Classifications

• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
  • A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
  • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
  • C07D487/04—Ortho-condensed systems

Definitions

• WO-A-99/41255 describes fungicidally active 1,2,4-triazolo [1,5-a] pyrimidine compounds which have, in the 5-position, a halogen atom, a cyano, haloalkoxy or alkoxy group and the 7-position carry an optionally substituted aliphatic, cycloaliphatic or aromatic radical.
• WO 03/004465 describes fungicidally active 1,2,4-triazolo [1, 5-a] pyrimidine compounds which have in the 7-position an optionally substituted aliphatic, cycloaliphatic or aromatic radical and in which Position carry an optionally substituted alkyl, alkenyl or alkynyl group.
• 1,2,4-triazolo [1,5-a] pyrimidines known from the prior art are in some cases unsatisfactory with respect to their fungicidal activity or have undesirable properties, such as a low compatibility with crops.
• the present invention is therefore based on the object to provide new compounds with better fungicidal activity and / or better crop compatibility.
• R 1 , R 2 independently of one another are hydrogen, C 1 -C 8 -alkyl, C 1 -C 8 -alkoxy, C 1 -C 8 -alkoxy, C 3 -C 8 -cycloalkyl, C 5 -C 10 -cycloalkyl, C 3 - C 8 -halocycloalkyl, C 2 -C 8 -alkenyl, C 4 -C 10 -alkadienyl, C 2 -C 8 -haloalkenyl, C 3 -C 6 -cycloalkenyl, C 3 -C 6 -halocycloalkenyl, C 2 -C 8 Alkynyl, C 2 -C 8 -haloalkynyl or phenyl, naphthyl, or a five- or six-membered saturated, partially unsaturated or aromatic heterocycle containing one, two, three or four heteroatoms from the group O, N or S,
• R 1 and R 2 may also together with the nitrogen atom to which they are attached form a five- or six-membered heterocyclyl or heteroaryl which is bonded via N and one, two or three further heteroatoms from the group O, N and S may contain as ring member and / or one or more Substi ⁇ tuents from the group halogen, CVCe-alkyl, CrC 6 -haloalkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -haloalkenyl, C 1 -C 6 - AIkOXy, d-Ce-alkoxycarbonyl, C r C 6 halo-alkoxy, C 3 -C 6 alkenyloxy, C 3 -C 6 haloalkenyloxy can carry and / or wherein two bonded to adjacent ring atoms substituents for d-C ⁇ -alkylene , Oxy-C 2 -C 4 -alkylene or OXy-
• R 1 and / or R 2 may carry one, two, three or four identical or different groups R a :
• R a is halogen, cyano, nitro, hydroxy, carboxyl, C r C 6 alkyl, C r C 6 haloalkyl, CrC ⁇ alkyl-carbonyl, C 3 -C 6 cycloalkyl, C r C 6 alkoxy, -C 6 haloalkoxy, CRCE alkoxycarbonyl, -C 6 -alkylthio, C r C 6 alkylamino, di-CrC 6 alkyl amino, d-Ce-alkylaminocarbonyl, di-CRCE-alkylaminocarbonyl,
• Groups R b can carry:
• R 3 are independently hydrogen, Ci-C 8 alkyl, CrC 8 -HalogenaIkyl,
• CRCS haloalkoxy, -C 8 alkoxy can be dC 8 -haloalkoxy or CrC-a-alkoxy-CiC- ⁇ -alkyl, where the 6 last-mentioned radicals carry one, two, three or four identical or different radicals R 0, wherein R ° has the meanings given for R a ;
• X is halogen, cyano, 5- or 6-membered saturated, partially unsaturated or aromatic heterocycle containing 1, 2 or 3 heteroatoms from the group O,
• R 5 , R 6 are independently selected from hydrogen, C 1 -C 6 -alkyl, C 2 -C 10 -alkyl, C 2 -C 10 -alkynyl, C 3 -C 6 -cycloalkyl or C 3 -C 6 - Cycloalkenyl, where the 5 last-mentioned radicals may be partially or completely halogenated or one, two, three or four radicals selected from cyano,
• a 1 represents hydrogen, hydroxy, Ci-C 8 alkyl, CRCS alkylamino or di- (C 1 -C 8 alkyl) amino;
• n 0, 1 or 2;
• a 2 is C 2 -C 8 alkenyl, C 1 -C 8 -alkoxy, CrC 6 haloalkoxy, amino, or one of said at A 1 groups is;
• R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 and R 15 are independently selected from hydrogen, C 1 -C 6 alkyl, C 3 -C 6 cycloalkyl, C C 2 -C 6 alkenyl or C 2 -C 6 alkynyl, where the four last-mentioned radicals may have one, two, three, four, five or six radicals R a ; or R 7 and R 8 , R 10 and R 11 , R 12 and R 13 and / or R 14 and R 15 together with the nitrogen atom to which they are attached, a four-, five- or six-membered saturated or partially unsaturated Ring, which can carry one, two, three or four, independently selected from R a selected substituents;
• n 0, 1, 2, 3, 4 or 5;
• the present invention thus relates to the 7-aminomethyl-1, 2-4-triazolo [1, 5-a] compounds of the general formula I and their agriculturally acceptable salts.
• the present invention furthermore relates to an agent for controlling harmful fungi, comprising at least one compound of the general formula I and / or an agriculturally acceptable salt thereof and at least one liquid or solid carrier.
• the compounds of the formula I can have one or more centers of chirality and are then present as enantiomer or diastereomer mixtures.
• the invention relates to both the pure enantiomers or diastereomers and mixtures thereof.
• Suitable compounds of general formula I also include all possible stereoisomers (cis / trans isomers) and mixtures thereof.
• transition metals preferably manganese, copper, zinc and iron, and the ammonium ion, which may if desired carry one to four C 1 -C 4 -alkyl substituents and / or a phenyl or benzyl substituent, preferably diisopropylammonium, tetramethylammonium, Tetrabutylammonium, trimethylbenzyl ammonium, further phosphonium ions, sulfonium ions, preferably tri (C r C 4 alkyl) sulfonium and Sulfoxoniumionen, preferably Tn (C 1 -C 4 alkyl) sulfoxonium, into consideration.
• Anions of useful acid addition salts are primarily chloride, bromide, fluoride, hydrogen sulfate, sulfate, dihydrogen phosphate, hydrogen phosphate, phosphate, nitrate, bicarbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate, and the anions of C r C 4 alkanoic acids, preferably formate, Acetate, propionate and butyrate. They can be formed by reaction of I with an acid of the corresponding anion, preferably hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid or nitric acid.
• Halogen fluorine, chlorine, bromine and iodine
• Alkyl saturated, straight-chain or branched hydrocarbon radicals having 1 to 4, 6 or 8 carbon atoms, e.g. C 1 -C 6 -alkyl, such as methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1, 1-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2 , 2-dimethylpropyl, 1-ethylpropyl, hexyl, 1, 1-dimethylpropyl, 1, 2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1, 1-dimethylbutyl, 1, 2 Dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-
• Haloalkyl straight-chain or branched alkyl groups having 1 to 2, 4, 6 or 8 carbon atoms (as mentioned above!), In which groups the hydrogen atoms may be partially or completely replaced by halogen atoms as mentioned above: in particular CrC 2 - Haloalkyl such as chloromethyl, bromomethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-chloroethyl, 1-bromoethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2, 2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl
• Alkenyl monounsaturated, straight-chain or branched hydrocarbon radicals having 2 to 4, 2 to 6, 2 to 8 or 2 to 10 carbon atoms and a double bond in any position, for example C 2 -C 6 -alkenyl, such as ethenyl, 1-propenyl, 2 -Propenyl, 1-methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl , 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl-1-butenyl, 3-methyl-1-butenyl, 1-methyl-2-butenyl, 2 Methyl 2-butenyl, 3-methyl-2-butenyl,
• Alkadienyl diunsaturated, straight-chain or branched hydrocarbon radicals having 4 to 10 carbon atoms and two double bonds in any position, for example 1, 3-butadienyl, 1-methyl-1,3-butadienyl, 2-methyl-1, 3 butadienyl, penta-1,3-dien-1-yl, hexa-1, 4-dien-1-yl, hexa-1,4-dien-3-yl, hexa-1,4-dien-6-yl, Hexa-1, 5-dien-1-yl, hexa-1, 5-dien-3-yl, hexa-1, 5-dien-4-yl, hepta-1, 4-dien-1-yl, hepta- 1, 4-dien-3-yl, hepta-1, 4-dien-6-yl, hepta-1, 4-dien-7-yl, hepta-1, 5-dien-1-yl, hepta-1, 5-dien-3
• Alkynyl straight-chain or branched hydrocarbon groups having 2 to 4, 2 to 6, 2 to 8 or 2 to 10 carbon atoms and one or two triple bonds in any position, for example C 2 -C 6 -alkynyl, such as ethynyl, 1-propynyl, 2 Propynyl, 1-butynyl,
• Cycloalkyl monocyclic, saturated hydrocarbon groups having 3 to 8 carbon ring members, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl;
• Bicycloalkyl bicyclic hydrocarbon radical having 5 to 10 C atoms, such as bicyclo [2.2.1] hept-1-yl, bicyclo [2.2.1] hept-2-yl, bicyclo [2.2.1] hept-7-yl, bicyclo [2.2.2] oct-1-yl, bicyclo [2.2.2] oct-2-yl, bicyclo [3.3.0] octyl, bicyclo [4.4.0] decyl and the like;
• C 1 -C 4 -alkoxy for an oxygen-bonded alkyl group having 1 to 4 carbon atoms: z. Methoxy, ethoxy, n-propoxy, 1-methylethoxy, butoxy, 1-methylpropoxy, 2-methylpropoxy or 1, 1-dimethylethoxy;
• -C 4 -haloalkoxy a C r C 4 alkoxy as mentioned above, the, chlorine, bromine / or iodine and is preferably fluorine stituiert sub ⁇ by partially or fully by fluorine, ie.
• 2,2,2-trichloroethoxy, OC 2 F 5 2-fluoropropoxy, 3-fluoropropoxy, 2,2-difluoropropoxy, 2,3-difluoropropoxy, 2-chloropropoxy, 3-chloropropoxy, 2,3-dichloropropoxy, 2-bromopropoxy , 3-bromopropoxy, 3,3,3-trifluoropropoxy, 3,3,3-trichloropropoxy, OCH 2 -C 2 F 5 , OCF 2 -C 2 F 5 , 1- (CH 2 F) -2-fluoroethoxy, 1 - (CH 2 Cl) -2-chloroethoxy, 1 - (CH 2 Br) -2-bromoethoxy, 4-fluorobutoxy, 4-chlorobutoxy, 4-bromobutoxy or monafluorobutoxy;
• d-Ce-haloalkoxy for CrC 4 haloalkoxy, as mentioned above, and z.
• Alkynyloxy alkynyl as mentioned above, which is bonded via an oxygen atom, for.
• B. C 3 -C 6 alkynyloxy such as 2-propynyloxy, 2-butynyloxy, 3-butynyloxy, 1-methyl-2-propynyloxy, 2-pentynyloxy, 3-pentynyloxy, 4-pentynyloxy, 1-methyl-2-butynyloxy, 1-methyl-3-butynyloxy, 2-methyl-3-butynyloxy,
• Seven-membered saturated or partially unsaturated heterocycle containing one, two, three or four heteroatoms from the group consisting of oxygen, nitrogen and sulfur as ring members e.g. mono- and bicyclic heterocycles having 7 Ring ⁇ members containing in addition to carbon ring members one to three nitrogen atoms and / or an oxygen or sulfur atom or one or two oxygen and / or sulfur atoms, for example tetra- and Hexahydroazepinyl as 2,3,4,5 -Tetrahydro [1 H] azepine-1, -2, -3, -A, 5, 6 or 7-yl, 3,4,5,6-tetrahydro [2H] azepine 2-, 3-, -A-, -5-, -6- or -7-yl,
• Sulfur or oxygen atom as ring members such as 2-furyl, 3-furyl, 2-thienyl, 3-thienyl, 2-pyrrolyl, 3-pyrrolyl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 3-isothiazolyl, 4-isothiazolyl , 5-isothiazolyl, 3-pyrazolyl, 4-pyrazolyl, 5-pyrazolyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 2-imidazolyl, 4-imidazolyl, 1 , 2,4-oxadiazol-3-yl, 1, 2,4-oxadiazol-5-yl, 1, 2,4-thiadiazol-3-yl, 1, 2,4-thiadiazol-5-yl, 1, 2,4-triazol-3-yl, 1, 3,4-oxadiazol-2-yl, 1, 3,4-thiadiazol-2-y
• 6-membered heteroaryl containing one to three nitrogen atoms as ring members such as pyridin-2-yl, pyridin-3-yl, pyridin-4-yl, 3-pyridazinyl, 4-pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 5- Pyrimidinyl, 2-pyrazinyl, 1, 3,5-triazin-2-yl and 1, 2,4-triazin-3-yl;
• Alkylene divalent linear chains of 1 to 6 CH 2 groups, e.g. B. CH 2 , CH 2 CH 2 , CH 2 CH 2 CH 2 , CH 2 CH 2 CH 2 CH 2 , CH 2 CH 2 CH 2 CH 2 , CH 2 CH 2 CH 2 CH 2 CH 2 and CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 J
• Oxyalkylene divalent unbranched chains of 2 to 4 CH 2 groups, wherein a valence is bonded via an oxygen atom to the skeleton, z. OCH 2 CH 2 , OCH 2 CH 2 CH 2 and OCH 2 CH 2 CH 2 CH 2 ;
• Oxyalkylenoxy divalent unbranched chains of 1 to 3 CH 2 groups, wherein both valences are bonded via an oxygen atom to the skeleton, z. OCH 2 O, OCH 2 CH 2 O and OCH 2 CH 2 CH 2 O.
• the subscript m and the substituents R 1 , R 2 , R 3 , R 4 , X and L independently of one another and preferably in combination, particularly preferably have the following meanings:
• R 1 is d-Ce-alkyl, C 2 -C 6 -alkenyl -alkyl, C 2 -C 6 alkynyl or C r C is 8 haloalkyl.
• R 1 is a group B:
• Z 1 is hydrogen, fluorine or C 1 -C 6 -fluoroalkyl
• Z 2 is hydrogen or fluorine
• Z 1 and Z 2 together form a double bond; q is 0 or 1; and R 16 is hydrogen or methyl.
• R 1 is C 3 -C 6 -cycloalkyl, which may be substituted by C 1 -C 4 -alkyl.
• R 1 is different from hydrogen and R 2 is hydrogen.
• R 1 then preferably has one of the be ⁇ preferred, or particularly preferred meanings given.
• R 1 and R 2 are different from hydrogen.
• R 1 is methyl or ethyl.
• R 1 then preferably has one of the preferred, or particularly preferred, indicated meanings.
• R 1 and R 2 together with the nitrogen atom to which they are bonded represent saturated heterocyclyl as defined above and in particular form a piperidinyl, morpholinyl or thiomorpholinyl ring, especially a piperidinyl ring , Heterocyc ⁇ lyl then is unsubstituted or substituted in the manner described above, especially by 1, 2 or 3 substituents R a, where preferred substituents on heterocyclyl are selected from halogen, C r C 4 alkyl, and -C 4 haloalkyl.
• R 1 and R 2 together with the nitrogen atom to which they are attached form a 4-methylpiperidine ring or 3,4-dimethylpiperidine ring.
• R 1 and R 2 together with the nitrogen atom to which they are attached form a 5- or 6-membered heteroaryl as defined above, which may be unsubstituted or substituted , preferably by 1, 2 or 3 groups R a .
• the group NR 1 R 2 forms a pyrazole ring, which is optionally substituted in the manner described above, and especially by 1 or 2 of the following radicals: halogen, -C 4 alkyl or C 4 -haloalkyl, in particular by 2 methyl groups or 2 trifluoromethyl groups in 3,5-position.
• R 3 and R 4 unab ⁇ pendently hydrogen, C r C 4 alkyl or C r C 4 alkoxy, particularly preferably hydrogen, C r C 2 -alkyl, such as Methyl or ethyl or C 1 -C 2 -alkoxy, such as methoxy or ethoxy.
• radicals R 3 or R 4 are hydrogen and the other radical R 3 or R 4 has the abovementioned meanings and in particular represents hydrogen, methyl or ethyl.
• X is halogen, cyano, -C 4 alkyl, -C 4 haloalkyl, C 1 -C 4 -alkoxy or C 2 -haloalkoxy stands.
• compounds of general formula I are preferred in which X is halogen, -C 2 alkyl, cyano or C r C 2 alkoxy, such as chlorine, methyl, cyano, methoxy or ethoxy.
• X is especially halogen and especially chlorine.
• m is preferably 1, 2, 3 or 4 and in particular 1, 2 or 3.
• L are: halogen, cyano, nitro, C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, C 1 -C 6 -alkoxy, a group C (S) A 2 or a group C (O) A 2 , wor ⁇ in A 2 has the meanings given above and preferably C 1 -C 4 -alkoxy, NH 2, -C 4 alkylamino or di-C 1 -C 4 -alkylamino stands.
• radical L is located ortho to the point of attachment to the triazolopyrimidine skeleton.
• a radical L arranged in the ortho position is preferably selected from halogen, especially fluorine or chlorine.
• m is 2 or 3 and at least one residue L is located ortho to the point of attachment to the triazolopyrimidine skeleton.
• preferred compounds of the general formula I are those in which a radical L in the 2-position and a further radical L in the 5-position to the point of attachment to the triazolopyrimidine skeleton are arranged.
• L 1 is fluorine, chlorine, trifluoromethyl or methyl
• L 2 is hydrogen, chlorine or fluorine
• L 3 is hydrogen, CN, nitro, fluorine, chlorine, C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy, a group C (S) A 2a or a group C (O) A 2a , where A 2a is C r C 4 alkoxy, NH 2 , C 1 -C 4 alkylamino or di-C 1 -C 4 alkylamino; L 4 is hydrogen, chlorine or fluorine; and L 5 are hydrogen, fluorine, chlorine or C r C 4 alkyl.
• R 5 and R 6 independently of one another are preferably hydrogen or C r C 4 alkyl.
• R 7 and R 8 are each independently preferably protected ⁇ selected from hydrogen or C r C 6 alkyl, especially hydrogen or C r C 4 alkyl such as methyl, ethyl, n- Propyl or isopropyl, especially hydrogen.
• R 9 is preferably hydrogen or C 1 -C 6 -alkyl.
• R 10 and R 11 independently of one another preferably represent hydrogen or C 1 -C 6 -alkyl.
• R 12 , R 13 , R 14 and R 15 are preferably independently selected from hydrogen or C 1 -C 6 alkyl.
• a 1 is preferably hydrogen, C 1 -C 6 -alkyl or amino.
• the index n is preferably 0, 1 or 2.
• a 2 is preferably C 1 -C 4 -alkoxy, NH 2, -C 4 alkylamino or di-C 1 -C 4 alkylamino.
• a preferred embodiment of the invention relates to compounds of the formula 1.1
• GC 2 -C 6 -alkyl in particular ethyl, n- and i-propyl, n-butyl, sec-butyl, tert-butyl, and C-rCvrAlkoxymethyl, in particular ethoxymethyl, or C 3 -C 6 -cycloalkyl, in particular cyclopentyl or cyclohexyl;
• R 2 is hydrogen or methyl
• X is chlorine, methyl, cyano, methoxy or ethoxy
• L is halogen, cyano, nitro, -C 6 alkyl, -C 6 haloalkyl, C 1 -C 6 -alkoxy, a group C (S) A 2 or a group C (O) A 2, wherein A 2 is C r C 4 is alkoxy, NH 2 , d-C 1 alkylamino or di-C 1 -C 4 alkylamino; and m is 0, 1, 2, 3, 4 or 5.
• D together with the nitrogen atom forms a five- or six-membered heterocyclyl or heteroaryl as defined above which is bonded via N and contains a further heteroatom from the group O, N and S as ring member and / or one or more substituents from the group halogen,
• R 3 and R 4 are independently hydrogen or C 1 -C 4 alkyl
• X is chlorine, methyl, cyano, methoxy or ethoxy
• L is halogen, cyano, nitro, C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, C 1 -C 6 -alkoxy, a group C (S) A 2 or a group C (O) A 2 , where A 2 is C r C 4- alkoxy, NH 2 ,
• Another preferred embodiment of the invention relates to compounds of the formula 1.3.
• Y is hydrogen or C 1 -C 4 -alkyl, in particular for methyl and ethyl,
• R 3 and R 4 are independently hydrogen or C r C 4 alkyl
• L is halogen, cyano, nitro, d-Ce-alkyl, d-Ce-haloalkyl, C 1 -C 6 -alkoxy, a
• R 1 , R 2 and L m are as defined above.
• R 3 and R 4 ste ⁇ hen independently hydrogen or optionally substituted C 8 - alkyl.
• Hal and Hal 'independently represent halogen, preferably chlorine or bromine.
• a 5,7-Dihalogentriazolopyrimidin the general formula II with an organometallic compound of formula VI
• the reaction is carried out under transition metal catalysis, such as Ni or Pd catalysis.
• transition metal catalysis such as Ni or Pd catalysis. This reaction can be carried out, for example, by the following methods: J. Chem. Soc. Perkin Trans. 1, 1187 (1994), Ibid 1, 2345 (1996); WO-A 99/41255; Aust. J. Chem., Vol. 43, 733 (1990); J. Org.
• step ii) The subsequent bromination of the 7-alkyl-6-aryltriazolopyrimidine compound of the general formula III in step ii) gives the 6-aryl-7- (bromoalkyl) -triazolopyrimidine
• Suitable brominating agents are, for example, N-bromoimides, such as N-bromosuccinimide, N-bromohydantoin, bromine or pyridinium tribromide.
• a radical initiator for example an organic peroxide such as dibenzoyl peroxide or an azo compound such as azobisisobutyronitrile or irradiation with light, may be advantageous for the course of the reaction.
• a catalytic amount is usually sufficient.
• Suitable solvents are, for example, aliphatic or aromatic hydrocarbons which may also be halogenated, for example carbon tetrachloride, trichloromethane, dichloromethane, organic acids such as acetic acid, inorganic acids, pyridine, ethers such as tetrahydrofuran or dioxane, sulfides, sulfoxides, sulfones and mixtures thereof ,
• the reaction temperature is usually between 10 0 C and the boiling point of the solvent.
• R 1 and R 2 have the meanings given above.
• This reaction is advantageously carried out at 0 to 70 0 C, preferably 10 to 35 0 C.
• Suitable solvents include ethers such as dioxane, diethyl ether, methyl tertiary butyl ether or especially tetrahydrofuran, halogenated hydrocarbons such as dichloromethane and aromatic Hydrocarbons such as toluene, xylene and the like, and mixtures thereof. [see. WO-A 98/46608].
• the reaction may be carried out in the presence of a base of, for example, a tertiary amine such as triethylamine or an inorganic base, e.g. B. alkaline earth metal carbonates, Erdal- kalimetallhydrogencarbonate, alkali metal carbonates or alkali metal bicarbonates such as sodium carbonate, sodium bicarbonate, potassium carbonate or cesium take place; Excess amine of the formula VII can also serve as a base.
• a base of, for example, a tertiary amine such as triethylamine or an inorganic base e.g. B. alkaline earth metal carbonates, Erdal- kalimetallhydrogencarbonate, alkali metal carbonates or alkali metal bicarbonates such as sodium carbonate, sodium bicarbonate, potassium carbonate or cesium take place; Excess amine of the formula VII can also serve as a base.
• the amines HNR 1 R 2 are generally commercially available or can be prepared by known methods.
• the compounds of the formula III can also be obtained, for example, advantageously by reacting compounds II with a cyanide (step iv in Scheme 1) and subsequently reacting the resulting 7-cyano-5-halogeno-triazolopyrimidine V with a organometallic reagent ( Step v in Scheme 1).
• a 5,7-dihalo-triazolopyrimidine II is first reacted with a cyanide of the formula M-CN to give a 7-cyano-5-halo-triazolopyrimidine V.
• the cation M has little significance, but for practical reasons ammonium, tetramethylammonium or tetraethylammonium cyanide, transition metal cyanides such as zinc cyanide or alkali metal or alkaline earth metal cyanides are usually preferred.
• the reaction is preferably carried out in a solvent.
• Suitable solvents are ethers such as diethyl ether, methyl tert-butyl ether, dioxane or tetrahydrofuran, aromatic hydrocarbons such as toluene, carbonitriles such as acetonitrile or propionitrile and mixtures thereof.
• the reaction temperature is in the range of 0 to 120 ° C., preferably 0 to 40 ° C.
• the 7-cyano-5-halo-triazolopyrimdin V thus obtained is subsequently reacted with an organo-metallic compound, for example a Grignard compound of the formula (CHR 3 R 4 ) -Mg-Hal or an organolithium compound of the formula (CHR 3 R 4 ) -Li, wherein R 3 and R 4 are independently hydrogen or optionally substituted CrCs-alkyl and Hal is bromine or chlorine, reacted (step v).
• an organo-metallic compound for example a Grignard compound of the formula (CHR 3 R 4 ) -Mg-Hal or an organolithium compound of the formula (CHR 3 R 4 ) -Li, wherein R 3 and R 4 are independently hydrogen or optionally substituted CrCs-alkyl and Hal is bromine or chlorine, reacted (step v).
• an organic solvent are ethers, such as diethyl ether, dibutyl ether,
• Methyl tert-butyl ether, tetrahydrofuran, aromatic hydrocarbons such as toluene and mixtures thereof may be advantageous to carry out the reaction in the presence of catalytic or, in particular, at least equimolar amounts of transition metal salts and / or compounds, in particular in the presence of Cu salts, such as Cu (I) halides, such as Cu (I) iodide perform.
• the reaction temperature is usually in a range of -100 to +100 ° C, preferably below 0 0 C and in particular in the range of -20 to -78 0 C.
• the cation M 1 in formula VIII has little significance; For practical reasons, ammonium, tetraalkylammonium salts such as tetramethylammonium or tetraethylammonium salts or alkali metal or alkaline earth metal salts are usually preferred (Scheme 2).
• the reaction temperature is usually 0 to 120 ° C., preferably 10 to 40 ° C. [cf. J. Heterocycl. Chem., Vol. 12, pp. 861-863 (1975)].
• Suitable solvents include ethers, such as dioxane, diethyl ether, methyl tert-butyl ether and, preferably, tetrahydrofuran, halogenated hydrocarbons, such as dichloromethane or dichloroethane, aromatic hydrocarbons, such as toluene, and mixtures thereof.
• Compounds of formula I in which X is dC 4 alkyl, -C 4 haloalkyl, C 2 -C 8 alkenyl, C 2 -C 6 haloalkenyl, C 2 -C 8 alkynyl, or C 2 -C 8 haloalkynyl may be prepared in an advantageous manner by reacting compounds I in which X is lied for Ha ⁇ , with organometallic compounds X a -mt, wherein X a is C r C 4 alkyl, -C 4 haloalkyl, C 2 -C 8 - Alkenyl, C 2 -C 8 -haloalkenyl, C 2 -C 8 -alkynyl or
• the reaction is preferably carried out in the presence of catalytic or in particular at least equimolar amounts of transition metal salts and / or compounds, in particular in the presence of Cu salts such as Cu (I) halides and especially Cu (I) iodide.
• the reaction is carried out in an inert organic solvent, for example one of the abovementioned ethers, in particular tetrahydrofuran, an aliphatic or cycloaliphatic hydrocarbon such as hexane, cyclohexane and the like, an aromatic hydrocarbon such as toluene or in a mixture of these solvents.
• the temperatures required for this purpose are in the range of -100 to + 10O 0 C and especially in the range of -80 0 C to + 40 0 C. Ver ⁇ drive this are known, for. B. from the cited prior art (see, for example, WO 03/004465)
• compounds of the formula I in which X is C 1 -C 4 -alkyl can also be prepared by reacting compounds I in which X is halogen, in particular chlorine, with malonates of the formula IX.
• This synthetic route is shown in Scheme 3.
• IX X "is hydrogen or C r C 3 alkyl and RC r C 4 alkyl.
• the compounds I are converted into compounds of the formula X, which anschlie ⁇ ruinedd after saponification be decarboxylated to give compounds I [cp. US 5,994,360] ,
• the subsequent saponification of the ester X is carried out under generally customary conditions.
• the alkaline or acidic saponification of the compounds X may be advantageous.
• the decarboxylation to I can already take place completely or partially.
• the decarboxylation is normally carried out at temperatures from 20 0 C to 180 0 C, preferably 50 0 C to 120 0 C, in an inert solvent, optionally in the Ge genwart an acid.
• Suitable acids are hydrochloric acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, p-toluenesulfonic acid.
• Suitable solvents are water, aliphatic hydrocarbons such as pentane, hexane, cyclohexane and petroleum ether, aromatic Hydrocarbons such as toluene, o-, m- and p-xylene, halogenated hydrocarbons such as methylene chloride, chloroform and chlorobenzene, ethers such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, dioxane, anisole and tetrahydrofuran, nitriles such as acetonitrile and propionitrile, ketones such as Acetone, methyl ethyl ketone, diethyl ketone and tert-butyl methyl ketone, alcohols such as methanol, ethanol
• reaction mixtures are worked up in a conventional manner, for. B. by mixing with water, separation of the phases and optionally chromatographic purification of the crude products.
• the intermediate and end products fall z. T. in the form of colorless or pale brownish, viscous oils, which are freed or purified under reduced pressure and at moderately elevated temperature of volatile fractions. If the intermediate and end products are obtained as solids, the purification can also be carried out by recrystallization or trituration.
• isomer mixtures are obtained in the synthesis, separation is generally not necessary since the individual isomers interconvert in part during preparation for use or during use (for example under the action of light, acid or base) can. Corresponding conversions can also take place after use, for example in the treatment of plants in the treated plant or in the harmful fungus to be controlled.
• the compounds I are suitable as fungicides. They are distinguished by their excellent activity against a broad spectrum of phytopathogenic fungi, in particular from the classes of the Ascomycetes, Deuteromycetes, Oomycetes and Bassiomycetes. They are in part systemically effective and can be used in crop protection as foliar and soil fungicides.
• Botrytis cinerea (gray mold) on strawberries, vegetables, ornamental plants and vines
• the fungicidal compositions generally contain between 0.1 and 95, preferably between 0.5 and 90 wt .-% active ingredient.
• the application rate of active ingredient depends on the type of application and the desired effect.
• Usual Wall quantities are in the material protection, for example, 0.001 g to 2 kg, preferably 0.005 g to 1 kg of active ingredient per cubic meter of treated material.
• the compounds I can be converted into the customary formulations, for.
• solutions emulsions, suspensions, dusts, powders, pastes and granules.
• the application form depends on the respective purpose; In each case, it should ensure a fine and uniform distribution of the compound according to the invention.
• the formulations are prepared in a known manner, for. By stretching the active ingredient with solvents and / or excipients, if desired using emulsifiers and dispersants.
• Suitable solvents / auxiliaries are essentially:
• solvent mixtures can also be used, carriers such as ground natural minerals (eg kaolins, clays, talc,
• Chalk and ground synthetic minerals (eg highly disperse silica, silicates); Emulsifiers such as nonionic and anionic emulsifiers (for example polyoxyethylene fatty alcohol ethers, alkyl sulfonates and arylsulfonates) and dispersants such as lignin-sulphite liquors and methylcellulose.
• Emulsifiers such as nonionic and anionic emulsifiers (for example polyoxyethylene fatty alcohol ethers, alkyl sulfonates and arylsulfonates) and dispersants such as lignin-sulphite liquors and methylcellulose.
• the surface-active substances used are alkali metal, alkaline earth metal, ammonium salts of lignin sulfonic acid, naphthalenesulfonic acid, phenolsulfonic acid, dibutylnaphthalenesulfonic acid, alkylarylsulfonates, alkyl sulfates, alkyl sulfonates, fatty alcohol sulfates, fatty acids and sulfated fatty alcohol glycol ethers, and condensation products of sulfonated naphthalene and naphthalene derivatives with formaldehyde , Condensation products of naphthalene or naphthalenesulfonic acid with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctylphenol, octylphenol, nonylphenol, alkylphenol polyglycol ethers, tributylphenyl
• mineral oil fractions of medium to high boiling point such as kerosene or diesel oil, also coal tar oils and oils of vegetable or animal origin.
• crack aliphatic, cyclic and aromatic hydrocarbons, eg. As toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, Me ⁇ ethanol, ethanol, propanol, butanol, cyclohexanol, cyclohexanone, isophorone, strong polar solvents, such.
• dimethyl sulfoxide N-methylpyrrolidone or water into consideration.
• Powders, dispersants and dusts may be prepared by mixing or co-grinding the active substances with a solid carrier.
• Granules, for. B. coated, impregnated and homogeneous granules can be prepared by binding the active compounds to solid carriers.
• Solid carriers are z.
• mineral earths such as silica gels, silicates, talc, kaolin, Attaclay, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium, fat, magnesium oxide, milled plastics, fertilizers such.
• ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas and vegetable products such as cereal flour, tree bark, wood and Nußschalenmehl, cellulose powder and other fes ⁇ te carriers.
• the formulations generally contain between 0.01 and 95 wt .-%, preferably between 0.1 and 90 wt .-% of the active ingredient.
• the active ingredients are used in a purity of 90% to 100%, preferably 95% to 100% (according to NMR spectrum).
• formulations are: 1. Products for dilution in water
• a compound of the invention 10 parts by weight of a compound of the invention are dissolved in water or a water-soluble solvent. Alternatively, wetting agents or other auxiliaries are added. When diluted in water, the active ingredient dissolves.
• a compound according to the invention 40 parts by weight of a compound according to the invention are dissolved in xylene with addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5%).
• This mixture is introduced by means of an emulsifier (Ultraturax) in water and brought to a homogeneous emulsion. Dilution in water results in emulsification.
• Agitator ball mill to a fine suspension of active ingredient crushed. Dilution in water results in a stable suspension of the active ingredient.
• Water-dispersible and Water-soluble Granules 50 parts by weight of a compound according to the invention are finely ground with the addition of dispersants and wetting agents and by means of technical equipment (eg extrusion, spray tower, fluidized bed) as water-dispersible or water-soluble granules produced. Dilution in water results in a stable dispersion or solution of the active ingredient.
• WP, SP Water-dispersible and Water-Soluble Powders (WP, SP) 75 parts by weight of a compound according to the invention are ground in a rotor-stator mill with the addition of dispersants and wetting agents and silica gel. Dilution in water results in a stable dispersion or solution of the active substance.
• 0.5 parts by weight of a compound according to the invention are finely ground and combined with 95.5% excipients. Common methods are the extrusion, the
• the active compound concentrations in the ready-to-use preparations can be varied within wide ranges. In general, they are between 0.0001 and 10%, preferably between 0.01 and 1%.
• wetting agents To the active ingredients oils of various types, wetting agents, adjuvants, herbicides, fungicides, other pesticides, bactericides, possibly also just immediately before use (tank mix), are added. These agents can be added to the compositions according to the invention in a weight ratio of 1:10 to 10: 1.
• the agents according to the invention can also be present in the application form as fungicides zu ⁇ together with other active ingredients, the z.
• fungicides zu ⁇ As with herbicides, insecticides, growth regulators, fungicides or with fertilizers.
• fertilizers When mixing the compounds I or the agents containing them in the application form as fungicides with other fungicides is obtained in many cases, an enlargement of the fungicidal spectrum of activity.
• the following list of fungicides with which the compounds according to the invention can be used together is intended to illustrate, but not limit, the possible combinations.
• Acylalanines such as benalaxyl, metalaxyl, ofurace, oxadixyl;
• Anilinopyrimidines such as pyrimethanil, mepanipyrim or cyrodinyl; • antibiotics such as cycloheximide, griseofulvin, kasugamycin, natamycin, polyoxin or streptomycin;
• Dicarboximides such as iprodione, myclozoline, procymidone, vinclozolin;
• Dithiocarbamates such as Ferbam, Nabam, Maneb, Mancozeb, Metam, Metiram, Propineb, Polycarbamate, Thiram, Ziram, Zineb;
• Copper fungicides such as Bordeaux broth, copper acetate, copper oxychloride, basic copper sulfate;
• Nitrophenyl derivatives such as binapacryl, dinocap, dinobutone, nitrophthalic-isopropyl;
• Phenylpyrroles such as fenpiclonil or fludioxonil
• Sulfenic acid derivatives such as captafol, captan, dichlofluanid, folpet, tolylfluanid;
• Cinnamic acid amides and analogues such as dimethomorph, flumetover or flumorph.
• Example 1 5-Chloro-7- (4-methylpiperidin-1-ylmethyl) -6- (2,4,6-trifluorophenyl) [1,2,4] triazolo [1,5-a] pyrimidine and 5- (4-methylpiperidin-1-yl) -7- (4-methylpiperidin-1-ylmethyl) -6- (2,4,6-trifluorophenyl) [1,2,4] triazolo [1, 5-a] pyrimidine
• Paprika seedlings of the cultivar "Neusiedler Ideal Elite" were sprayed to drip point with an aqueous suspension in the concentration of active compound specified below, after 2 to 3 leaves had developed well.
• the treated plants were inoculated with a spore suspension of Botrytis cinerea containing 1.7 ⁇ 10 6 spores / ml in a 2% aqueous biomalt solution.
• the test plants were placed in a climatic chamber with 22 to 24 0 C, darkness and high humidity. After 5 days, the extent of fungal infection on the leaves could be determined visually in%.

Landscapes

• Life Sciences & Earth Sciences (AREA)
• Organic Chemistry (AREA)
• Chemical & Material Sciences (AREA)
• Dentistry (AREA)
• Health & Medical Sciences (AREA)
• Engineering & Computer Science (AREA)
• Plant Pathology (AREA)
• General Health & Medical Sciences (AREA)
• Wood Science & Technology (AREA)
• Zoology (AREA)
• Environmental Sciences (AREA)
• Pest Control & Pesticides (AREA)
• Agronomy & Crop Science (AREA)
• Agricultural Chemicals And Associated Chemicals (AREA)
• Plural Heterocyclic Compounds (AREA)

Applications Claiming Priority (2)

Publications (1)

Family

ID=35539356

Family Applications (1)

Country Status (6)

Families Citing this family (2)

Family Cites Families (4)

• 2005
  • 2005-09-27 US US11/663,982 patent/US20080076785A1/en not_active Abandoned
  • 2005-09-27 CN CNA2005800404555A patent/CN101065383A/zh active Pending
  • 2005-09-27 BR BRPI0516140-1A patent/BRPI0516140A/pt not_active IP Right Cessation
  • 2005-09-27 WO PCT/EP2005/010440 patent/WO2006034848A1/de active Application Filing
  • 2005-09-27 EP EP05788730A patent/EP1797097A1/de not_active Withdrawn
• 2007
  • 2007-03-13 IL IL181900A patent/IL181900A0/en unknown

Non-Patent Citations (1)

Also Published As

Similar Documents

Legal Events