 for a compound corresponds in each case to one row of Table A.
• Radicals R 1 and R 2 for a compound corresponds in each case to one row of Table A.
• Suitable diluents for carrying out the process a) according to the invention are acids, such as acetic acid, formic acid, alcohols, such as methanol, water or halogenated hydrocarbons, such as dichloromethane or chloroform. Mixtures of these solvents can also be used. Preference is given to acetic acid or in the case of Oxone as the oxidant methanol / water mixtures.
• Suitable oxidizing agents for carrying out the process a) according to the invention are, for example, hydrogen peroxide, perwolfram acid, peracetic acid, 3-chloroperbenzoic acid, perphthalic acid, chlorine, oxygen and Oxone® (KHSO5).
• reaction temperatures can be varied within a substantial range when carrying out the process a) according to the invention.
• 0 C preferably at temperatures from O to 100 0 C at temperatures of from 1O 0 C to 50 0 C (see FIG. WO 02/074753 and references cited therein).
• process b) according to the invention for the preparation of the compounds of the formula (T) in general from 1 to 5 mol, preferably from 1 to 2 mol, of compound of the formula (IV) are employed per mole of the compound of the formula (III).
• R 1 , R 2 and R 5 preferably or in particular have those meanings which have already been mentioned as preferred in connection with the description of the substances of the formula (I) according to the invention
• R 4 is halogen, C r C 4 - Alkyl or C r C 4 haloalkyl and R 6 is C r C 6 alkyl.
• R 1, R 2 and R 5 have preferably or in particular have those meanings which are given above in connection with the description of the substances of the formula (I) according to the invention as being preferred
• R 4 is halogen, Ci-C 4 - Alkyl or C 1 -C 4 -haloalkyl and R 6 is C 1 -C 6 -alkyl
• n can be 1 or 2.
• Suitable acid acceptors in carrying out the process b) according to the invention are all inorganic or organic bases customary for such reactions.
• Sodium hydroxide, potassium hydroxide, sodium acetate, potassium acetate, calcium acetate, sodium carbonate, potassium carbonate, potassium bicarbonate and sodium bicarbonate, and also ammonium compounds such as ammonium hydroxide, ammonium acetate and ammonium carbonate, and tertiary amines such as trimethylamine, triethylamine, tributylamine, N, N- Dimethylaniline, N, N-dimethylbenzylamine, pyridine, N-methylpiperidine
• R 3 preferably or in particular has those meanings which have already been mentioned as preferred in connection with the description of the substances of the formula (I) according to the invention, with the proviso that R 3 must have at least one nitrogen atom via which the Connection to the pyrimidine ring in compounds of formula (F) takes place.
• the starting materials of the formula (IV) are known and / or can be prepared by known methods.
• R 4 is halogen, C r C 4 alkyl or Ci-C 4 haloalkyl and R 6 is Ci-C 6 alkyl and Hal for
• R 1 and R 2 have the meanings given above,
• the amines furthermore required for carrying out the process f) according to the invention as starting materials are generally defined by the formula (VI).
• R ⁇ and R.2 preferably those meanings which have already been mentioned in connection with the description of the compounds of formula (I) according to the invention for R ⁇ and R ⁇ as being preferred.
• the amines of the formula (VI) are known or can be prepared by known methods.
• Suitable diluents for carrying out the process f) according to the invention are all customary organic solvents.
• halogenated hydrocarbons such as, for example, chlorobenzene, dichlorobenzene, dichloromethane, chloroform, tetrachloromethane, dichloroethane or trichloroethane
• Ethers such as diethyl ether, diisopropyl ether, methyl t-butyl ether, methyl t-amyl ether, dioxane, tetrahydrofuran, 1, 2-dimethoxyethane, 1, 2-diethoxy- ethane or anisole
• Nitriles such as acetonitrile, propionitrile, n- or i-butyronitrile or benzonitrile
• Amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylformanilide, N-methylpyr
• Suitable acid acceptors in carrying out the process f) according to the invention are all inorganic or organic bases customary for such reactions.
• Suitable catalysts for carrying out the process f) according to the invention are all reaction promoters customary for such reactions.
• Preferably usable are fluorides such as sodium fluoride, potassium fluoride or ammonium fluoride.
• reaction temperatures can be varied within a substantial range when carrying out the process f) according to the invention. In general, one works at temperatures between 0 0 C and 15O 0 C, preferably at temperatures between 0 0 C and 8O 0 C.
• 0.5 to 10 mol, preferably 0.8 to 2 mol, of amine of the formula (VI) are employed per mole of halopyrimidine of the formula (EX).
• the workup is carried out by conventional methods.
• R 4 is C 4 alkyl or Ci-C is 4 -haloalkyl and R 5 and R 6 have the meanings given above,
• Suitable halogenating agents for carrying out the process g) are all components customary for the replacement of hydroxyl groups by halogen. Preference is given to using phosphorus trichloride, phosphorus tribromide, phosphorus pentachloride, phosphorus oxychloride, thionyl chloride, thionyl bromide or mixtures thereof or phosgene, di- or triphosgene.
• the corresponding fluorine compounds can be prepared from the chlorine or bromine compounds by reaction with potassium fluoride.
• Suitable diluents for carrying out the process g) according to the invention are all solvents customary for such halogenations.
• halogenated aliphatic or aromatic hydrocarbons such as chlorobenzene.
• the diluent may also be the halogenating agent itself, for example phosphorus oxychloride or a mixture of halogenating agents.
• Suitable acid acceptors for carrying out the process g) according to the invention are all organic bases customary for such reactions.
• tertiary amines such as triethylamine, tri-n-butylamine and N, N-dimethylaniline.
• the temperatures can also be varied within a relatively wide range when carrying out process g). In general, one works at temperatures between 0 0 C and 150 0 C, preferably between 10 0 C and 120 0 C.
• the compound of the formula (X) is generally reacted with an excess of halogenating agent.
• the workup is carried out by conventional methods.
• R 4 is C 4 alkyl or C t -C 4 haloalkyl and R 5 has the meanings indicated above,
• R 6 is C 1 -C 6 -alkyl and X is a leaving group cleavable by nucleophiles, if appropriate in a diluent in the presence of a base.
• Formula (Xu) generally represents conventional alkylating agents, such as C 1 -C 6 -alkyl halides, especially methyl chloride and methyl bromide, sulfuric acid-di-C 1 -C 4 -alkyl esters, such as dimethyl sulfate, or a methanesulfonic acid-C 1 -C 6 -alkyl ester, such as methyl methanesulfonate.
• Suitable diluents for carrying out the process according to the invention are h) water; Alcohols or dipolar aprotic solvents such as e.g. N, N-dimethylformamide in question (see US 5,250,689).
• alkali metal or alkaline earth metal hydroxides such as KOH, NaOH, NaHCO 3, Na 2 CO 3, sodium methylate and sodium ethylate in question, but also nitrogen bases such as pyridine in consideration.
• the temperatures can also be varied within a relatively wide range when carrying out the process h). In general, one works at temperatures between 0 0 C and 100 0 C, preferably between 10 0 C and 6O 0 C.
• the components are used in approximately stoichiometric ratio. However, it may be advantageous to use the alkylating agent (XII) in excess.
• the starting materials of the formula (XII) are known and / or can be prepared by known methods.
• R 4 is 4 alkyl or Ci-G t -haloalkyl is C, R 5 has the meanings indicated above.
• R 4 is 4 -haloalkyl Ci-Q-alkyl or C r C,
• R 7 is C 1 -C 4 -alkyl
• R 5 has the meanings given above
• Suitable diluents for carrying out the process according to the invention are i) protic solvents such as e.g. Alcohols, especially ethanol into consideration.
• aprotic solvents such as pyridine, N, N-dimethylformamide, N, N-dimethylacetamide or mixtures thereof are also suitable (compare US Pat. No. 4,331,590, Org., Prep, and Proced. Int., Vol. 10, pp. 21-27) Heteroat. Chem., Vol. 10, pp. 17-23 (1999); Czech Chem. Commun., Vol. 58, pp. 2215-2221).
• the acid acceptor are alkali metal or alkaline earth metal, - bicarbonates, - carbonates and alcoholates, such as KOH, NaOH, NaHCO 3, Na 2 CO 3, sodium methylate and sodium, but also nitrogen bases such as pyridine and Tributlyamin in question.
• the temperatures can also be varied within a relatively wide range when carrying out the process i). In general, one works at temperatures between 2O 0 C and 250 0 C, preferably between 7O 0 C and 22O 0 C.
• the components are used in approximately stoichiometric ratio. However, it may be advantageous to use excess thiourea (XFV).
• Thiourea is known (XIV).
• the starting materials of the formula (Xm) are known (cf., EP-A-1002 788; DE3942952) and / or can be prepared by known methods.
• R 5 and R 6 have the meanings given above,
• the compounds of formula XV can also be in the following form:
• Suitable halogenating agents for carrying out process j) are all halogenating agents specified for carrying out process g).
• Suitable diluents for carrying out the process j) according to the invention are all diluents for carrying out the process g).
• Suitable acid acceptors for carrying out the process j) according to the invention are all acid acceptors specified for carrying out the process g).
• the temperatures can also be varied within a substantial range when carrying out process j). In general, one works at temperatures between 0 0 C and 150 0 C, preferably between 1O 0 C and 12O 0 C.
• the compound of formula (XV) is generally reacted with an excess of halogenating agent. The workup is carried out by conventional methods.
• R 5 and R 6 have preferably or in particular have those meanings which have already been mentioned in connection with the description of the substances of the formula (I) according to the invention as being preferred.
• R 5 has the meaning given above
• Formula (XII) generally represents common alkylating agents, such as C 1 -C 6 -alkyl halides, in particular methyl chloride and methyl bromide, sulfuric acid di- (for CpC ⁇ -alkyl esters, such as dimethyl sulfate, or a methanesulfonic Ci-C ⁇ -alkyl ester, such as methanesulfonic acid methyl ester ,
• the compounds of formula XVI may also be in the following form:
• Suitable diluents for carrying out the process k) according to the invention are water, alcohols or dipolar aprotic solvents, such as e.g. N, N-dimethylformamide in question (see US 5,250,689).
• Suitable acid acceptors for carrying out the process k) alkali metal or alkaline earth metal hydroxides according to the invention, - hydrogen carbonates, carbonates and alkoxides such as KOH, NaOH, NaHCO 3, Na 2 CO 3, sodium methylate or ethylate, but also nitrogen bases such as pyridine in question ,
• the temperatures can also be varied within a relatively wide range when carrying out the process k). In general, one works at temperatures between 0 0 C and 100 0 C, preferably between 1O 0 C and 60 0 C.

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