Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
  • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
  • C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
• • 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
  • C07D239/34—One oxygen atom
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
  • A61P33/00—Antiparasitic agents
  • A61P33/14—Ectoparasiticides, e.g. scabicides
• • 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
• • 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
• • 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 new pyrazolylpyrimidines, several processes for their preparation and their use as pesticides.
• Insecticidal pyrazolylpyrimidines are not yet known.
• R 1 and R 2 independently of one another are hydrogen, halogen, nitro, cyano, alkyl, haloalkyl, alkoxy, haloalkoxy, alkenyl, alkynyl, alkenyloxy, haloalkenyloxy, alkynyloxy, haloalkynyloxy, -S (O) p R 3 , -NR 4 R 5 , -COR 6 , -CO 2 R 7 , -CSR 6 , -CONR 4 R 5 , -NHCO 2 R 8 , cycloalkyl; or for each optionally by halogen, alkyl, haloalkyl, alkoxy,
• R 1 and R 2 also together represent alkyls or alkenyls, where the carbon chain can be interrupted by 1 to 3 heteroatoms from the series nitrogen and oxygen and the ring formed in this way can in turn optionally be substituted by halogen or alkyl,
• X for halogen, nitro, cyano, hydroxy, alkyl, haloalkyl, alkoxy, haloalkoxy, alkenyl, alkynyl, alkenyloxy, haloalkenyloxy, alkynyloxy,
• n 0, 1, 2 or 3, where X stands for identical or different radicals if n stands for 2 or 3,
• Y stands for a direct bond, oxygen, -S (O) p - or -NR 9 -,
• p 0, 1 or 2
• t and w independently of one another represent 0, 1, 2, 3 or 4,
• A represents oxygen, sulfur or NR 15 ,
• E stands for -OR 16 , -SR 16 , -O ⁇ M, -S ⁇ M or -NR 17 R 18 ,
• M also stands for an alkaline earth metal ion, where two molecules of a compound each form a salt with such an ion
• R 3 represents hydrogen, alkyl, haloalkyl, cycloalkyl, cycloalkylalkyl; or for aryl, arylalkyl, saturated or unsaturated heterocyclyl or heterocyclylalkyl with 1 to 4 heteroatoms from the series nitrogen, oxygen and sulfur, optionally substituted by halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio,
• R 4 represents hydrogen, alkyl, haloalkyl, cycloalkyl or alkylcarbonyl,
• R 5 represents hydrogen, amino, formyl, alkyl, alkenyl, alkynyl, haloalkyl, cycloalkyl, alkoxy, alkoxyalkyl, alkylcarbonyl, alkoxycarbonyl, oxamoyl,
• R 4 and R 5 also together for alkylidene; or represent benzylidene optionally substituted by halogen, nitro, alkyl, haloalkyl;
• R 4 and R together with the nitrogen atom to which they are attached, form a saturated or unsaturated heterocycle which may optionally contain a further nitrogen, oxygen or sulfur atom and which may optionally be substituted by alkyl,
• R 6 represents hydrogen, alkyl, haloalkyl or arylalkyl
• R 7 represents hydrogen, alkyl, haloalkyl, cycloalkyl, cycloalkylalkyl, aryl or arylalkyl,
• R 8 represents alkyl or haloalkyl
• R 9 represents hydrogen, alkyl, haloalkyl, cycloalkyl, cycloalkylalkyl; or for aryl, arylalkyl optionally substituted by halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, saturated or unsaturated heterocyclyl or heterocyclylalkyl with 1 to 4 heteroatoms from the series nitrogen, oxygen and sulfur,
• R 10 represents halogen, alkyl, alkylcarbonyl, alkoxycarbonyl, cycloalkyl, cycloalkylalkyl; or represents aryl or arylalkyl, which in turn can be substituted by halogen or alkyl in the aryl part,
• R 1 ' represents hydrogen or alkyl
• R and R independently of one another represent hydrogen, hydroxyl, alkyl or alkoxy
• R 14 represents hydrogen, alkyl or haloalkyl
• R 15 represents hydrogen, alkyl, alkoxy, cyano or dialkylamino
• R 17 represents hydrogen or alkyl
• R 18 is hydrogen, hydroxy, amino, -SO 2 R 8 , alkyl, alkenyl; or for cycloalkyl, cycloalkylalkyl, aryl, arylalkyl, heteroaryl or heteroarylalkyl with 1 to 4 heteroatoms from the series nitrogen, oxygen and sulfur, optionally substituted by halogen, hydroxy, alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, oxyalkyleneoxy,
• R 17 and R 18 together with the nitrogen atom to which they are attached, for a 5- or 6-membered saturated or unsaturated heterocycle, which can contain 1 or 2 further heteroatoms from the series nitrogen, oxygen and sulfur and which, if appropriate, by Alkyl can be substituted,
• the compounds of the formula (I) can optionally be present as geometric and / or optical isomers or regioisomers or their isomer mixtures in different compositions. Both the pure isomers and the isomer mixtures are claimed according to the invention. Likewise, compounds of the formula (I) may be present in various tautomeric forms, depending on the type and number of the substituents. All tautomers are claimed according to the invention.
• R 1 , R 2 , X, n, Z and A have the meanings given above and
• E 1 represents -OR 16 , -SR 16 or -NR 17 R 18 ,
• R 1 , R 2 , Z, A and E 1 have the meanings given above and
• R 1 , R 2 , X, n, Z and R have the meanings given above and
• Y 1 represents -SO- or -SO 2 -, obtained by
• R 1 , R 2 , X, n, Z and R have the meanings given above,
• Y 2 represents oxygen or -NR 9 -, R a stands for one of the following groupings
• R 1 , R 2 , X, n, Z, R 9 and R 14 have the meanings given above,
• R 1 , R 2 , Y 2 , Z and R a have the meanings given above,
• X and n have the meanings given above, if appropriate in the presence of a base, if appropriate in the presence of a diluent and if appropriate in the presence of a catalyst, or
• R, R, X, n, Z and R a have the meanings given above,
• R, R, X and n have the meanings given above,
• R, R, X, n and Z have the meanings given above,
• trialkyltin azides if appropriate in the presence of a diluent, or
• Y stands for a direct bond, oxygen, sulfur or -NR -
• E 2 stands for -O " M or -S ⁇ M
• R, R, X, n, Z, A, M and R have the meanings given above,
• R 1 , R 2 , X, n, Y 3 , Z and A have the meanings given above,
• R> b stands for one of the following groupings
• R 1 , R 2 , X, n, Z and R 14 have the meanings given above and
• R, ⁇ , R, X, n, Y and Z have the meanings given above,
• R 1 , R 2 , X, n, Y 3 and Z have the meanings given above, optionally hydrogenated in the presence of a diluent and in the presence of a catalyst,
• R, R, X, n, Y and Z have the meanings given above,
• the pyrazolylpyrimidines according to the invention are generally defined by the formula (I).
• R 1 and R 2 independently of one another preferably represent hydrogen, halogen, nitro, cyano, C 6 -alkyl, C 6 haloalkyl, CC 6 -alkoxy, C 6 genalkoxy -Halo-, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 2 -C 6 alkenyloxy, C 2 -C 6 -
• R 1 and R 2 together also preferably represent C 3 -C 5 alkylene or C 3 -C 4 alkenylene, the carbon chain being composed of 1 or 2 heteroatoms which are 0 to 2 nitrogen atoms and / or 0 to 1 oxygen atom can, can be interrupted and the ring thus formed can in turn be optionally substituted once or several times, identically or differently, by halogen or C 1 -C 6 alkyl;
• X preferably represents halogen, nitro, cyano, hydroxy, C 1 -C 6 alkyl, C 1 -C 6 -
• Haloalkyl C ⁇ -C 6 -alkoxy, C 6 haloalkoxy, C 2 -C 6 alkenyl, C 2 -C 6 -
• n is preferably 0, 1, 2 or 3, where X is the same or different
• Radicals is when n is 2 or 3;
• Y preferably represents a direct bond, oxygen, -S (O) p - or -NR 9 -
• Z preferably stands for - (CH 2 ) r -, - (CH 2 ) t - (CHR 10 ) - (CH 2 ) w -, - (CH 2 ) r -C (O) - (CH 2 ) r , - (CH 2 ) r -O- (CH 2 ) t -, - (CH 2 ) r -S (O) p - (CH 2 ) t -, - (CH 2 ) r -N (R ' ⁇ - (CH ,), - or
• r preferably represents 1, 2, 3, 4, 5 or 6;
• t and w independently of one another are preferably 0, 1, 2, 3 or 4;
• R preferably stands for the grouping
• A preferably represents oxygen, sulfur or NR 15 ;
• E preferably represents -OR 16 , -SR 16 , -O ⁇ M, -S " M or -NR , 7 R 18 ;
• M preferably represents optionally up to four times, identical or different, ammonium substituted by C] -C 6 -alkyl, aryl or aryl -CC-C 6 -alkyl or a lithium cation (Li + ), a sodium cation (Na + ) or a potassium cation (K + );
• M also preferably represents a magnesium cation (Mg) or a calcium + cation (Ca), where two molecules of a compound each form a salt with such an ion;
• R 3 preferably represents hydrogen, C i -C 6 alkyl, C i -C 6 haloalkyl, C 3 -C 7 cycloalkyl, C 3 -C 7 cycloalkyl-C r C 6 alkyl; or in each case optionally monosubstituted or polysubstituted by identical or different halogen, Cj-C ö alkyl, Ci-C ö haloalkyl, C ⁇ -C 6 -alkoxy, C 6 - haloalkoxy, C ⁇ -C 6 - alkylthio, dC 6 -Halogenalkylthio substituted aryl, aryl -CC 6 alkyl, 5- or 6-membered, saturated or unsaturated heterocyclyl or heterocyclyl -C 6 -alkyl having 1 to 4 heteroatoms, which has 0 to 4 nitrogen atoms, 0 to 2 contains non-adjacent oxygen atoms and / or 0 to 2
• R 5 preferably represents hydrogen, amino, formyl, C] -C 6 - alkyl, C -C 6 alkenyl, C 2 -C 6 alkynyl, C ⁇ -C 6 haloalkyl, C 3 -C 7 cycloalkyl, C .-C 6 alkoxy, C] -C6 -
• R 4 and R 5 also together preferably represent -C 6 alkylidene; or for benzylidene which is optionally mono- or polysubstituted, identically or differently, by halogen, nitro, C 1 -C 6 -alkyl, dC ⁇ -haloalkyl;
• R 4 and R 5 together with the nitrogen atom to which they are attached are preferably a 5- or 6-membered, saturated or unsaturated
• Heterocycle which may optionally contain a further nitrogen, oxygen or sulfur atom and which may optionally be mono- or polysubstituted, identically or differently, by C 1 -C 6 -alkyl;
• R 6 preferably represents are hydrogen, C 6 - alkyl, C ⁇ -C 6 haloalkyl, or aryl C ⁇ -C6 alkyl;
• R 7 preferably represents are hydrogen, C 6 -alkyl, C 6 haloalkyl, C 3 -C - cycloalkyl, C 3 -C 7 cycloalkyl-C ⁇ -C 6 alkyl, aryl or aryl C ⁇ -C 6 alkyl;
• R 8 preferably represents Ci-C ö alkyl or C ⁇ -C 6 haloalkyl
• R 9 preferably represents hydrogen, C.-C 6 -alkyl, -C-C 6 -haloalkyl, C 3 -C 7 -
• R 10 preferably represents halogen, CC 6 -alkyl, C r C 6 -alkylcarbonyl, Ci-Ce-alkoxycarbonyl, C 3 -C -cycloalkyl, C 3 -C 7 -cycloalkyl-dC 6 -alkyl; or for aryl or aryl -CC 6 alkyl, which in turn can be substituted one or more times in the aryl part, identically or differently, by halogen or -C 6 alkyl;
• R 1 ' preferably represents hydrogen or -CC 6 alkyl
• R 12 and R 13 independently of one another preferably represent hydrogen, hydroxy, C
• R 14 preferably represents hydrogen, dC 6 alkyl or C ⁇ -C 6 haloalkyl
• R 15 preferably represents hydrogen, C 1 -C 6 -alkyl, C 1 -C 6 -alkoxy, cyano or di (C i -C 6 -alkyl) amino;
• Halogenalkoxy C ( -C 6 - alkylthio, C ⁇ -C 6 -haloalkylthio, dC 6 - alkoxy- carbonyl, Ci-C ö alkylcarbonyloxy substituted aryl, aryl-C ⁇ -C 6 alkyl, C 3 - C 7 cycloalkyl, C 3 -C 7 cycloalkyl-C ⁇ -C 6 -alkyl, 4- to 6-membered, saturated or unsaturated heterocyclyl or heterocyclyl -CC 6 -alkyl each having 1 to 4 heteroatoms which contain 0 to 4 nitrogen atoms, 0 to 2 non-adjacent acidic atoms and / or 0 to 2 non-adjacent sulfur atoms;
• R 17 preferably represents hydrogen or C 1 -C 6 alkyl
• R 18 preferably represents hydrogen, hydroxy, amino, -SO 2 R 8 , -CC 6 alkyl, C 2 - C ⁇ alkenyl; or in each case optionally monosubstituted or polysubstituted by identical or different halogen, hydroxy, C ⁇ -C 6 - alkyl, C ⁇ -C 6 haloalkyl, CpC 6 - alkoxy, C ⁇ -C 6 haloalkoxy, dC 6 - alkylthio, C ⁇ -C 6 -haloalkylthio, oxy- (-C-C 6 -alkylene) oxy-substituted C 3 -C 7 -cycloalkyl, C 3 -C 7 -cycloalkyl-C ⁇ -C 6 - alkyl, aryl, aryl-C ⁇ -C 6 -alkyl, Heteroaryl or heteroaryl -CC 6 alkyl each having 1 to 4 heteroatoms, which contain 0 to 4 nitrogen
• R 17 and R 18 together with the nitrogen atom to which they are attached are preferably a 5- or 6-membered saturated or unsaturated heterocycle, the 1 or 2 further heteroatoms which have 0 to 2 nitrogen atoms, 0 or 1 oxygen atom and may be / or 0 or 1 sulfur atom, may contain and is optionally monosubstituted or polysubstituted by identical or different substituents dC ö - may be substituted alkyl;
• R 1 and R 2 independently of one another particularly preferably represent hydrogen
• R 1 and R 2 together also particularly preferably represent C 3 -C 5 alkylene or C 3 -C alkenylene, the carbon chain being formed by 1 or 2 heteroatoms, which can be 0 to 2 nitrogen atoms and / or 0 or 1 oxygen atom, can be interrupted and the ring thus formed can in turn be optionally substituted up to four times, identically or differently, by fluorine, chlorine, bromine or -CC alkyl;
• X particularly preferably represents fluorine, chlorine, bromine, nitro, cyano, hydroxyl, C 1 -C 4 -alkyl, dC 4 -haloalkyl having 1 to 9 fluorine, chlorine and / or bromine atoms, C 1 -C 4 alkoxy, C 1 -C 4 -haloalkoxy with 1 to 9 fluorine, chlorine and / or bromine atoms, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, -S (O) p R 3 , -SO 2 NR 4 R 5 , -NR 4 R 5 , -COR 6 , -CO 2 R 7 , -CSR 6 , -CONR 4 R 5 , -NHCO 2 R 8 , C 3 -C 6 cycloalkyl; or for each optionally single to quadruple, the same or different by fluorine, chlorine, bromine, dC 4 - alkyl,
• X also particularly preferably stands for iodine.
• n particularly preferably represents 0, 1, 2 or 3, where X represents the same or different radicals if n represents 2 or 3;
• Y particularly preferably represents a direct bond, oxygen, -S (O) p - or -NR 9 -;
• p particularly preferably represents 0, 1 or 2;
• Z particularly preferably represents - (CH 2 ). - (CH 2 ), - (CHR 10 ) - (CH 2 ) W -, - (CH 2 ) r -C (O) - (CH 2 ) r , - (CH 2 ) r -O- (CH 2 ) t -, - (CH 2 ) r -S (O) p - (CH 2 ) t -,
• r particularly preferably represents 1, 2, 3 or 4;
• t and w independently of one another are particularly preferably 0, 1, 2, 3 or 4;
• R particularly preferably stands for the grouping
• E particularly preferably represents -OR 16 , -SR 16 , -O ⁇ M, -S " M or -NR 17 R 18 ;
• M particularly preferably represents ammonium which is optionally monosubstituted to tetrasubstituted, identically or differently by C 4 -C 4 -alkyl, phenyl, benzyl or phenylethyl, or a sodium cation (Na + ) or a potassium cation (K + );
• M also particularly preferably represents a magnesium cation (Mg) or a calcium cation (Ca 2+ ), two molecules of a compound each forming a salt with such an ion;
• R 3 particularly preferably represents hydrogen, -CC alkyl, -CC 4 haloalkyl having 1 to 9 fluorine, chlorine and / or bromine atoms, C 3 -C 6 cycloalkyl, C 3 -C 6 cycloalkyl -C-C 4 alkyl; or for each optionally single to fourfold, identical or different by fluorine, chlorine, bromine, -CC 4 -alkyl, -C-C 4 -haloalkyl with 1 to 9 fluorine, chlorine and / or bromine atoms, Cj-C -alkoxy , -C-C 4 haloalkoxy with 1 to 9 fluorine, chlorine and / or bromine atoms, -C-C 4 - alkylthio, C 1 -C 9 -haloalkylthio with 1 to 9 fluorine, chlorine and / or bromine atoms substituted aryl (in particular phenyl), aryl -CC-al
• R 5 particularly preferably represents hydrogen, amino, formyl, C ⁇ -C 4 alkyl, C 2 - C 4 alkenyl, C 2 -C 4 alkynyl, C ⁇ -C 4 -haloalkyl having 1 to 9 fluorine, chlorine and / or bromine atoms, C 3 -C 6 cycloalkyl, C ⁇ -C - alkoxy, C ⁇ -C 4 alkoxy-C ⁇ - C 4 -alkyl, C - alkylcarbonyl, C ⁇ -C alkoxycarbonyl, oxamoyl;
• R 4 and R s together also particularly preferably represent C] -C -alkylidene; or for optionally up to fourfold, identical or different by fluorine, chlorine, bromine, nitro, -CC alkyl, -C-C-haloalkyl with 1 to 9 fluorine, chlorine and / or bromine atoms, substituted benzylidene;
• R 4 and R 5 together with the nitrogen atom to which they are attached also particularly preferably represent a 5- or 6-membered, saturated or unsaturated heterocycle which may optionally contain a further nitrogen, oxygen or sulfur atom and which, if appropriate may simply be different substituents to tetrasubstituted by identical or by C 4 alkyl;
• R 6 is particularly preferably are hydrogen, C 4 - alkyl, C ⁇ -C 4 -haloalkyl having 1 to 9 fluorine, chlorine and / or bromine atoms or aryl C ⁇ -C alkyl;
• R 7 particularly preferably represents hydrogen, dC 4 -alkyl, -CC 4 -haloalkyl having 1 to 9 fluorine, chlorine and / or bromine atoms, C 3 -C 6 -cycloalkyl, C 3 -C 6 - cycloalkyl-C ⁇ -C 4 alkyl, aryl (especially phenyl) or aryl -CC -C 4 alkyl;
• R particularly preferably represents C ⁇ -C 4 alkyl or C ⁇ -C 4 -haloalkyl having 1 to 9 fluorine, chlorine and / or bromine atoms;
• R 9 particularly preferably represents hydrogen, dC 4 -alkyl, -CC 4 -haloalkyl having 1 to 9 fluorine, chlorine and / or bromine atoms, C 3 -C 6 -cycloalkyl, C 3 -C 6 - cycloalkyl-C i -C 4 alkyl; or for each optionally single to fourfold, the same or different by fluorine, chlorine, bromine, -CC 4 alkyl, dC 4 haloalkyl with 1 to 9
• R 10 particularly preferably represents fluorine, chlorine, bromine, iodine, C
• R 1 ' particularly preferably represents hydrogen or -CC 4 alkyl
• R and R independently of one another particularly preferably represent hydrogen, hydroxy, C ⁇ -C 4 - alkyl or C ⁇ -C 4 alkoxy;
• R particularly preferably represents hydrogen, C 1 -C 4 -alkyl or dC 4 -halogenylalkyl having 1 to 9 fluorine, chlorine and / or bromine atoms;
• R 16 particularly preferably represents hydrogen; for C] -C] 6 haloalkyl with 1 to 31 fluorine, chlorine and / or bromine atoms, C -C 12 haloalkenyl with 1 to 21 fluorine, chlorine and / or bromine atoms, C 2 -C 8 - Haloalkynyl with 1 to 11 fluorine, chlorine and / or bromine atoms; for each optionally single to fourfold, identical or different by amino, hydroxy, cyano, nitro, Cj-C 4 - alkoxy, dC 4 -haloalkoxy with 1 to 9 fluorine, chlorine and / or bromine atoms, dC 4 - alkylthio, C ⁇ -C 4 -Halogen- alkylthio with 1 to 9 fluorine, chlorine and / or bromine atoms, C
• Haloalkylthio with 1 to 9 fluorine, chlorine and / or bromine atoms, dC - alkoxycarbonyl, dC 4 -alkylcarbonyloxy-substituted aryl (especially phenyl), aryl -CC 4 -alkyl, C 3 -C 6 -cycloalkyl, C 3 - C 6 -cycloalkyl-C r C 4 -alkyl, 4- to 6-membered, saturated or unsaturated, heterocyclyl or heterocyclic-C 1 -C 4 -alkyl, each with 1 to 3 heteroatoms, which have 0 to 3 nitrogen atoms, Contain 0 to 2 non-adjacent oxygen atoms and / or 0 to 2 non-adjacent sulfur atoms;
• R 17 particularly preferably represents hydrogen or C i -C - alkyl
• R 18 particularly preferably represents hydrogen, hydroxy, amino, -SO 2 R 8 , -CC 4 - alkyl, C 2 -C alkenyl; or for each optionally single to quadruple, the same or different, by fluorine, chlorine, bromine, hydroxy, C 1 -C 4 -alkyl, C 1 -C 6 -haloalkyl having 1 to 9 fluorine, chlorine and / or bromine atoms, C 1 -C 4 -Alkoxy, -CC 4 -haloalkoxy with 1 to 9 fluorine, chlorine and / or bromine atoms, dC 4 - alkylthio, d- C 4 haloalkylthio with 1 to 9 fluorine, chlorine and / or bromine atoms, oxy- (-C -alkylene) oxy-substituted C 3 -C 6 -cycloalkyl, C 3 -C 6 -cycloalkyl-C !
• aryl especially phenyl
• aryl -CC 4 -alkyl heteroaryl or hetero-aryl -CC 4 -alkyl each having 1 to 3 heteroatoms which have 0 to 3 nitrogen atoms, 0 to 2 contain non-adjacent oxygen atoms and / or 0 to 2 non-adjacent sulfur atoms;
• R 17 and R 18 together with the nitrogen atom to which they are attached also particularly preferably represent a 5- or 6-membered saturated or unsaturated heterocycle, the 1 or 2 further heteroatoms which are 0 to 2
• Nitrogen atoms, 0 or 1 oxygen atom and / or 0 or 1 sulfur atom can be contained and which can optionally be monosubstituted to trisubstituted, identically or differently, by C 1 -C 4 -alkyl;
• R 1 and R 2 independently of one another very particularly preferably represent hydrogen, fluorine, chlorine, bromine, nitro, cyano, methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, i-butyl, t- Butyl, -CF 3 , -CC1 3 , -CHF 2 , -CC1F 2 , -CHC1 2 , -CF 2 CHFC1,
• X very particularly preferably represents fluorine, chlorine, bromine, nitro, cyano,
• X also very particularly preferably represents iodine
• n very particularly preferably represents 0, 1, 2 or 3, where X represents the same or different radicals if n represents 2 or 3;
• Y very particularly preferably represents a direct bond, oxygen, -S (O) p or -NR 9 -; p very particularly preferably represents 0, 1 or 2;
• Z very particularly preferably represents -CH 2 -, - (CH 2 ) 2-, - (CH 2 ) 3 -, - (CH 2 ) -,
• R very particularly preferably stands for the grouping
• E very particularly preferably represents -OR 16 , -SR 16 , -O " M or -NR 17 R 18 ;
• M very particularly preferably stands for tetrabutylammonium, trimethylbenzylammonium or for a sodium cation (Na + ) or a potassium cation (K + );
• M also very particularly preferably represents a magnesium cation (Mg 2+ ) or a calcium cation (Ca 2+ ), where two molecules of a compound each form a salt with such an ion;
• R 4 very particularly preferably represents hydrogen, methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, i-butyl, t-butyl, -COMe;
• R 5 very particularly preferably represents hydrogen, amino, formyl, methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, i-butyl, t-butyl, vinyl, allyl,
• R 4 and R 5 together also very particularly preferably represent ethylidene, i-propylidene, s-butylidene, benzylidene, nitrobenzylidene;
• R 4 and R 5 together with the nitrogen atom to which they are attached, very particularly preferably represent a 5- or 6-membered saturated heterocycle from the series of morpholine, piperidine, thiomorpholine, pyrrolidine, which may be mono- or pseudo, identical or different through
• Methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, i-butyl, t-butyl may be substituted;
• R 9 very particularly preferably represents hydrogen, methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, i-butyl, t-butyl, -CH 2 CF 3 , -CH 2 CF 2 H, -CH 2 CF 2 CF 3 ,
• R 10 very particularly preferably represents fluorine, chlorine, bromine, methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, i-butyl, t-butyl, -COMe, -COEt, -CO 2 Me, -CO 2 Et, cyclohexyl; or for phenyl or benzyl, which in turn can be substituted one to four times in the aryl part, identically or differently, by fluorine, chlorine, bromine or methyl;
• R 14 very particularly preferably represents hydrogen, methyl, ethyl, n-propyl, i-
• R 16 very particularly preferably represents hydrogen; for -CC 2 -haloalkyl with 1 to 23 fluorine, chlorine and / or bromine atoms, d-CIO-haloalkenyl with 1 to 17 fluorine, chlorine and / or bromine atoms, C 2 - C 6 haloalkynyl with 1 to 7 fluorine, chlorine and / or bromine atoms; for each one if necessary up to three times, the same or different
• R 17 very particularly preferably represents hydrogen, methyl or ethyl
• R 18 very particularly preferably represents hydrogen, hydroxyl, amino, -S ⁇ 2Me, -SO 2 Et, methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, i-butyl, t-butyl,
• allyl for each optionally single to triple, identical or different, by fluorine, chlorine, hydroxy, methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, i-butyl, t-butyl, trifluoromethyl, trichloromethyl, Methoxy, ethoxy, trifluoromethoxy, methylthio, trifluoromethylthio, -O-CH -O- substituted phenyl, benzyl, phenylethyl, cyclopropyl, cyclopropylmethyl, cyclohexyl,
• R 17 and R 18 together with the nitrogen atom to which they are attached, very particularly preferably represent a 5- or 6-membered saturated heterocycle from the series piperazine, mopholin, piperidine, pyrrolidine, which may be one to three times the same or can be differently substituted by methyl, ethyl, n-propyl or i-propyl;
• R, ⁇ , R, X, n, p, Z and R have the meanings given above.
• R 1 , R 2 , X, n, Z, R and R 9 have the meanings given above.
• R 1 , R 2 , X, n, Z and R have the meanings given above.
• R, R, X, n, Z and R have the meanings given above.
• the radicals R 1 , R 2 , X, n, Z, R and R 9 are preferably, particularly preferably or very particularly preferably those meanings which are used in the description of the substances according to the invention of the general formula (I) for these radicals as being preferred, particularly preferred, etc.
• X for fluorine, chlorine, bromine, nitro, cyano, hydroxy, methyl, ethyl, trifluoromethyl, methoxy, ethoxy, i-propoxy, trifluoromethoxy, trifluoromethylthio, vinyl, ethynyl, -SO 2 Me, -NH 2 , -NHMe, -NMe 2 , -COMe; or represents furyl, phenyl, chlo ⁇ henyl; or when n is 2 or 3, two adjacent radicals X together also represent butylene or butadienylene,
• n 0, 1, 2 or 3, where X stands for identical or different radicals if n stands for 2 or 3,
• R 9 represents hydrogen, methyl, ethyl, n-propyl, -CH 2 CF 3 , -CH 2 CF 2 CF 3 or cyclopropyl.
• Saturated hydrocarbon radicals such as alkyl
• heteroatoms e.g. in alkoxy, where possible, be straight-chain or branched.
• halopyrimidines required as starting materials when carrying out processes (A), (B) and (C) according to the invention are general by the formula (II)
• R, R, Z and A are preferably, particularly preferably or very particularly preferably those meanings which, in connection with the description of the substances of the formula (I) according to the invention, are preferred, particularly preferred, etc. for these radicals .
• E 1 preferably represents -OR 16 , -SR 16 or -NR 17 R 18 .
• Shark 1 preferably represents fluorine, chlorine, bromine or iodine, particularly preferably chlorine, bromine or iodine, very particularly preferably chlorine or bromine.
• halopyrimidines of the formula (II) are known in some cases and / or can be prepared by known processes (cf. US 3,910,910).
• Formula (III) provides a general definition of the pyrazole compounds required as starting materials when carrying out processes (A), (B) and (C) according to the invention.
• X and n are preferred, particularly preferred or very particularly preferred for those meanings which are already related with the description of the substances of the formula (I) according to the invention for these radicals as being preferred, particularly preferred etc. have been mentioned.
• Pyrazole compounds of the formula (III) are known and / or can be prepared by known processes.
• Suitable diluents for carrying out processes (A), (B) and (C) are all customary inert organic solvents.
• Halogenated aliphatic, alicyclic or aromatic hydrocarbons such as petroleum ether, hexane, heptane,
• dimethylformamide is particularly preferably used.
• Xylene is particularly preferably used when carrying out process (C) according to the invention.
• Suitable bases for carrying out process (A) according to the invention are all inorganic and organic bases customary for such reactions.
• potassium carbonate or cesium carbonate is particularly preferably used.
• DBU is particularly preferably used when carrying out process (B) according to the invention.
• potassium carbonate cesium carbonate, sodium tert-butanolate or potassium phosphate are particularly preferably used.
• any commercially available microwave apparatus suitable for this reaction can be used (e.g. ETHOS 1600 from MLS GmbH, Leutkirch, Germany).
• a palladium catalyst is generally used, which in turn can be used with or without the addition of further ligands.
• Pd (OAc) 2 very particularly preferably Pd (OAc) 2 .
• Triarylphosphines, trialkylphosphines or arsines are suitable as ligands.
• reaction temperatures can be varied over a wide range when carrying out processes (A), (B) and (C). In general, temperatures between -20 ° C and 200 ° C, preferably between 0 ° C and 150 ° C.
• the crude product is freed of any existing impurities by customary methods, such as chromatography or recrystallization.
• Formula (I-c) provides a general definition of the pyrazolylpyrimidines required as starting materials when carrying out process (D) according to the invention.
• R 19 of this formula are preferably R, R, X, n, Z and R, particularly preferably or very particularly preferably for those meanings which are already preferred for these radicals in connection with the description of the substances of the formula (I) according to the invention, were particularly preferred, etc.
• the pyrazolylpyrimidines of the formula (I-c) come under the definition of the compounds of the formula (I) according to the invention. They can be produced, for example, by one of the processes (A), (B), (C), (G), (H), (J) or (K) according to the invention.
• Suitable oxidizing agents for carrying out process (D) according to the invention are all customary oxidizing agents which can be used for sulfur oxidation.
• Hydrogen peroxide, organic peracids, such as, for example, peracetic acid, m-chloroperbenzoic acid, p-nitroperbenzoic acid or atmospheric oxygen are particularly suitable.
• Inert organic solvents are also suitable as diluents for carrying out process (D) according to the invention.
• Hydrocarbons such as gasoline, benzene, toluene, hexane or petroleum ether, are preferably used; chlorinated hydrocarbons, such as dichloromethane, 1, 2-dichloroethane, chloroform, carbon tetrachloride or chlorobenzene; Ethers, such as diethyl ether, dioxane or tetrahydrofuran; Carboxylic acids, such as acetic acid or propionic acid, or dipolar aprotic Solvents such as acetonitrile, acetone, ethyl acetate or dimethylformamide.
• process (D) according to the invention can be carried out in the presence of an acid binder.
• an acid binder As such, all commonly used organic and inorganic acid binders come into question. Alkaline earth metal or alkali metal hydroxides, acetates or carbonates, such as calcium hydroxide, sodium hydroxide, sodium acetate or sodium carbonate, are preferably used.
• process (D) according to the invention can be carried out in the presence of a suitable catalyst.
• a suitable catalyst All metal salt catalysts customarily used for such sulfur oxidations are suitable as such. Examples include ammonium molybdate and sodium tungstate.
• reaction temperatures can be varied within a substantial range when carrying out process (D) according to the invention. In general, temperatures between -20 ° C and + 70 ° C, preferably at temperatures between 0 ° C and + 50 ° C.
• Compound of formula (Ic) generally 1.8 to 3.0 mol, preferably double molar amounts of oxidizing agent. However, it is also possible to use the reaction components in other ratios.
• the processing takes place according to the usual procedures. In general, the procedure is that the reaction mixture is concentrated, extracted, the organic phase is washed, dried, filtered and concentrated. The residue is optionally removed using customary methods, such as matography or recrystallization, freed of any impurities that may still be present.
• Formula (IV) provides a general definition of the halopyrimidines required as starting materials when carrying out process (E) according to the invention.
• R 1 , R 2 and Z are preferably, particularly preferably or very particularly preferably those meanings which, in connection with the description of the substances of the formula (I) according to the invention, are preferred for these radicals, particularly preferably etc. . were called.
• Shark preferably represents fluorine, chlorine, bromine or iodine, particularly preferably chlorine, bromine or iodine, very particularly preferably chlorine or bromine.
• R a has the meanings given above.
• the halopyrimidines of the formula (IV) are new. They can be made by
• a base e.g. triethylamine
• a diluent e.g. dioxane
• Formula (XII) provides a general definition of the pyrimidine compounds required as starting materials when carrying out process (a). In this
• Formula Shark 2 preferably represents fluorine, chlorine, bromine or iodine, particularly preferably chlorine, bromine or iodine.
• Y 2 preferably represents oxygen or -NR 9 -.
• R 1 , R 2 and R 9 are preferably, particularly preferably or very particularly preferably those meanings which have already been mentioned as preferred, particularly preferred, etc. in connection with the description of the substances of the formula (I) according to the invention for these radicals.
• Pyrimidine compounds of the formula (XII) are known and / or can be prepared by known methods.
• Formula (XIII) provides a general definition of the compounds required as further starting materials when carrying out process (a).
• Y 2 preferably represents oxygen or -NR 9 -.
• Z and R 9 are preferably, particularly preferably or very particularly preferably those meanings which have already been associated with the description of the substances according to the invention
• Suitable diluents for carrying out process (E) according to the invention are all customary inert, organic solvents.
• Halogenated aliphatic, alicyclic or aromatic hydrocarbons such as petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene or decalin; Chlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, 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-diethoxyethane 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-methylpyrrolidone or hexamethylphosphoric triamide. N-Methylpyrrolidone or xylene is particularly preferably used.
• Suitable bases for carrying out process (E) according to the invention are all inorganic and organic bases customary for such reactions.
• Alkaline earth or alkali metal hydroxides such as sodium hydroxide, calcium hydroxide, potassium hydroxide, or also ammonium hydroxide
• alkali metal hydrides such as sodium hydride
• alkali metal carbonates such as sodium carbonate, potassium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate, cesium carbonate
• tertiary amines such as trimethylamine, triethylamine, tri-butylamine, N, N-dimethylaniline, pyridine, N-methylpiperidine, N, N-dimethylamino-pyridine, diazabicyclooctane (DABCO), diazabicyclonones (DBN) or diazabicyclo- undecene (DBU ).
• Process (E) according to the invention can also be carried out in the presence of a catalyst.
• a palladium catalyst is generally used, which in turn can be used with or without the addition of further ligands.
• Pd 2 (dba) 3 [dba dibenzylidene acetone] or Pd (OAc) 2 , particularly preferably PdCl 2 (dppf), Pd (PPh 3 ) 4 , PdCl 2 (PPh 3 ) 2 , or Pd (OAc) 2 , very particularly preferably Pd (OAc) 2 .
• Triarylphosphines, trialkylphosphines or arsines are suitable as ligands.
• reaction temperatures can be varied within a substantial range when carrying out process (E) according to the invention. In general, temperatures between -20 ° C and 200 ° C, preferably between 0 ° C and 150 ° C.
• the pyrazolylpyrimidine halides required as starting materials when carrying out process (F) according to the invention are general by the formula (V) Are defined.
• R 1 , R 2 , X and n are preferably, particularly preferably or very particularly preferably those meanings which, in connection with the description of the substances of the formula (I) according to the invention, are preferred, particularly preferred, etc. for these radicals .
• Shark 3 preferably represents fluorine, chlorine, bromine or iodine, particularly preferably chlorine, bromine or iodine.
• X and n have the meanings given above, if appropriate in the presence of a base (for example cesium carbonate) and if appropriate in the presence of a diluent (for example dioxane).
• a base for example cesium carbonate
• a diluent for example dioxane
• Formula (XIV) provides a general definition of the pyrimidine compounds required as starting materials when carrying out process (b). In this
• Formula R 1 and R 2 are preferred, particularly preferred or very particularly preferred, for those meanings which have already been mentioned as preferred, particularly preferred, etc. in connection with the description of the substances of the formula (I) according to the invention for these radicals.
• Shark is preferably fluorine, chlorine, bromine or iodine, particularly preferably chlorine, bromine or iodine.
• Pyrimidine compounds of the formula (XIV) are known and / or can be prepared by known methods.
• Formula (VI) provides a general definition of the organometallic compounds required as starting materials when carrying out process (FI) according to the invention.
• Z, A and E are preferred, particularly preferred or very particularly preferred for those meanings which have already been mentioned as preferred, particularly preferred, etc. for these radicals in connection with the description of the substances of the formula (I) according to the invention.
• Organometallic compounds of the formula (VI) are known and / or can be prepared by known processes.
• Formula (VII) provides a general definition of the organometallic compounds required as starting materials when carrying out process (F2) according to the invention.
• Z is preferred, particularly preferred or very particularly preferred for those meanings which have already been mentioned as preferred, particularly preferred etc. in connection with the description of the substances of the formula (I) according to the invention for these radicals.
• Organometallic compounds of the formula (VII) are known and / or can be prepared by known processes.
• trialkyltin azides required for carrying out process (F2) according to the invention are known. Trimethyltin azide or tri (n-butyl) tin azide is preferably used.
• Suitable diluents for carrying out process (F) according to the invention are all customary inert, organic solvents.
• Halogenated aliphatic, alicyclic or aromatic hydrocarbons such as petroleum ether, hexane, heptane, cyclohexane, may preferably be used.
• Suitable bases for carrying out process (F) according to the invention are all inorganic and organic bases customary for such reactions.
• Alkaline earth or alkali metal hydroxides such as sodium hydroxide, calcium hydroxide, potassium hydroxide, or else ammonium hydroxide
• alkali metal hydrides such as sodium hydride
• alkali metal carbonates such as sodium carbonate, potassium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate, are preferably usable.
• Alkali or alkaline earth metal acetates such as sodium acetate, potassium acetate, calcium acetate, and also tertiary amines such as trimethylamine, triethylamine, tributylamine, N, N-dimethylaniline, pyridine, N-methylpiperidine, N, N-dimethylaminopyridine, diazabicyclo-octane (DABCO), DABCO) (DBN) or diazabicycloundecene (DBU).
• tertiary amines such as trimethylamine, triethylamine, tributylamine, N, N-dimethylaniline, pyridine, N-methylpiperidine, N, N-dimethylaminopyridine, diazabicyclo-octane (DABCO), DABCO) (DBN) or diazabicycloundecene (DBU).
• a palladium catalyst is generally used, which in turn can be used with or without the addition of further ligands.
• Triarylphosphines, trialkylphosphines or arsines are suitable as ligands.
• reaction temperatures can be varied over a wide range when carrying out process (F) according to the invention. In general, temperatures between -20 ° C and 200 ° C, preferably between 0 ° C and 150 ° C.
• 1 mol or a slight excess of compound of the formula (VI) is generally employed per mol of compound of the formula (V) or, alternatively, 1 mol or a slight excess in a first stage Compound of formula (VII) and then in a second stage 1 mol or a slight excess of a trialkyltin azide.
• the reaction components in other ratios.
• the processing takes place according to usual methods. In general, the reaction mixture is concentrated, extracted, the organic phase is washed, dried, filtered and concentrated. The residue if necessary, any impurities still present are removed by customary methods, such as chromatography or recrystallization.
• Formula (Ig) provides a general definition of the pyrazolylpyrimidines required as starting materials when carrying out process (G) according to the invention.
• Y 3 preferably represents a direct bond, oxygen, sulfur or -NR 9 -.
• R 1 , R 2 , X, n, Z, A and R 9 are preferred, particularly preferred or very particularly preferred for those meanings which are already preferred for these radicals in connection with the description of the substances of the formula (I) according to the invention , particularly preferred, etc. were mentioned.
• Pyrazolylpyrimidines of the formula (I-g) are also compounds according to the invention which can be prepared, for example, by using
• R 1 , R 2 , X, n, Y 3 , A and R 16 have the meanings given above,
• Pyrazolylpyrimidines of formula (Ir) are also part of this invention. They can be produced, for example, by one of the processes (A), (B), (C) or (G) according to the invention.
• Formula (IX) provides a general definition of the hydroxides required as starting materials when carrying out process (G) according to the invention.
• M is preferably, particularly preferably or very particularly preferably those meanings which have already been mentioned as preferred, particularly preferred, etc. for these radicals in connection with the description of the substances of the formula (I) according to the invention.
• Hydroxides of the formula (IX) are known and / or can be prepared by known processes.
• Suitable diluents for carrying out the process (G) according to the invention are all customary protic solvents.
• Water or alcohols such as methanol, ethanol; Nitriles, such as acetonitrile, propionitrile, n- or i-butyronitrile or benzonitrile. Water or alcohols are particularly preferably used.
• reaction temperatures can be varied over a wide range when carrying out process (G) according to the invention.
• temperatures between 0 ° C and 200 ° C, preferably between 0 ° C and 150 ° C, most preferably between 20 ° C and 100 ° C.
• reaction mixture is concentrated, extracted, the organic phase is washed, dried, filtered and concentrated. geengt. The residue is optionally freed of any impurities that may still be present, using customary methods, such as chromatography or recrystallization.
• Formula (X) provides a general definition of the nitriles required as starting materials when carrying out process (H) according to the invention.
• this formula
• R, R, X, n and Z are preferred, particularly preferred or very particularly preferred for those meanings which, in connection with the description of the substances of the formula (I) according to the invention, are preferred for these radicals, particularly preferred, etc. were called.
• Nitriles of the formula (X) are new. They can be made by
• R 1 , R 2 , X and n have the meanings given above,
• a diluent e.g. toluene
• an acid binder e.g. sodium hydroxide
• R, R, X and n are preferably, particularly preferably or very particularly preferably those meanings which have already been mentioned as preferred, particularly preferred, etc. for these radicals in connection with the description of the substances of the formula (I) according to the invention were.
• Thiols of formula (XV) are new. They can be made, for example, by
• Formula (XVI) provides a general definition of the chlorinated nitriles required as starting materials when carrying out process (d).
• Z is preferably, particularly preferably or very particularly preferably those meanings which have already been mentioned as preferred, particularly preferred, etc. for these radicals in connection with the description of the substances of the formula (I) according to the invention.
• trialkyltin azides required for carrying out process (H) according to the invention are known. Trimethyltin azide or is preferably used
• Suitable diluents for carrying out process (H) according to the invention are all customary inert, organic solvents.
• Halogenated aliphatic, alicyclic or aromatic hydrocarbons such as petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene or decalin, may optionally be used; Chlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, 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-diethoxyethane 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-methylpyrrolidone or hexamethylphosphoric triamide; Esters such as methyl acetate or ethyl acetate; Sulfoxides, such as dimethyl sulfoxide or sulfones, such as sulfolane. Toluene is particularly preferably used.
• reaction mixture is concentrated, extracted, the organic phase is washed, dried, filtered and concentrated.
• residue is optionally freed of any impurities that may still be present, using customary methods, such as chromatography or recrystallization.
• pyrazolylpyrimidines required as starting materials when carrying out process (J) according to the invention are generally defined by the formula (Ik).
• Y 3 preferably represents a direct bond, oxygen, sulfur or
• R 1 , R 2 , X, n, Z and R 9 are preferably, particularly preferably or very particularly preferably those meanings which are particularly preferred for these radicals already in connection with the description of the substances of the formula (I) according to the invention preferred etc. were mentioned.
• Pyrazolylpyrimidines of the formula (I-k) are new. They can be made by
• R, ⁇ , R, X and n have the meanings given above,
• Formula (XVII) provides a general definition of the succinimides required as starting materials for process (f).
• Y 4 preferably represents oxygen, sulfur or -NR 9 -.
• Z and R 9 are preferably, particularly preferably or very particularly preferably those meanings which have already been mentioned as preferred, particularly preferred etc. in connection with the description of the substances of the formula (I) according to the invention for these radicals.
• Formula (XVIII) provides a general definition of the Grignard compounds required as starting materials for process (f).
• Z is preferably, particularly preferably or very particularly preferably those meanings which have already been mentioned as preferred, particularly preferred, etc. for these radicals in connection with the description of the substances of the formula (I) according to the invention.
• Formula (XIX) provides a general definition of the methylsulfonylpyrimidines required as starting materials when carrying out process (f).
• R 1 , R 2 , X and n are preferred, particularly preferred or very particularly preferred for those meanings which are already associated with the
• Methylsulfonylpyrimidines of the formula (XIX) are new. They can be made by g) methylthiopyrimidines of the formula (XX)
• R, R, X and n have the meanings given above, with an oxidizing agent (e.g. m-chloro-benzoic acid) optionally in
• a diluent e.g. chloroform
• Formula (XX) provides a general definition of the methylthiopyrimidines required as starting materials when carrying out process (g).
• R 1 , R 2 , X and n are preferred, particularly preferred or very particularly preferred for those meanings which, in connection with the description of the substances of the formula (I) according to the invention, are preferred, particularly preferred, etc. for these radicals . were called.
• Methylthiopyrimidines of formula (XX) are new. They can be made by
• a base e.g. cesium carbonate
• a diluent e.g. N-methylpyrrolidone
• Formula (XXI) provides a general definition of the pyrimidine derivatives required as starting materials when carrying out process (h).
• R 1 and R 2 are preferably, particularly preferably or very particularly preferably, those meanings which have already been mentioned as preferred, particularly preferred, etc. for these radicals in connection with the description of the substances of the formula (I) according to the invention.
• R 1 and R 2 have the meanings given above,
• a chlorinating agent eg POCl 3
• Formula (XXII) provides a general definition of the methylthiopyrimidines required as starting materials when carrying out process (j).
• R 1 and R 2 are preferably, particularly preferably or very particularly preferably, those meanings which have already been mentioned as preferred, particularly preferred, etc. for these radicals in connection with the description of the substances of the formula (I) according to the invention.
• Suitable diluents for carrying out process (J) according to the invention are all customary inert, organic solvents.
• Nitriles such as acetonitrile, propionitrile, n- or i-butyronitrile or benzonitrile can preferably be used;
• Amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylformanilide, N-methylpyrrolidone or hexamethylphosphoric triamide;
• Ethers such as diethyl ether, diisopropyl ether, methyl t-butyl ether, methyl t-amyl ether,
• the catalyst used is when carrying out the process according to the invention.
• reaction temperatures can be carried out when carrying out the process according to the invention.
• Process (J) can be varied over a wide range. In general, temperatures between -20 ° C and 200 ° C, preferably between 0 ° C and 150 ° C.
• Compound of formula (I-k) generally 1-10 mol% of a catalyst and carries out the reaction under a hydrogen pressure of 1 to 50 bar. However, it is also possible to use the reaction components in other ratios.
• the processing takes place according to usual methods. In general, the reaction mixture is concentrated and the organic one is extracted
• the residue is optionally freed of any impurities that may still be present, using customary methods, such as chromatography or recrystallization.
• Formula (XI) provides a general definition of the keto compounds required as starting materials when carrying out process (K) according to the invention.
• Y 3 preferably represents a direct bond, oxygen, sulfur or -NR 9 -.
• R 1 , R 2 , X, n, Z and R 9 are preferred, particularly preferred or very particularly preferred for those meanings which are already associated with the Description of the substances of the formula (I) according to the invention for these radicals as being preferred, particularly preferred, etc.
• Keto compounds of the formula (XI) are new. They can be made by
• R 1 , R 2 , X, n and Y 4 have the meanings given above,
• a diluent for example tetrahydrofuran
• an acid binder for example triethylamine
• a diluent for example tetrahydrofuran
• an acid binder for example triethylamine
• a catalyst for example Pd (PPh 3 ) 4 .
• Formula (XXIII) provides a general definition of the compounds required as starting materials in carrying out process (k).
• Y 4 preferably represents oxygen, sulfur or -NR 9 -.
• R 1 , R 2 , X, n and R 9 are preferably, particularly preferably or very particularly preferably those meanings which have already been associated with the description of the substances according to the invention
• Formula (XXIV) provides a general definition of the methyl ketones required as starting materials when carrying out process (k).
• Z is preferably, particularly preferably or very particularly preferably those meanings which have already been mentioned as preferred, particularly preferred, etc. for these radicals in connection with the description of the substances of the formula (I) according to the invention.
• Methyl ketones of the formula (XXIV) are known and / or can be prepared by known processes.
• Formula (XXV) provides a general definition of the pyrazolylpyrimidine halides required as starting materials when carrying out process (1). In this
• Formula R 1 , R 2 , X and n are preferred, particularly preferred or very particularly preferred for those meanings which have already been mentioned as preferred, particularly preferred, etc. for these radicals in connection with the description of the substances of the formula (I) according to the invention were.
• Shark 4 preferably represents chlorine, bromine or iodine, particularly preferably bromine or iodine, very particularly preferably iodine.
• Pyrazolylpyrimidine halides of formula (XXV) can e.g. are produced according to process (b).
• Suitable diluents for carrying out process (K) according to the invention are all customary inert, organic solvents.
• Halogenated aliphatic, alicyclic or aromatic hydrocarbons such as petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene or decalin; Chlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, 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-diethoxyethane 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-methylpyrrolidone or hexamethylphosphoric triamide
• Esters such as methyl acetate or ethyl acetate
• Sulfoxides such as dimethyl sulfoxide or sulfones, such as sulfolane. Toluene is particularly preferably used.
• the active compounds according to the invention are suitable, with good plant tolerance and favorable warm-blood toxicity, for combating animal pests, in particular insects, arachnids and nematodes which occur in agriculture, in forests, in the protection of stored products and materials and in the hygiene sector. They can preferably be used as pesticides. They are effective against normally sensitive and resistant species as well as against all or individual stages of development.
• the pests mentioned above include: From the order of the Isopoda, for example Oniscus asellus, Armadillidium vulgare, Porcellio scaber. From the order of the Diplopoda, for example, Blaniulus guttulatus.
• Phthiraptera e.g. Pediculus humanus co ⁇ oris, Haematopinus spp., Linognathus spp., Trichodectes spp., Damalinia spp.
• Thysanoptera e.g. Hercinothrips femoralis, Thrips tabaci, Thrips palmi, Frankliniella accidentalis.
• Heteroptera e.g. Eurygaster spp., Dysdercus intermedius
• From the order of the Homoptera for example Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Aphis fabae, Aphis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Phylloxera vastpp, Pemphigusum spp ., Phorodon humuli, Rhopalosiphum padi, Empoasca spp., Euscelis bilobatus, Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Laodelphax striatellus, Nilaparvata lugens, Aoni- diella aurantii, Aspidiotus hederae, Pseudococcus spp., Psylla
• Ephestia kuehniella Galleria mellonella, Tineola bisselliella, Tinea pellionella, Hofmannophila pseudospretella, Cacoecia podana, Capua reticulana, Choristoneura fumiferana, Clysia ambiguella, Homona magnanima, Tortrix viridana, Cnaphaloculus s.
• Hymenoptera e.g. Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis, Vespa spp.
• Plant-parasitic nematodes include e.g. Pratylenchus spp., Radopholus similis, Ditylenchus dipsaci, Tylenchulus semipenetrans, Heterodera spp., Globodera spp., Meloidogyne spp., Aphelenchoides spp., Longidorus spp., Xiphinema spp., Trichodorus spp., Bursaph.
• the compounds of the formula (I) according to the invention are distinguished in particular by an excellent action against caterpillars, beetle larvae, spider mites, aphids and leaf miners.
• the compounds according to the invention can also be used in certain concentrations or application rates as herbicides and microbicides, for example as fungicides, antifungal agents and bactericides. If appropriate, they can also be used as intermediates or products for the synthesis of further active ingredients.
• Plants are understood to mean all plants and plant populations, such as desired and undesirable wild plants or cultivated plants (including naturally occurring cultivated plants).
• Cultivated plants can be plants which can be obtained by conventional breeding and optimization methods or by biotechnological and genetic engineering methods or combinations of these methods, including the transgenic plants and including the plant cultivars which can or cannot be protected by plant breeders' rights.
• Plant parts are to be understood to mean all above-ground and underground parts and organs of plants, such as sprout, leaf, flower and root, examples being leaves, needles, stems, stems, flowers, fruiting bodies, fruits and seeds as well as roots, tubers and rhizomes.
• the plant parts also include crops and vegetative and generative propagation material, for example cuttings, tubers, rhizomes, offshoots and seeds.
• the treatment of the plants and parts of plants with the active compounds according to the invention is carried out directly or by acting on their surroundings, living space or storage space according to the customary treatment methods, e.g. by dipping, spraying, vaporizing, atomizing, scattering, spreading and, in the case of propagation material, in particular seeds, furthermore by single- or multi-layer coating.
• the active compounds according to the invention can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusts, pastes, soluble powders, granules, suspension emulsion concentrates, active substance-impregnated natural and synthetic substances and very fine encapsulations in polymeric substances ,
• formulations are prepared in a known manner, for example by mixing the active compounds according to the invention with extenders, that is to say liquid solvents and / or solid carriers, if appropriate using surface-active agents, ie emulsifiers and / or dispersants and / or foam-generating agents. If water is used as an extender, organic solvents can, for example, also be used as auxiliary solvents.
• extenders that is to say liquid solvents and / or solid carriers, if appropriate using surface-active agents, ie emulsifiers and / or dispersants and / or foam-generating agents.
• surface-active agents ie emulsifiers and / or dispersants and / or foam-generating agents.
• organic solvents can, for example, also be used as auxiliary solvents.
• aromatics such as xylene, toluene, or alkylnaphthalenes
• chlorinated aromatics and chlorinated aliphatic hydrocarbons such as chlorobenzenes, chlorethylenes or methylene chloride
• aliphatic hydrocarbons such as cyclohexane or paraffins, for example petroleum fractions, mineral and vegetable oils
• Alcohols such as butanol or glycol, and their ethers and esters
• ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone
• strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, and water.
• Ammonium salts and natural rock powders such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock powders, such as highly disperse silica, aluminum oxide and silicates, are suitable as solid carriers for granules: e.g. broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules from inorganic and organic flours as well as granules from organic material such as sawdust, coconut shells, corn cobs and tobacco stems;
• nonionic and anionic emulsifiers such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. Alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates;
• Possible dispersants are: e.g. Lignin sulfite waste liquors and methyl cellulose.
• Adhesives such as carboxymethyl cellulose, natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and natural phospho- lipids such as cephalins and lecithins and synthetic phospholipids.
• Other additives can be mineral and vegetable oils.
• Dyes such as inorganic pigments, e.g. Iron oxide, titanium oxide, ferrocyan blue and organic dyes such as alizarin, azo and metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc can be used.
• the formulations generally contain between 0.1 and 95% by weight of active compound, preferably between 0.5 and 90%.
• the active compounds according to the invention can be present in commercially available formulations and in the use forms prepared from these formulations, in a mixture with other active compounds, such as insecticides, attractants, sterilants, bactericides, acaricides, nematicides, fungicides, growth-regulating substances or herbicides.
• Insecticides include, for example, phosphoric acid esters, carbamates, carboxylic acid esters, chlorinated hydrocarbons, phenyl ureas, substances produced by microorganisms, etc.
• Famoxadone Fenapanil, Fenarimol, Fenbuconazole, Fenfuram, Fenitropan, Fenpiclonil, Fenpropidin, Fenpropimo ⁇ h, Fentinacetat, Fentinhydroxyd, Ferbam, Ferimzon, Fluzizina, Flumetover, Fluoromid, Fluquinconazol, Flusulfilamidol, Flufulfilamidol,
• Flutolanil Flutriafol, Folpet, Fosetyl-Alminium, Fosetyl-Sodium, Fthalide, Fuberidazole, Furalaxyl, Furametpyr, Furcarbonil, Furconazole, Furconazol-cis, Furmecyclox, Guazatin, Hexachlorobenzol, Hexaconazole, Hymexazol, Hymexazol
• Iodocarb Ipconazol, Iprobefos (IBP), Iprodione, Irumamycin, Isoprothiolan, Isovaldione,
• copper preparations such as: copper hydroxide, copper phthalate, copper oxychloride, copper sulfate, copper oxide, oxy-copper and
• Mancopper Mancozeb, Maneb, Meferimzone, Mepanipyrim, Mepronil, Metalaxyl, Metconazol, Methasulfocarb, Methfuroxam, Metiram, Metomeclam, Metsulfovax, Mildiomycin, Myclobutanil, Myclozolin,
• Paclobutrazole pefurazoate, penconazole, pencycuron, phosdiphene, pimaricin, piperalin,
• Tebuconazole Tebuconazole, tecloftalam, tecnazen, tetcyclacis, tetraconazole, thiabendazole, thicyofen, thifluzamide, thiophanate-methyl, thiram, dioxymid, tolclofos-methyl, tolylfluanid, triadimefon, triadimenol, triazbicyclidolid, triazbutichlaid, triazbutillamidolid Triflumizole, triforin, triticonazole,
• Methantetrathiol sodium salt Methyl-l- (2,3-dihydro-2,2-dimethyl-lH-inden-l-yl) -lH-imidazol-5-carboxylate,
• N-formyl-N-hydroxy-DL-alanine sodium salt O, O-diethyl- [2- (dipropylamino) -2-oxoethyl] ethylphosphoramidothioate,
• Cadusafos Carbaryl, Carbofuran, Carbophenothion, Carbosulfan, Cartap, Chloetho- carb, Chlorethoxyfos, Chlorfenapyr, Chlorfenvinphos, Chlorfluazuron, Chlormephos, Chlo ⁇ yrifos, Chlo ⁇ yrifos M, Chlovaporthrin, Cis-Resmethrin, Cispermethrin
• Fenamiphos Fenazaquin, Fenbutatin oxide, Fenitrothion, Fenothiocarb, Fenoxacrim, Fenoxycarb, Fenpropathrin, Fenpyrad, Fenpyrithrin, Fenpyroximate, Fenvalerate,
• Fipronil fluazuron, flubrocythrinate, flucycloxuron, flucythrinate, flufenoxuron,
• Granuloseviruses Halofenozide, HCH, Heptenophos, Hexaflumuron, Hexythiazox, Hydroprene,
• Metolcarb Metoxadiazone, Mevinphos, Milbemectin, Monocrotophos,
• Paecilomyces fumosoroseus Parathion A, Parathion M, Permethrin, Phenthoat, Phorat, Phosalone, Phosmet, Phosphamidon, Phoxim, Pirimicarb, Pirimiphos A,
• Pirimiphos M Profenofos, Promecarb, Propoxur, Prothiofos, Prothoat, Pymetrozine, Pyraclofos, pyresmethrin, pyrethrum, pyridaben, pyridathione, pyrimidifen, pyriproxyfen,
• Tefluthrin Temephos, Temivinphos, Terbufos, Tetrachlorvinphos, Theta-cyper-methrin, Thiamethoxam, Thiapronil, Thiatriphos, Thiocyclam hydrogen oxalate,
• Thiodicarb thiofanox, thuringiensin, tralocythrin, tralomethrin, triarathenes, triazamates, triazophos, triazuron, trichlophenidines, trichlorfon, triflumuron, trimethacarb,
• the active compounds according to the invention can furthermore be present in their commercially available formulations and in the use forms prepared from these formulations in a mixture with synergists.
• Synergists are compounds which increase the activity of the active compounds according to the invention without the added synergist itself having to be active.
• the active substance content of the use forms prepared from the commercially available formulations can vary within wide ranges.
• Application forms can be from 0.0000001 to 95% by weight of active compound, preferably between 0.0001 and 1% by weight.
• the application takes place in a customary manner adapted to the application forms.
• the active ingredient is distinguished by an excellent residual action on wood and clay as well as a good stability to alkali on limed substrates.
• plants and their parts can be treated according to the invention.
• transgenic plants and plant cultivars which may be obtained by genetic engineering methods are treated.
• Plants of the plant varieties which are in each case commercially available or in use are particularly preferably treated according to the invention.
• Plant cultivars are understood to mean plants with certain properties (“traits”) which have been obtained by conventional breeding, by mutagenesis or by recombinant DNA techniques. These can be cultivars, bio- and genotypes.
• the treatment according to the invention can also have additive (“synergistic”) effects.
• additive for example, reduced application rates and / or widening of the activity spectrum and / or an increase in the effect of the substances and agents which can be used according to the invention, better plant growth, increased tolerance to high or low temperatures, increased tolerance to drought or to water or soil salt content, increased flowering performance, easier harvesting, acceleration of ripening, higher crop yields, higher yields Quality and / or higher nutritional value of the meat products, higher storability and / or workability products that go beyond the expected effects.
• the preferred transgenic plants or plant cultivars to be treated according to the invention include all plants which have received genetic material through the genetic engineering modification, which gives these plants particularly advantageous, valuable properties (“traits”). Examples of such properties are better plant growth, Increased tolerance to high or low temperatures, increased tolerance to drought or to water or soil salt content, increased flowering performance, easier harvesting, acceleration of ripening, higher harvest yields, higher quality and / or higher nutritional value of the crop products, higher storability and / or workability of the Other and particularly highlighted examples of such properties are an increased defense of the plants against animal and microbial pests, such as against insects, mites, phytopathogenic fungi,
• transgenic plants Bacteria and / or viruses and an increased tolerance of the plants to certain herbicidal active ingredients.
• transgenic plants are the important cultivated plants, such as cereals (wheat, rice), corn, soybeans, potatoes, cotton, rapeseed and fruit plants (with the fruits apples, pears, citrus fruits and grapes), with corn, soybeans, potatoes , Cotton and rapeseed are highlighted.
• insects are particularly emphasized of the plants' increased defense against insects by toxins which arise in the plants, in particular those which are caused by the genetic material from Bacillus thuringenisis (for example by the genes Cry ⁇ A (a), Cry ⁇ A (b ), Cry ⁇ A (c), CryllA, CrylllA, CryIIIB2, Cry9c Cry2Ab, Cry3Bb and CrylF as well as their combinations) in the plants' increased defense against insects by toxins which arise in the plants, in particular those which are caused by the genetic material from Bacillus thuringenisis (for example by the genes Cry ⁇ A (a), Cry ⁇ A (b ), Cry ⁇ A (c), CryllA, CrylllA, CryIIIB2, Cry9c Cry2Ab, Cry3Bb and CrylF as well as their combinations) in the
• Plants are produced (hereinafter referred to as "Bt plants”).
• the properties also particularly emphasize the increased defense of plants against fungi, bacteria and viruses through systemic acquired resistance (SAR), systemin, phytoalexins, elicitors and resistance genes and appropriately expressed proteins and toxins.
• the traits that are particularly emphasized are the increased tolerance of the plants to certain herbicides. active substances, for example imidazolinones, sulfonylureas, glyphosate or phosphinotricin (for example "PAT” gene).
• the genes which impart the desired properties can also occur in combinations with one another in the transgenic plants.
• Bt plants are corn varieties, cotton varieties, soy varieties and potato varieties that are sold under the trade names YIELD GARD ® (e.g. corn, cotton, soy), KnockOut ® (e.g. corn), StarLink ® (e.g. corn), Bollgard ® ( Cotton), Nucotn ® (cotton) and NewLeaf ® (potato).
• YIELD GARD ® e.g. corn, cotton, soy
• KnockOut ® e.g. corn
• StarLink ® e.g. corn
• Bollgard ® Cotton
• Nucotn ® cotton
• NewLeaf ® potato
• herbicide-tolerant plants are corn varieties, cotton varieties and soybeans sold under the trade names Roundup Ready ® (tolerance to glyphosates such as corn,
• the herbicide-resistant plants include the varieties sold under the name Clearfield (eg maize). Of course, these statements also apply to plant varieties developed in the future or coming onto the market in the future with these or future-developed genetic properties (“traits”).
• the plants listed can be treated particularly advantageously according to the invention with the compounds of the general formula (I) or the active compound mixtures according to the invention.
• the preferred ranges given above for the active substances or mixtures also apply to the treatment of these plants.
• Plant treatment with the compounds or mixtures specifically listed in the present text should be particularly emphasized.
• the active compounds according to the invention act not only against plant, hygiene and
• ectoparasites animal parasites
• ectoparasites such as tortoise ticks, leather ticks, space mites, running mites, flies (stinging and licking), parasitic fly larvae, lice, featherlings, featherlings and fleas.
• parasites include: From the order of the Anoplurida, for example Haematopinus spp., Linognathus spp., Pediculus spp., Phtirus spp., Solenopotes spp.
• Nematocerina and Brachycerina e.g. Aedes spp., Anopheles spp., Culex spp., Simulium spp., Eusimulium spp., Phlebotomus spp., Lutzomyia spp., Culicoides spp., Chrysops spp., Hybomitra spp., Atylotus spp., Tabanus spp., Haematopota ., Philipomyia spp., Braula spp., Musca spp., Hydrotaea spp., Stomoxys spp., Haematobia spp., Morellia spp., Fannia spp., Glossina spp., Calliphora spp., Glossina spp., Calliphora spp., Glossina spp.,
• Siphonaptrida e.g. Pulex spp., Ctenocephalides spp., Xenopsylla spp., Ceratophyllus spp.
• Mesostigmata e.g. Argas spp., Ornithodorus spp., Otobius spp., Ixodes spp., Amblyomma spp., Boophilus spp., Dermacentor spp., Haemophysalis spp., Hyalomma spp., Rhipicephalus spp., Dermanyssus spp., Raillietia Pneumonyssus spp., Sternostoma spp., Varroa spp.
• Acarapis spp. Cheyletiella spp., Omithocheyletia spp., Myobia spp., Psorergates spp., Demodex spp., Trombicula spp., Listropho s spp., Acarus spp., Tyrophagus spp., Caloglyphus spp., Hypodectes spp., Pterolichus spp., Psoroptes spp., Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp., Knemidocoptes spp., Cytodites spp., Laminosiop
• the active compounds of the formula (I) according to the invention are also suitable for controlling arthropods which are used in agricultural animals, e.g. Cattle, sheep, goats, horses, pigs, donkeys, camels, buffalo, rabbits, chickens, turkeys, ducks, geese, bees, other pets such as e.g. Dogs, cats, house birds, aquarium fish and so-called experimental animals, such as Hamsters, guinea pigs, rats and
• Infest mice By combating these arthropods, deaths and reduced performance (in the case of meat, milk, wool, skins, eggs, honey, etc.) are to be reduced, so that the use of the active compounds according to the invention enables more economical and simple animal husbandry.
• the active compounds according to the invention are used in the veterinary sector in a known manner by enteral administration in the form of, for example, tablets, capsules, drinkers, drenches, granules, pastes, boluses, the feed-through method, suppositories, by parenteral administration, for example by Injections (intramuscular, subcutaneous, intravenous, intraperitoneal, etc.), implants, through nasal
• the active compounds of the formula (I) according to the invention can be used as formulations (for example powders, emulsions, flowable agents) which contain the active compounds according to the invention in an amount of 1 to 80% by weight, apply directly or after 100 to 10,000-fold dilution or use it as a chemical bath.
• insects may be mentioned by way of example and preferably, but without limitation:
• Lyctus brunneus Lyctus africanus
• Lyctus planicollis Lyctus linearis
• Lyctus pubes- cens Trogoxylon aequale
• Minthes rugicollis Xyleborus spec. Tryptodendron spec.
• Termites such as Kalotermes flavicolhs, Cryptotermes brevis, Heterotermes indicola, Reticulitermes flavipes, Reticulitermes santonensis, Reticulitermes lucihegus, Mastotermes darwiniensis, Zootermopsis nevadensis, Coptotermes formosanus.
• Bristle tails such as Lepisma saccharina.
• technical materials are to be understood as non-living materials, such as preferably plastics, adhesives, glues, papers and cartons, leather, wood, wood processing products and paints.
• the one to be protected against insect attack is very particularly preferably
• Wood and wood processing products which can be protected by the agent according to the invention or mixtures containing it are to be understood as examples:
• the active compounds according to the invention can be used as such, in the form of concentrates or generally customary formulations such as powders, granules, solutions, suspensions, emulsions or pastes.
• the formulations mentioned can be prepared in a manner known per se, e.g. by mixing the active ingredients according to the invention with at least one solvent or diluent, emulsifier, dispersant and / or binder or fixative, water repellant, optionally siccatives and UV stabilizers and optionally dyes and pigments and further processing aids.
• the insecticidal compositions or concentrates used to protect wood and wood-based materials contain the active compound according to the invention in a concentration of 0.0001 to 95% by weight, in particular 0.001 to 60% by weight.
• the amount of the agents or concentrates used depends on the type and occurrence of the insects and on the medium. The optimal amount can be determined in each case by test series. In general, however, it is sufficient to use 0.0001 to 20% by weight, preferably 0.001 to 10% by weight, of the active compound, based on the material to be protected.
• organic-chemical solvent or solvent mixture and / or an oily or oily or low-volatility organic-chemical solvent or solvent mixture and / or a polar organic-chemical solvent or solvent mixture and / or water and optionally an emulsifier and / or wetting agents.
• the organic chemical solvents used are preferably oily or oily solvents with an evaporation number above 35 and a flash point above 30 ° C., preferably above 45 ° C.
• Corresponding mineral oils or their aromatic fractions or mineral oil-containing solvent mixtures, preferably white spirit, petroleum and / or alkylbenzene, are used as such low-volatility, water-insoluble, oily and oily solvents.
• Mineral oils with a boiling range of 170 to 220 ° C, white spirit with a boiling range of 170 to 220 ° C, spindle oil with a boiling range of 250 to 350 ° C, petroleum or aromatics with a boiling range of 160 to 280 ° C, Te ⁇ entinöl and Like. Used.
• liquid aliphatic hydrocarbons with a boiling range from 180 to 210 ° C. or high-boiling mixtures of aromatic and aliphatic hydrocarbons with a boiling range from 180 to 220 ° C. and / or spindle oil and / or monochloronaphthalene, preferably ⁇ -monochloronaphthalene, are used.
• organic non-volatile oily or oily solvents with an evaporation number above 35 and a flash point above 30 ° C, preferably above 45 ° C can be partially replaced by slightly or medium-volatile organic chemical solvents, with the proviso that the solvent mixture also has an evaporation number 35 and a flash point above 30 ° C, preferably above 45 ° C, and that the insecticide-fungicide mixture is soluble or emulsifiable in this solvent mixture.
• part of the organic chemical solvent or solvent mixture or an aliphatic polar organic chemical solvent or solvent mixture is replaced.
• Aliphatic organic chemical solvents containing hydroxyl and / or ester and / or ether groups, such as, for example, glycol ethers, esters or the like, are preferably used.
• the organic-chemical binders which are known are water-dilutable and / or synthetic resins which are soluble or dispersible or emulsifiable in the organic-chemical solvents used and / or binding drying oils, in particular binders consisting of or containing an acrylate resin, a vinyl resin, e.g. Polyvinyl acetate, polyester resin, polycondensation or polyaddition resin, polyurethane resin, alkyd resin or modified alkyd resin, phenolic resin, hydrocarbon resin such as indene-coumarone resin, silicone resin, drying vegetable and / or drying oils and / or physically drying binders based on a natural and / / or synthetic resin used.
• binders consisting of or containing an acrylate resin, a vinyl resin, e.g. Polyvinyl acetate, polyester resin, polycondensation or polyaddition resin, polyurethane resin, alkyd resin or modified alkyd resin, phenolic resin, hydrocarbon resin such
• the synthetic resin used as a binder can be used in the form of an emulsion, dispersion or solution. Bitumen or bituminous substances up to 10% by weight can also be used as binders. In addition, known dyes, pigments, water-repellents, odor correctors and
• At least one alkyd resin or modified alkyd resin and / or a drying vegetable oil is preferably contained in the agent or in the concentrate as the organic chemical binder.
• Alkyd resins with an oil content of more than 45% by weight, preferably 50 to 68% by weight, are preferably used according to the invention.
• binder All or part of the binder mentioned can be replaced by a fixative (mixture) or a plasticizer (generic). These additives are intended to prevent volatilization of the active ingredients and crystallization or precipitation. They preferably replace 0.01 to 30% of the binder (based on
• the plasticizers come from the chemical classes of phthalic acid esters such as dibutyl, dioctyl or benzyl butyl phthalate, phosphoric acid esters such as tributyl phosphate, adipic acid esters such as di- (2-ethylhexyl) adipate, stearates such as butyl stearate or
• Amyl stearate, oleates such as butyl oleate, glycerol ether or higher molecular weight glycol ether, glycerol ester and p-toluenesulfonic acid ester.
• Fixing agents are chemically based on polyvinyl alkyl ethers such as e.g. Polyvinyl methyl ether or ketones such as benzophenone, ethylene benzophenone.
• Water is also particularly suitable as a solvent or diluent, if appropriate in a mixture with one or more of the above-mentioned organic chemical solvents or diluents, emulsifiers and dispersants.
• a particularly effective wood protection is achieved through industrial impregnation processes, e.g. Vacuum, double vacuum or pressure process.
• the ready-to-use compositions can optionally contain further insecticides and, if appropriate, one or more fungicides.
• the insecticides and fungicides mentioned in WO 94/29 268 are preferably suitable as additional admixing partners.
• the compounds mentioned in this document are an integral part of the present application.
• Insecticides such as chloro-riphos, phoxime, silafluofin, alphamethrin, cyfluthrin, cypermethrin, deltamethrin, permethrin, imidacloprid, NI-25, flufenoxuron, hexaflumuron, transfluthrin, methoxyclonoxyrid, thifloxuronophenrid, thifloxuronophenrid, thifloxuronophenid, thifloxuronophenrine, and fungloxidoxin fasciole, hexaconazole, azaconazole, propiconazole, tebuconazole, cyproconazole, metconazole, imazalil, dichlorofluoride, tolylfluanid, 3-iodo-2-propynyl butyl carbamate,
• the compounds according to the invention can be used to protect objects, in particular ship hulls, sieves, nets, structures, quay systems and signaling systems which come into contact with sea or brackish water.
• Baianus or pollicipes species increases the frictional resistance of ships and consequently leads to a significant increase in operating costs due to increased energy consumption and, in addition, frequent dry dock stays.
• heavy metals such as e.g. in bis (trialkyltin) sulfides, tri - «- butyltin laurate, tri-n-butyltin chloride, copper (I) oxide, triethyltin chloride, tri- ⁇ -butyl (2-phenyl-4-chlorophenoxy) tin, tributyltin oxide, molybdenum disulphide, antimony oxide, polymeric butyl titanate, phenyl- (bispyridine) - bismuth chloride, tri-rt-butylzinnfluorid, Manganethylenbisthiocarbamat, Zinkdime- thyldithiocarbamat, Zinkethylenbisthiocarbamat, zinc and copper salts of 2-pyridine-1-oxide dinthiol, Bisdimethyldithiocarbamoylzinkethylenbis
• the ready-to-use antifouling paints can also be used if necessary
• Active ingredients preferably algicides, fungicides, herbicides, molluscicides or others
• Suitable combination partners for the antifouling agents according to the invention are preferably:
• Molluscicides such as fentin acetate, metaldehyde, methiocarb, niclosamide, thiodicarb and trimethacarb; or conventional antifouling agents such as
• the antifouling agents used contain the active compound according to the invention of the compounds according to the invention in a concentration of 0.001 to 50% by weight, in particular of 0.01 to 20% by weight.
• the antifouling agents according to the invention further contain the usual ingredients such as e.g. in Ungerer, Chem. Ind. 1985, 37, 730-732 and Williams, Antifouling Marine Coatings, Noyes, Park Ridge, 1973.
• antifouling paints contain in particular binders.
• Examples of recognized binders are polyvinyl chloride in a solvent system, chlorinated rubber in a solvent system, acrylic resins in one
• Solvent system especially in an aqueous system, vinyl chloride-vinyl acetate copolymer systems in the form of aqueous dispersions or in the form of organic solvent systems, butadiene / styrene / acrylonitrile rubbers, drying oils, such as linseed oil, resin esters or modified hard resins in combination with tar or bitumen, Asphalt as well as epoxy compounds, minor
• Paints may also contain inorganic pigments, organic pigments or dyes, which are preferably insoluble in sea water. Paints may also contain materials such as rosin to enable controlled release of the active ingredients. The paints may also contain softening agents, modifying agents which influence the rheological properties and other conventional constituents.
• the compounds according to the invention or the abovementioned mixtures can also be incorporated into self-polishing antifouling systems.
• the active compounds according to the invention are also suitable for controlling animal
• Pests especially insects, arachnids and mites, which live in closed spaces such as apartments, factories, offices, vehicle cabins, etc. occurrence.
• they can be used alone or in combination with other active ingredients and auxiliaries in household insecticide products. They are against sensitive and resistant species as well as against all
• Stages of development effective. These pests include:
• Sco ⁇ ionidea e.g. Buthus occitanus.
• Acarina e.g. Argas persicus, Argas reflexus, Bryobia ssp., Dermanyssus gallinae, Glyciphagus domesticus, Omithodorus moubat, Rhipicephalus sanguineus, Trombicula alfreddugesi, Neutrombicula autumnalis, Dermatophageides pteronissimus, Dermatophagoides forinae.
• Opiliones e.g. Pseudosco ⁇ iones chelifer, Pseudosco ⁇ iones cheiridium, Opiliones phalangium.
• Diplopoda e.g. Blaniulus guttulatus, Polydesmus spp.
• Lepidoptera e.g. Achroia grisella, Galleria mellonella, Plodia inte ⁇ unctella, Tinea cloacella, Tinea pellionella, Tineola bisselliella.
• Ctenocephalides canis Ctenocephalides felis, Pulex irritans, Tunga penetrans, Xenopsylla cheopis.
• Hymenoptera e.g. Camponotus herculeanus, Lasius fuliginosus, Lasius niger, Lasius umbratus, Monomorium pharaonis, Paravespula spp.
• Nitro-lH-pyrazole, 0.65 g (4.3 mmol) l, 8-diazabicyclo [5.4.0] undec-7-ene (DBU) are dissolved in 10 ml DMF and in a microwave apparatus to 140 within 3 min ° C heated. After 20 minutes, the mixture is cooled to about 70 ° C. and then heated again to 140 ° C. for 20 minutes. The mixture is cooled, concentrated and purified by preparative HPLC.
• Eluents for determination in the acidic range 0.1% aqueous phosphoric acid, acetonitrile; linear gradient from 10% acetonitrile to 90% acetonitrile.
• the calibration was carried out using unbranched alkan-2-ones (with 3 to 16 carbon atoms) whose LogP values are known (determination of the LogP values on the basis of the retention times by linear interpolation between two successive alkanones).
• the lambda max values are determined on the basis of the UV spectra from 200 nm to 400 nm in the maxima of the chromatographic signals.
• HPLC-MS analysis is carried out under the following conditions:
• active compound 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier and the concentrate is diluted with water to the desired concentration.
• Vessels are filled with sand, active ingredient solution, Meloidogyne incognita egg larva suspension and lettuce seeds.
• the lettuce seeds germinate and the plantlets develop.
• the galls develop at the roots.
• the nematicidal effect is determined in% using the formation of bile. 100% means that no galls were found; 0% means that the number of galls on the treated plants corresponds to that of the untreated control.
• Emulsifier 1 part by weight of alkylaryl polyglycol ether
• Emulsifier 2 parts by weight of alkylaryl polyglycol ether
• Cabbage leaves (Brassica oleracea), which are heavily infested with peach aphids (Myzus persicae), are treated by being dipped into the preparation of active compound of the desired concentration.
• the kill is determined in%. 100% means that all aphids have been killed; 0% means that no aphids have been killed.
• Emulsifier 1 part by weight of alkylaryl polyglycol ether
• Emulsifier 1 part by weight of alkylaryl polyglycol ether
• Emulsifier 1 part by weight of alkylaryl polyglycol ether
• Seedlings of the broad bean (Vicia faba minor), which are infested with the green peach aphid (Myzus persicae), are immersed in an active ingredient preparation of the desired concentration and placed in a plastic can.
• the kill is determined in%. 100% means that all animals have been killed; 0% means that no animals have been killed.
• Emulsifier 1 part by weight of alkylaryl polyglycol ether
• Test insect Aphis gossypii
• Emulsifier 1 part by weight of alkylaryl polyglycol ether
• active compound 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier and the concentrate is diluted with water to the desired concentration.
• the active ingredient preparation is intimately mixed with the soil.
• concentration of the active substance in the preparation is practically irrelevant.
• the soil is filled into pots and planted with cucumber plants in the cotyledon stage. The active ingredient can thus be absorbed by the plant and transported to the leaves.
• the leaves are populated with the test animals mentioned above after 7 days. After another 7 days, the evaluation is carried out by counting or estimating the dead animals.
• the root systemic effect of the active ingredient is derived from the kill numbers. It is 100% when all test animals have been killed and 0% when as many test insects are still alive as in the untreated control.
• Test insect Aphis gossypii
• Emulsifier 1 part by weight of alkylaryl polyglycol ether
• Emulsifier 2 parts by weight of alkylaryl polyglycol ether
• active compound 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier and the concentrate is diluted to the desired concentration with water containing emulsifier.
• Cotton leaves which are heavily infested with the cotton aphid (Aphis gossypii), are treated by dipping into the active ingredient preparation of the desired concentration.
• the kill is determined in%. 100% means that all aphids have been killed; 0% means that no aphids have been killed.
• Emulsifier 2 parts by weight of alkylaryl polyglycol ether
• Emulsifier 2 parts by weight of alkylaryl polyglycol ether
• Cabbage leaves (Brassica oleracea) are treated by being dipped into the preparation of active compound of the desired concentration and populated with larvae of the horseradish leaf beetle (Phaedon cochleariae) while the leaves are still moist.
• the kill is determined in%. 100% means that all beetle larvae have been killed; 0% means that no beetle larvae have been killed.
• Emulsifier 2 parts by weight of alkylaryl polyglycol ether
• Emulsifier 1 part by weight of alkylaryl polyglycol ether
• active compound 1 part by weight of active compound is mixed with the stated amount of solvent, the stated amount of emulsifier is added and the concentrate is diluted with water to the desired concentration.
• the active ingredient preparation is poured onto the floor.
• the concentration of the active ingredient in the preparation is practically irrelevant, the only decisive factor is the amount of active ingredient per unit volume of soil, which is given in ppm (mg / 1). You fill the bottom in 0.25 1 pots and let them stand at 20 ° C.
• Emulsifier 1 part by weight of alkylaryl polyglycol ether
• Soybean shoots (Glycine max) of the Roundup Ready variety (trademark of Monsanto Comp. USA) are treated by dipping into the preparation of active compound of the desired concentration and populated with the tobacco bud caterpillar Heliothis virescens while the leaves are still moist.
• the kill is determined in%. 100% means that all caterpillars have been killed; 0% means that no caterpillars have been killed.

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• Organic Chemistry (AREA)
• Chemical & Material Sciences (AREA)
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• Veterinary Medicine (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Animal Behavior & Ethology (AREA)
• Medicinal Chemistry (AREA)
• Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
• Tropical Medicine & Parasitology (AREA)
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• Life Sciences & Earth Sciences (AREA)
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• Plural Heterocyclic Compounds (AREA)
• Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
• Agricultural Chemicals And Associated Chemicals (AREA)
• Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

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• 2001
  • 2001-02-22 DE DE10108480A patent/DE10108480A1/de not_active Withdrawn
• 2002
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  • 2002-02-11 KR KR1020037010576A patent/KR100854583B1/ko not_active IP Right Cessation
  • 2002-02-11 US US10/468,371 patent/US7087616B2/en not_active Expired - Fee Related
  • 2002-02-11 HU HU0303241A patent/HUP0303241A2/hu unknown
  • 2002-02-11 CN CNB028054326A patent/CN1301992C/zh not_active Expired - Fee Related
  • 2002-02-11 JP JP2002567926A patent/JP2004524315A/ja active Pending
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  • 2002-02-11 MX MXPA03007433A patent/MXPA03007433A/es active IP Right Grant
  • 2002-02-11 WO PCT/EP2002/001400 patent/WO2002068413A1/de active Application Filing
  • 2002-02-11 EP EP02711857A patent/EP1363905A1/de not_active Withdrawn
  • 2002-02-21 TW TW091102971A patent/TWI236475B/zh not_active IP Right Cessation
• 2003
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