Patent Application
20080227796
The present invention relates to novel 7-amino-6-hetaryl-1,2,4-triazolo[1,5-a]pyrimidine compounds and to their use for controlling harmful fungi, and also to crop protection compositions comprising at least one such compound as active component.
EP-A 71 792, EP-A 550 113, EP-A 834 513 and WO-A 98/46608 describe fungicidally active 1,2,4-triazolo[1,5-a]pyrimidines which carry an optionally substituted phenyl ring in the 6-position, a halogen atom in the 5-position and an amino group in the 7-position.
WO 02/50077 describes similar 1,2,4-triazolo[1,5-a]pyrimidines which may furthermore carry a heterocyclic radical in the 6-position. Compounds carrying a 6-membered heteroaromatic radical in this position are not described.
EP-A 613 900 describes fungicidally active 1,2,4-triazolo[1,5-a]pyrimidine compounds which have a hydrogen atom or halogen atom in the 5-position and a secondary or tertiary amino group in the 7-position. These compounds have a cycloalkyl radical or heterocyclyl radical, for example a 3-thienyl radical, in the 6-position. Compounds carrying a 6-membered heteroaromatic radical in this position are not described.
WO 04/0011467 in turn describes fungicidally active 1,2,4-triazolo[1,5-a]pyrimidine compounds which have a halogen atom, a cyano group, an alkoxy group, an alkylthio group, an alkylsulfinyl group, an alkylsulfonyl group, an alkylamino group or an alkoxycarbonyl group in the 5-position. In the 7-position, these compounds may, inter alia, carry a tertiary amino group. In the 6-position, these compounds have a 5- or 6-membered heterocyclyl radical selected from the group consisting of optionally substituted pyrrolyl, thienyl, pyrazolyl, imidazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl and pyrimidyl.
Some of the 1,2,4-triazolo[1,5-a]pyrimidines known from the prior art are, with respect to their fungicidal action, not satisfactory, or they have unwanted properties, such as low crop plant compatibility.
Accordingly, it is an object of the present invention to provide novel compounds having improved fungicidal activity and/or better crop plant compatibility.
Surprisingly, this object is achieved by 7-amino-6-hetaryl-1,2,4-triazolo[1,5-a]pyrimidine compounds of the formula I defined below, and by the agriculturally acceptable salts of the compounds I.
Accordingly, the present invention relates to 7-amino-6-hetaryl-1,2,4-triazolo-[1,5-a]pyrimidine compounds of the formula I
and to the agriculturally acceptable salts of compounds of the formula I where the substituents R1, R2, Het, X and Y in formula I are as defined below:
The invention furthermore provides compounds of the formula I and salts thereof where R1, Het, X and Y are as defined above and R2 is an organic radical which contains 3 to 13 carbon atoms and one or more, for example 1, 2 or 3, silicon atoms, and optionally 1 to 3 identical or different heteroatoms from the group consisting of oxygen, nitrogen and sulfur, and which is unsubstituted or carries 1, 2, 3 or 4 identical or different substituents selected from the group consisting of halogen atoms and the substituents Ra. The invention furthermore provides compounds of the formula I in which Het, X and Y are as defined above and in which R1 and R2 together with the nitrogen atom to which they are attached are a heterocyclic ring which preferably has 3 to 12 ring members, which has one or more, for example 1, 2 or 3 silicon atoms and which is unsubstituted or carries 1, 2, 3 or 4 identical or different substituents selected from the group consisting of halogen atoms and the substituents Ra.
The present invention furthermore provides the use of the 7-amino-1,2,4-triazolo-[1,5-a]pyrimidine compounds of the formula I and their agriculturally acceptable salts for controlling phytopathogenic fungi (=harmful fungi), and a method for controlling phytopathogenic harmful fungi which comprises treating the fungi or the materials, plants, the soil or seed to be protected against fungal attack with an effective amount of at least one compound of the formula I and/or an agriculturally acceptable salt of I.
The present invention furthermore provides a composition for controlling harmful fungi, which composition comprises at least one compound of the formula I and/or an agriculturally acceptable salt thereof and at least one liquid or solid carrier.
Depending on the substitution pattern, the compounds of the formula I may have one or more centers of chirality, in which case they are present as mixtures of enantiomers or diastereomers. The invention provides both the pure enantiomers or diastereomers and their mixtures. Suitable compounds of the formula I also include all possible stereoisomers (cis/transisomers) and mixtures thereof.
Suitable agriculturally useful salts are especially the salts of those cations or the acid addition salts of those acids whose cations and anions, respectively, have no adverse effect on the fungicidal action of the compounds I. Thus, suitable cations are in particular the ions of the alkali metals, preferably sodium and potassium, of the alkaline earth metals, preferably calcium, magnesium and barium, and of the transition metals, preferably manganese, copper, zinc and iron, and also the ammonium iron which, if desired, may carry one to four C1-C4-alkyl substituents and/or one phenyl or benzyl substituent, preferably diisopropylammonium, tetramethylammonium, tetrabutylammonium, trimethylbenzylammonium, furthermore phosphonium ions, sulfonium ions, preferably tri(C1-C4-alkyl)sulfonium, and sulfoxonium ions, preferably tri(C1-C4-alkyl)sulfoxonium.
Anions of useful acid addition salts are primarily chloride, bromide, fluoride, hydrogen sulfate, sulfate, dihydrogenphosphate, hydrogenphosphate, phosphate, nitrate, bicarbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate, and also the anions of C1-C4-alkanoic acids, preferably formate, acetate, propionate and butyrate. They can be formed by reacting I with an acid of the corresponding anion, preferably hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid or nitric acid.
In the definitions of the variables given in the formulae above, collective terms are used which are generally representative for the substituent in question. The term Cn-Cm indicates the number of carbon atoms possible in each case in the substituent or substituent moiety in question:
halogen: fluorine, chlorine, bromine and iodine;
alkyl and the alkyl moieties in alkyloxy, alkylthio, alkylsulfinyl and alkylsulfonyl: saturated straight-chain or branched hydrocarbon radicals having 1 to 4, 6 or 8 carbon atoms, for example C1-C6-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-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl, 1-ethyl-2-methylpropyl and the like;
haloalkyl: straight-chain or branched alkyl groups having 1 to 2, 4, 6 or 8 carbon atoms (as mentioned above), where some or all of the hydrogen atoms in these groups may be replaced by halogen atoms as mentioned above: in particular C1-C2-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, pentafluoroethyl or 1,1,1-trifluoroprop-2-yl;
alkenyl and the alkenyl moieties in alkenyloxy: 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 C2-C6-alkenyl, such as ethenyl, 1-propenyl, 2-propenyl, 1-methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl-1-butenyl, 3-methyl-1-butenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, 1,1-dimethyl-2-propenyl, 1,2-dimethyl-1-propenyl, 1,2-dimethyl-2-propenyl, 1-ethyl-1-propenyl, 1-ethyl-2-propenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-1-pentenyl, 2-methyl-1-pentenyl, 3-methyl-1-pentenyl, 4-methyl-1-pentenyl, 1-methyl-2-pentenyl, 2-methyl-2-pentenyl, 3-methyl-2-pentenyl, 4-methyl-2-pentenyl, 1-methyl-3-pentenyl, 2-methyl-3-pentenyl, 3-methyl-3-pentenyl, 4-methyl-3-pentenyl, 1-methyl-4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyl, 1,1-dimethyl-2-butenyl, 1,1-dimethyl-3-butenyl, 1,2-dimethyl-1-butenyl, 1,2-dimethyl-2-butenyl, 1,2-dimethyl-3-butenyl, 1,3-dimethyl-1-butenyl, 1,3-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl, 2,2-dimethyl-3-butenyl, 2,3-dimethyl-1-butenyl, 2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, 3,3-dimethyl-1-butenyl, 3,3-dimethyl-2-butenyl, 1-ethyl-1-butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 2-ethyl-1-butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl, 1,1,2-trimethyl-2-propenyl, 1-ethyl-1-methyl-2-propenyl, 1-ethyl-2-methyl-1-propenyl, 1-ethyl-2-methyl-2-propenyl and the like;
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-yl, hepta-1,5-dien-4-yl, hepta-1,5-dien-7-yl, hepta-1,6-dien-1-yl, hepta-1,6-dien-3-yl, hepta-1,6-dien-4-yl, hepta-1,6-dien-5-yl, hepta-1,6-dien-2-yl, octa-1,4-dien-1-yl, octa-1,4-dien-2-yl, octa-1,4-dien-3-yl, octa-1,4-dien-6-yl, octa-1,4-dien-7-yl, octa-1,5-dien-1-yl, octa-1,5-dien-3-yl, octa-1,5-dien-4-yl, octa-1,5-dien-7-yl, octa-1,6-dien-1-yl, octa-1,6-dien-3-yl, octa-1,6-dien-4-yl, octa-1,6-dien-5-yl, octa-1,6-dien-2-yl, deca-1,4-dienyl, deca-1,5-dienyl, deca-1,6-dienyl, deca-1,7-dienyl, deca-1,8-dienyl, deca-2,5-dienyl, deca-2,6-dienyl, deca-2,7-dienyl, deca-2,8-dienyl and the like;
haloalkenyl: unsaturated straight-chain or branched hydrocarbon radicals having 2 to 10 carbon atoms and a double bond in any position (as mentioned above), where some or all of the hydrogen atoms in these groups may be replaced by halogen atoms as mentioned above, in particular fluorine, chlorine and bromine;
alkynyl and the alkynyl moieties in alkynyloxy: 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 C2-C6-alkynyl, such as ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-methyl-2-butynyl, 1-methyl-3-butynyl, 2-methyl-3-butynyl, 3-methyl-1-butynyl, 1,1-dimethyl-2-propynyl, 1-ethyl-2-propynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, 1-methyl-2-pentynyl, 1-methyl-3-pentynyl, 1-methyl-4-pentynyl, 2-methyl-3-pentynyl, 2-methyl-4-pentynyl, 3-methyl-1-pentynyl, 3-methyl-4-pentynyl, 4-methyl-1-pentynyl, 4-methyl-2-pentynyl, 1,1-dimethyl-2-butynyl, 1,1-dimethyl-3-butynyl, 1,2-dimethyl-3-butynyl, 2,2-dimethyl-3-butynyl, 3,3-dimethyl-1-butynyl, 1-ethyl-2-butynyl, 1-ethyl-3-butynyl, 2-ethyl-3-butynyl, 1-ethyl-1-methyl-2-propynyl and the like;
cycloalkyl and the cycloalkyl moieties in cycloalkoxy: monocyclic saturated hydrocarbon groups having 3 to 8 carbon ring members, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl;
cycloalkenyl: monocyclic monounsaturated hydrocarbon groups having 3 to 8, preferably 5 to 6, carbon ring members, such as cyclopenten-1-yl, cyclopenten-3-yl, cyclohexen-1-yl, cyclohexen-3-yl, cyclohexen-4-yl and the like;
bicycloalkyl: a bicyclic hydrocarbon radical having 5 to 10 carbon 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;
C1-C4-alkoxy: an alkyl group having 1 to 4 carbon atoms which is attached via an oxygen, for example, methoxy, ethoxy, n-propoxy, 1-methylethoxy, butoxy, 1-methylpropoxy, 2-methylpropoxy or 1,1-dimethylethoxy;
C1-C6-alkoxy: C1-C4-alkoxy as mentioned above, and also, for example, pentoxy, 1-methylbutoxy, 2-methylbutoxy, 3-methylbutoxy, 1,1-dimethylpropoxy, 1,2-dimethylpropoxy, 2,2-dimethylpropoxy, 1-ethylpropoxy, hexoxy, 1-methylpentoxy, 2-methylpentoxy, 3-methylpentoxy, 4-methylpentoxy, 1,1-dimethylbutoxy, 1,2-dimethylbutoxy, 1,3-dimethylbutoxy, 2,2-dimethylbutoxy, 2,3-dimethylbutoxy, 3,3-dimethylbutoxy, 1-ethylbutoxy, 2-ethylbutoxy, 1,1,2-trimethylpropoxy, 1,2,2-trimethylpropoxy, 1-ethyl-1-methylpropoxy or 1-ethyl-2-methylpropoxy;
C1-C4-haloalkoxy: a C1-C4-alkoxy radical as mentioned above which is partially or fully substituted by fluorine, chlorine, bromine and/or iodine, preferably by fluorine, i.e., for example, OCH2F, OCHF2, OCF3, OCH2Cl, OCHCl2, OCCl3, chlorofluoromethoxy, dichlorofluoromethoxy, chlorodifluoromethoxy, 2-fluoroethoxy, 2-chloroethoxy, 2-bromoethoxy, 2-iodoethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, 2-chloro-2-fluoroethoxy, 2-chloro-2,2-difluoroethoxy, 2,2-dichloro-2-fluoroethoxy, 2,2,2-trichloroethoxy, OC2F5, 2-fluoropropoxy, 3-fluoropropoxy, 2,2-difluoropropoxy, 2,3-difluoropropoxy, 2-chloropropoxy, 3-chloropropoxy, 2,3-dichloropropoxy, 2-bromopropoxy, 3-bromopropoxy, 3,3,3-trifluoropropoxy, 3,3,3-trichloropropoxy, OCH2—C2F5, OCF2—C2F5, 1-(CH2F)-2-fluoroethoxy, 1-(CH2Cl)-2-chloroethoxy, 1-(CH2Br)-2-bromoethoxy, 4-fluorobutoxy, 4-chlorobutoxy, 4-bromobutoxy or nonafluorobutoxy;
C1-C6-haloalkoxy: C1-C4-haloalkoxy as mentioned above and also, for example, 5-fluoropentoxy, 5-chloropentoxy, 5-bromopentoxy, 5-iodopentoxy, undecafluoropentoxy, 6-fluorohexoxy, 6-chlorohexoxy, 6-bromohexoxy, 6-iodohexoxy or dodecafluorohexoxy;
alkenyloxy: alkenyl as mentioned above which is attached via an oxygen atom, for example C3-C6-alkenyloxy, such as 1-propenyloxy, 2-propenyloxy, 1-methylethenyloxy, 1-butenyloxy, 2-butenyloxy, 3-butenyloxy, 1-methyl-1-propenyloxy, 2-methyl-1-propenyloxy, 1-methyl-2-propenyloxy, 2-methyl-2-propenyloxy, 1-pentenyloxy, 2-pentenyloxy, 3-pentenyloxy, 4-pentenyloxy, 1-methyl-1-butenyloxy, 2-methyl-1-butenyloxy, 3-methyl-1-butenyloxy, 1-methyl-2-butenyloxy, 2-methyl-2-butenyloxy, 3-methyl-2-butenyloxy, 1-methyl-3-butenyloxy, 2-methyl-3-butenyloxy, 3-methyl-3-butenyl, 1,1-dimethyl-2-propenyloxy, 1,2-dimethyl-1-propenyloxy, 1,2-dimethyl-2-propenyloxy, 1-ethyl-1-propenyloxy, 1-ethyl-2-propenyloxy, 1-hexenyloxy, 2-hexenyloxy, 3-hexenyloxy, 4-hexenyloxy, 5-hexenyloxy, 1-methyl-1-pentenyloxy, 2-methyl-1-pentenyloxy, 3-methyl-1-pentenyloxy, 4-methyl-1-pentenyloxy, 1-methyl-2-pentenyloxy, 2-methyl-2-pentenyloxy, 3-methyl-2-pentenyloxy, 4-methyl-2-pentenyloxy, 1-methyl-3-pentenyloxy, 2-methyl-3-pentenyloxy, 3-methyl-3-pentenyloxy, 4-methyl-3-pentenyloxy, 1-methyl-4-pentenyloxy, 2-methyl-4-pentenyloxy, 3-methyl-4-pentenyloxy, 4-methyl-4-pentenyloxy, 1,1-dimethyl-2-butenyloxy, 1,1-dimethyl-3-butenyloxy, 1,2-dimethyl-1-butenyloxy, 1,2-dimethyl-2-butenyloxy, 1,2-dimethyl-3-butenyloxy, 1,3-dimethyl-1-butenyloxy, 1,3-dimethyl-2-butenyloxy, 1,3-dimethyl-3-butenyloxy, 2,2-dimethyl-3-butenyloxy, 2,3-dimethyl-1-butenyloxy, 2,3-dimethyl-2-butenyloxy, 2,3-dimethyl-3-butenyloxy, 3,3-dimethyl-1-butenyloxy, 3,3-dimethyl-2-butenyloxy, 1-ethyl-1-butenyloxy, 1-ethyl-2-butenyloxy, 1-ethyl-3-butenyloxy, 2-ethyl-1-butenyloxy, 2-ethyl-2-butenyloxy, 2-ethyl-3-butenyloxy, 1,1,2-trimethyl-2-propenyloxy, 1-ethyl-1-methyl-2-propenyloxy, 1-ethyl-2-methyl-1-propenyloxy and 1-ethyl-2-methyl-2-propenyloxy;
alkynyloxy: alkynyl as mentioned above which is attached via an oxygen atom, for example C3-C6-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, 1-ethyl-2-propynyloxy, 2-hexynyloxy, 3-hexynyloxy, 4-hexynyloxy, 5-hexynyloxy, 1-methyl-2-pentynyloxy, 1-methyl-3-pentynyloxy and the like;
alkylthio: alkyl, as defined above which is attached via a sulfur atom;
alkylsulfinyl: alkyl as defined above which is attached via an SO group;
alkylsulfonyl: alkyl as defined above which is attached via an S(O)2 group;
a 5-, 6-, 7-, 8-, 9- or 10-membered saturated, partially unsaturated or aromatic heterocycle which contains 1, 2, 3 or 4 heteroatoms from the group consisting of oxygen, nitrogen and sulfur:
Examples of organic radicals which contain 3 to 13 carbon atoms and one or more silicon atoms and optionally 1 to 3 identical or different heteroatoms from the group consisting of oxygen, nitrogen and sulfur and which are unsubstituted or may carry 1 to 4 identical or different halogen atoms are SiMe3, SiMe2Et, SiMe2CHMe2, SiMe2CH2CHMe2, SiMe2CH2CMe3, SiMe2OCHMe2, SiMe2OCH2CHMe2, CH2SiMe3, CH2SiMe2Et, CH2SiMe2CHMe2, CH2SiMe2CH2CHMe, CH2SiMe2OMe, CH2SiMe2OCHMe2, CH2SiMe2OCH2CHMe2, CHMeSiMe3, CHMeSiMe2OMe, (CH2)2SiMe3, (CH2)2SiMe2Et, (CH2)2SiMe2CHMe2, (CH2)2SiMe2CMe3, (CH2)2SiMe2CH2CHMe2, (CH2)2SiMe2CH2CH2Me, (CH2)2SiMe2CH2CMe3, (CH2)2SiMe2OCHMe2, (CH2)2SiMe2OCH2CHMe2, CHMeCH2SiMe3, CHMeCH2SiMe2Et, CHMeCH2SiMe2CH2CH2Me, CHMeCH2—SiMe2CHMe2, CHMeCH2SiMe2CMe3, CHMeCH2SiMe2CH2CHMe2, CFMeCH2SiMe3, CHMeCH2CH2SiMe2OMe, CHMeCH2SiMe2OCHMe2, CHMeCH2SiMe2OCH2CHMe2, CH2CHMeSiMe3, CH2CHMeSiMe2Et, CH2CHMeSiMe2CHMe2, CHMeCHMeSiMe3, CMe2CH2SiMe3, (CH2)3SiMe3, (CH2)3SiMe2Et, (CH2)3Si-Me2CHMe2, (CH2)3SiMe2CH2CHMe2, (CH2)3SiMe2OMe, (CH2)3SiMe2OCHMe2, (CH2)3SiMe2OCH2CHMe2, CHMeCH2CH2SiMe3, CHMeCH2CH2SiMe2Et, CHMeCH2CH2SiMe2CHMe2, CHMeCH2CH2CH2SiMe2OMe, CHMeCH2—CH2SiMe2OCHMe2, CMe=CHSiMe3, CH2CH2SiMe2OMe, —C≡C—SiMe3, —CH2—C≡C—SiMe3 and —CHMe-C≡C—SiMe3, where Me is methyl and Et is ethyl.
With a view to the fungicidal activity, preference is given to compounds of the formula I in which at least one of the radicals R1 or R2 is different from hydrogen. Among these, preference is given to compounds of the formula I in which R1 is different from hydrogen and R2 is hydrogen. Preference is likewise given to compounds of the formula I in which R1 and R2 are different from hydrogen. Among these, preference is given to compounds of the formula I in which R2 is C1-C4-alkyl, especially methyl or ethyl.
For the fungicidal action of the compounds according to the invention, it is furthermore advantageous if the substituents R1, X and Y independently of one another and preferably in combination have particularly preferably the meanings given below:
Particularly preferably, at least one of the heteroatoms of the 6-membered heteroaromatic radical Het and/or one substituent L is located in the ortho-position to the point of attachment of Het to the triazolopyrimidine moiety. Preferred substituents L in the ortho-position are fluorine, chlorine, bromine, iodine, C1-C2-alkyl, such as methyl or ethyl, C1-C2-fluoroalkyl, such as trifluoromethyl, and C1-C2-alkoxy, such as methoxy, furthermore CN, methylthio, methylsulfinyl, methylsulfonyl, nitro or methoxymethyl. Particularly preferred are chlorine, bromine, iodine, CN, C1-C2-alkyl, such as methyl or ethyl, C1-C2-alkoxy, such as methoxy, methylthio, methylsulfinyl, methylsulfonyl, nitro and methoxymethyl, especially chlorine, bromine or iodine and very especially chlorine. Very particularly preferred substituents L in the ortho position also include CN, methyl, methoxy and methylthio.
A preferred embodiment of the invention relates to compounds of the formula I in which Het is pyridinyl which optionally has 1, 2 or 3 substituents L.
Among these, preference is given to compounds of the formula I in which Het is 2-pyridinyl which has 1 or 2 substituents L. Among these, particular preference is given to compounds in which one of the substituents L is located in the 5-position of the pyridinyl ring, i.e. para to the bond position. Particularly preferred among these compounds are furthermore compounds I in which one of the substituents L is located in the 3-position of the pyridinyl ring, i.e. ortho to the bond position. From among these, preference is furthermore given to compounds of the formula I in which the 2-pyridinyl radical carries a substituent L in the 3-position and a further substituent in the 5-position. Here, L has in particular the meanings mentioned as being preferred. The radical in the 3-position is in particular selected from the group consisting of chlorine, bromine, iodine, C1-C2-alkyl, such as methyl or ethyl, C1-C2-alkoxy, such as methoxy, methylthio, methylsulfinyl, methylsulfonyl, nitro and methoxymethyl, and is especially chlorine. The radical in the 5-position is selected in particular from the group consisting of fluorine, chlorine, bromine, cyano, nitro, C1-C2-alkyl, such as methyl or ethyl, C1-C2-alkoxy, such as methoxy, C1-C2-alkoxycarbonyl, such as methoxycarbonyl or ethoxycarbonyl, CONH2, C1-C2-alkylaminocarbonyl, such as methylaminocarbonyl or ethylaminocarbonyl, C1-C2-alkylcarbonyl, such as acetyl, and C(S)NH2. Preference is given in particular to compounds of the formula I in which Het is one of the radicals below of the formula Het-1, Het-2 or Het-3,
in which # is the point of attachment to the triazolopyrimidine unit and
Preference is furthermore given to compounds of the formula I in which Het is 3-pyridinyl which has optionally 1, 2 or 3 substituents L. From among these, preference is given to those compounds which have a substituent L in the 2-position (ortho to the point of attachment and to the nitrogen of the pyridine ring) and/or a substituent L in the 4-position of the pyridine ring (ortho to the point of attachment and para to the nitrogen of the pyridine ring). Preference is given in particular to compounds of the formula I in which Het is one of the radicals below of the formula Het-4, Het-5, Het-6, Het-7 or Het-8
in which # is the point of attachment to the triazolopyrimidine unit and
Preference is furthermore given to compounds of the formula I in which Het is 4-pyridinyl which optionally has 1 or 2 substituents L. Among these, preference is given to those compounds which have a substituent L in the 3-position and/or a substituent L in the 5-position of the pyridine ring. Preference is given in particular to compounds of the formula I in which Het is one of the radicals below of the formula Het-9 or Het-10
in which # is the point of attachment to the triazolopyrimidine unit and
A further preferred embodiment of the invention relates to compounds of the formula I in which Het is 2-pyrazinyl which optionally has 1, 2 or 3 substituents L.
A further preferred embodiment of the invention relates to compounds of the formula I in which Het is 3-pyridazinyl which optionally has 1, 2 or 3 substituents L.
A further preferred embodiment of the invention relates to compounds of the formula I in which Het is 1,3,5-triazinyl which optionally has 1 or 2 substituents L.
Besides, R5 and R6 independently of one another are preferably hydrogen or C1-C4-alkyl.
R7 is preferably hydrogen or, in particular, C1-C6-alkyl.
R8 and R9 independently of one another are preferably hydrogen or C1-C6-alkyl.
R10, R11, R12 and R13 independently of one another are preferably selected from the group consisting of hydrogen and C1-C6-alkyl.
Furthermore, A1 is preferably hydrogen, C1-C8-alkyl or amino. The index n is preferably 0, 1 or 2.
A2 is preferably C1-C4-alkoxy, NH2, C1-C4-alkylamino or di-C1-C4-alkylamino.
Examples of preferred compounds of the formula I are the compounds I compiled in tables 1 to 11430 below. The groups mentioned in tables 1 to 1430 for a substituent Het are furthermore per se, independently of the combination in which they are mentioned, a particularly preferred embodiment of the substituent in question.
Very particularly preferred compounds of the formula I are those in which Het is 3-chloropyridin-2-yl, 3,5-dichloropyridin-2-yl or 2,4-dichloro-6-methylpyridin-3-yl.
The compounds of the formula I according to the invention can be obtained by different routes analogously to processes of the prior art known per se, according to the syntheses shown in the schemes below:
Compounds of the formula I in which X is Hal can be prepared, for example, according to the synthesis shown in scheme 1.
In scheme 1, Y, R1, R2 and Het are as defined above. Hal is halogen, preferably chlorine or bromine.
In a first step, dihydroxytriazolopyrimidines of the formula II are, analogously to methods described in the prior art cited at the outset or in WO-A 94/20501, converted into the dihalo compounds of the formula III by reaction with a halogenating agent [HAL]. Advantageous for use as halogenating agents are phosphorus oxyhalides or phosphorus(V) halides such as phosphorus pentachloride, phosphorus oxybromide or phosphorus oxychloride, or a mixture of phosphorus oxychloride with phosphorus pentachloride. This reaction of II with the halogenating agent is usually carried out at from 0° C. to 150° C., preferably at from 80° C. to 125° C. [cf. also EP-A 770 615]. The reaction can be carried out in the absence of a solvent or in an inert solvent, for example in a halogenated hydrocarbon, such as dichloromethane or dichloroethane, or an aromatic hydrocarbon, such as, for example toluene, xylenes and the like, or in a mixture of the solvents mentioned above.
The reaction of III with amines IV is carried out analogously to the methods described in the prior art cited at the outset or in WO 98/46608, advantageously at temperatures in the range from 0° C. to 70° C., preferably from 10° C. to 35° C. The reaction is preferably carried out in an inert solvent, for example in an ether, such as dioxane, diethyl ether, diisopropyl ether, tert-butyl methyl ether or, in particular, tetrahydrofuran, a halogenated hydrocarbon, such as dichloromethane or dichloroethane, or an aromatic hydrocarbon, such as, for example, toluene, xylenes and the like, or in a mixture of the solvents mentioned above. It is preferred to use a base, such as a tertiary amine, for example triethylamine, biscyclohexylmethylamine, pyridine, picoline or an inorganic base, such as potassium carbonate; it is also possible for excess amine of the formula IV to serve as base.
The amines IV are commercially available or can be prepared by known processes.
The compounds of the formulae II and III and their agriculturally acceptable salts are novel and also form part of the subject-matter of the present invention. The compounds of the formulae II and III and their agriculturally acceptable salts are furthermore distinguished by their activity against plant-damaging fungi. Accordingly, their use for controlling plant-pathogenic fungi and the corresponding method and crop protection compositions comprising at least one compound of the formula II or III also form part of the subject-matter of the present invention.
Dihydroxytriazolopyrimidines of the formula II can be prepared analogously to methods described in the prior art cited at the outset or in Adv. Het. Chem. 57, (1993), 81 ff. by reacting a 3-amino-2H-1,2,4-triazole V with appropriately substituted hetarylmalonates of the formula VI. In formula VI, R is alkyl, preferably C1-C6-alkyl, in particular methyl or ethyl. Het and Y are as defined above.
This reaction is usually carried out at temperatures of from 80° C. to 250° C., preferably from 120° C. to 180° C., without solvent or in an inert organic solvent in the presence of a base [cf. EP-A 770 615] or in the presence of acetic acid, under the conditions known from Adv. Het. Chem. Vol. 57, p. 81ff. (1993).
Suitable solvents are aliphatic hydrocarbons, aromatic hydrocarbons, such as toluene, o-, m- and p-xylene, halogenated hydrocarbons, ethers, nitriles, ketones, alcohols, and also N-methylpyrrolidone, dimethyl sulfoxide, dimethylformamide and dimethyl-acetamide. With particular preference, the reaction is carried out without solvent or in chlorobenzene, xylene, dimethyl sulfoxide or N-methylpyrrolidone. It is also possible to use mixtures of the solvents mentioned. If appropriate, it may also be possible to add catalytic amounts of acids, such as p-toluene sulfonic acid, acetic acid or propionic acid.
Suitable bases are, in general, inorganic compounds, such as alkali metal and alkaline earth metal hydroxides, alkali metal and alkaline earth metal oxides, alkali metal and alkaline earth metal hydrides, alkali metal amides, alkali metal and alkaline earth metal carbonates, and also alkali metal bicarbonates, organometallic compounds, in particular alkali metal alkyls, alkylmagnesium halides, and also alkali metal and alkaline earth metal alkoxides and dimethoxymagnesium, moreover organic bases, for example tertiary amines, such as trimethylamine, triethylamine, diisopropylethylamine, tributylamine and N-methylpiperidine, N-methylmorpholine, pyridine, substituted pyridines, such as collidine, lutidine and 4-dimethylaminopyridine, and also bicyclic amines. Particular preference is given to tertiary amines, such as diisopropylethyl-amine, tributylamine, N-methylmorpholine or N-methylpiperidine.
The bases are generally employed in catalytic amounts; however, they can also be employed in equimolar amounts, in excess or, if appropriate, as solvent.
The starting materials are generally reacted with one another in equimolar amounts. In terms of yield, it may be advantageous to employ an excess of base and malonate VI, based on the triazole V.
Some of the hetarylmalonates of the formula VI are novel and also form part of the subject-matter of the present invention, i.e. if Het has 1, 2 or 3 substituents independently of one another selected from the group consisting of hydroxyl, cyanato (OCN), C1-C8-alkyl, C2-C10-alkenyl, C2-C10-alkynyl, C1-C6-haloalkyl, C2-C10-haloalkenyl, C1-C6-alkoxy, C2-C10-alkenyloxy, C2-C10-alkynyloxy, C1-C6-haloalkoxy, C3-C6-cycloalkyl, C3-C6-cycloalkenyl, C3-C6-cycloalkoxy, C1-C8-alkoximinoalkyl, C2-C10-alkenyloximinoalkyl, C2-C10-alkynyloximinoalkyl, C2-C10-alkynylcarbonyl, C3-C6-cycloalkylcarbonyl, C(═O)A2, C(═S)A2, a group —C(═N—OR7)(NR8R9) or a group —C(═N—NR10R11)(NR12R13), where A2, R7, R8, R9, R10, R11, R12 and R13 are as defined above, where Het may additionally also have 1, 2 or 3 further substituents selected from the group consisting of halogen and cyano, except for malonates of the formula VI in which Het is 5-trifluoromethylpyridin-2-yl, 6-trifluoromethylpyridin-2-yl, 3-chloro-5-trifluoromethylpyridin-2-yl, 3-chloro-6-trifluoromethylpyridin-2-yl, 3-cyano-5-trifluoromethylpyridin-2-yl, 3-cyano-6-isopropylpyridin-2-yl, 4,6-dimethoxy-1,3,5-triazin-2-yl, 3-trifluoromethyl-4-(1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl)pyridin-2-yl or 3,4,5-trifluoro-6-(1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl)pyridin-2-yl.
Hetarylmalonates of the formula VI can be prepared from hetaryl compounds of the formula VII by reacting one or two equivalents of a carbonic ester or a chloroformate (compound VIII) in the presence of a strong base (see scheme 3).
In scheme 3, Rz is hydrogen or a C1-C4-alkoxycarbonyl group. Q is halogen or C1-C4-alkoxy, in particular methoxy or ethoxy. Het has the meanings given above and R is C1-C4-alkyl. It will be evident to the person skilled in the art that in the case of Rz=H at least two equivalents of the compound VIII have to be employed to achieve complete conversion of VII.
The reaction shown in scheme 3 is usually carried out in the presence of strong bases. If Rz is hydrogen, the base employed will usually be an alkali metal amide, such as sodium amide or lithium diisopropylamide, or an organolithium compound, such as phenyllithium or butyllithium. In this case, the base will be employed in an at least equimolar amount, based on the compound VII, to achieve complete conversion. If Rz is an alkoxycarbonyl group, the base employed will preferably be an alkali metal alkoxide, for example sodium ethoxide or potassium ethoxide, sodium butoxide or potassium butoxide, sodium methoxide or potassium methoxide. For Rz=H, the reaction of VII with VIII can be carried out in one step or in two separate steps, where, in the latter case, the compound VII in which Rz is an alkoxycarbonyl group is obtained as intermediate. The reaction of VII with VIII can also be carried out analogously to the method described in J. Med. Chem. 25 (1982), 745.
Advantageously, malonates of the formula VI can also be prepared by reacting appropriate bromohetaryl compounds Br-Het with dialkyl malonates under Cu(I) catalysis [cf. Chemistry Letters (1981), 367-370; EP-A 10 02 788].
Compounds of the formula I in which X is H, C1-C4-alkyl, C2-C8-alkenyl or C2-C8-alkynyl or a corresponding halogenated radical can be prepared, for example, according to the synthesis shown in scheme 4.
In scheme 4, Y, R1, R2 and Het are as defined above. Hal is halogen, preferably chlorine or bromine. X′ is H, C1-C8-alkyl, C2-C8-alkenyl or C2-C8-alkynyl or a corresponding halogenated radical, and R is C1-C4-alkyl. The reactions shown in scheme 4 can be carried out analogously to the reactions illustrated for schemes 1 and 2.
Some of the compounds of the formula VIa are novel and also form part of the subject-matter of the present invention, i.e. if Het has 1, 2 or 3 substituents independently of one another selected from the group consisting of cyano, hydroxyl, cyanato (OCN), C1-C8-alkyl, C2-C10-alkenyl, C2-C10-alkynyl, C1-C6-haloalkyl, C2-C10-haloalkenyl, C1-C6-alkoxy, C2-C10-alkenyloxy, C2-C10-alkynyloxy, C1-C6-haloalkoxy, C3-C6-cycloalkyl, C3-C6-cycloalkenyl, C3-C6-cycloalkoxy, C2-C10-alkenyloxycarbonyl, C2-C10-alkynyloxy-carbonyl, C1-C8-alkoximinoalkyl, C2-C10-alkenyloximinoalkyl, C2-C10-alkynyloximinoalkyl, C1-C8-alkylcarbonyl, C2-C10-alkenylcarbonyl, C2-C10-alkynylcarbonyl, C3-C6-cycloalkylcarbonyl, S(═O)nA1, C(═O)A2, C(═S)A2, a group —C(═N—OR7)(NR8R9) or a group —C(═N—NR10R11)(NR12R13), in which A1, A2, R7, R8, R9, R10, R11, R12 and R13 are as defined above, where Het may additionally also have 1, 2 or 3 further halogen atoms as substituents L, except for compounds VIa in which Het is 5-ethoxycarbonylpyridin-2-yl, 2-methylpyridin-3-yl, 4-chloro-6-methoxy-1,3,5-triazin-2-yl or 4,6-dimethoxy-1,3,5-triazin-2-yl.
It is self-evident that the maximum number of substituents L on the 6-membered aromatic heterocycle in the compounds I, II, IIa, III, IIIa, VI and VIa is 5 minus the ring nitrogens.
Analogously to standard processes in the sense of a mixed ester condensation, the compounds of the formula VIa can be prepared from the corresponding hetarylacetic acid esters by reaction with the appropriate aliphatic alkyl C2-C5-carboxylates, such as ethyl acetate, ethyl propionate, ethyl butyrate or ethyl valerate or with a reactive derivative thereof, for example an acid chloride or an acid anhydride, in the presence of a strong base, for example an alkoxide, an alkali metal amide or an organolithium compound, for example analogously to the methods described in J. Chem. Soc. Perkin Trans (1967), 767 or in Eur. J. Org. Chem. (2002), 3986.
Advantageously, compounds of the formula I in which X is cyano, C1-C8-alkoxy, C1-C8-alkylthio or C1-C8-haloalkoxy can also be prepared by reacting compounds I in which X is halogen, preferably chlorine, with compounds M1-X′ (hereinbelow also referred to as compounds of the formula IX). Depending on the group X′ to be introduced, the compounds of the formula IX are inorganic cyanides, alkoxides, thiolates or haloalkoxides. The reaction is advantageously carried out in an inert solvent. The cation M1 in formula IX is of little importance; for practical reasons, ammonium salts, tetraalkylammonium salts such as tetramethylammonium or tetraethylammonium salts, or alkali metal salts or alkaline earth metal salts are usually preferred (Scheme 5).
(I)+M1-X′→(I)
(X=halogen) (IX) {X=X′=CN, C1-C4-alkoxy, C1-C4-haloalkoxy}
The reaction temperature is usually from 0 to 120° C., preferably from 10 to 40° C. [cf. J. Heterocycl. Chem. 12 (1975), 861-863].
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 the formula I, in which X is C1-C8-alkyl, C1-C8-haloalkyl, C2-C8-alkenyl, C2-C8-haloalkenyl, C2-C8-alkynyl or C2-C8-haloalkynyl can advantageously be prepared by reacting compounds I in which X is halogen with organometallic compounds Xa-Mt, where Xa is C1-C4-alkyl, C1-C4-haloalkyl, C2-C8-alkenyl, C2-C8-haloalkenyl, C2-C8-alkynyl or C2-C8-haloalkynyl and Mt is lithium, magnesium or zinc. 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 generally carried out in an inert organic solvent, for example one of the ethers mentioned above, 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 from −100 to +100° C. and especially in the range from −80° C. to +40° C. The appropriate methods are known, for example from the prior art cited at the outset (see, for example, WO 03/004465).
In principle, compounds of the formula I, in which X is C1-C8-alkyl can also be prepared by reacting compounds I in which X is halogen, in particular chlorine, with malonates of the formula X. This synthesis route is shown in scheme 6. In formula X, X″ is hydrogen or C1-C3-alkyl and R is C1-C4-alkyl. The compounds I are converted into compounds of the formula XI which are subsequently, after hydrolysis, decarboxylated to give compounds I [cf. U.S. Pat. No. 5,994,360].
The malonates X are known from the literature, for example from J. Am. Chem. Soc. 64 (1942), 2714; J. Org. Chem. 39 (1974), 2172; Helv. Chim. Acta 61, (1978), 1565, or they can be prepared in accordance with the literature cited.
The subsequent hydrolysis of the ester XI is carried out under generally customary conditions. Depending on the various structural elements, alkaline or acidic hydrolysis of the compounds XI may be advantageous. Under the conditions of ester hydrolysis, there may already be complete or partial decarboxylation to I. Usually, decarboxylation takes place at temperatures of from 20° C. to 180° C., preferably from 50° C. to 120° C., in an inert solvent, if appropriate in the presence of 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, n-propanol, isopropanol, n-butanol and tert-butanol, and also dimethyl sulfoxide, dimethylformamide and dimethylacetamide; with particular preference, the reaction is carried out in hydrochloric acid or acetic acid. It is also possible to use mixtures of the solvents mentioned.
The reaction mixtures are worked up in a customary manner, for example by mixing with water, separating the phases and, if appropriate, chromatographic purification of the crude products. Some of the intermediates and end products are obtained in the form of colorless or slightly brownish viscous oils which can be purified or freed from volatile components under reduced pressure and at moderately elevated temperature. If the intermediates and end products are obtained as solids, purification can also be carried out by recrystallization or digestion.
If individual compounds I cannot be obtained by the routes described above, they can be prepared by derivatization of other compounds I.
If the synthesis yields mixtures of isomers, a separation is generally not necessarily required since in some cases the individual isomers can be interconverted during work-up for use during application (for example under the action of light, acids or bases). Such conversions may also take place after use, for example, in the case of treatment of plants, in the treated plants, or in the harmful fungus to be controlled.
The compounds I are suitable as fungicides. They are distinguished by an outstanding effectiveness against a broad spectrum of phytopathogenic fungi, especially from the classes of the Ascomycetes, Deuteromycetes, Oomycetes and Basidiomycetes. Some are systemically effective and they can be used in plant protection as foliar fungicides, as fungicides for seed dressing and as soil fungicides.
They are particularly important in the control of a multitude of fungi on various cultivated plants, such as wheat, rye, barley, oats, rice, corn, grass, bananas, cotton, soya, coffee, sugar cane, vines, fruits and ornamental plants, and vegetables, such as cucumbers, beans, tomatoes, potatoes and cucurbits, and on the seeds of these plants.
They are especially suitable for controlling the following plant diseases:
The compounds (I) are furthermore suitable for controlling harmful fungi in the protection of materials (for example wood, paper, paint dispersions, fibers or fabrics) and in the protection of stored products. In the protection of wood, particular attention is paid to the following harmful fungi: Ascomycetes, such as Ophiostoma spp., Ceratocystis spp., Aureobasidium pullulans, Sclerophoma spp., Chaetomium spp., Humicola spp., Petriella spp., Trichurus spp.; Basidiomycetes, such as Coniophora spp., Coriolus spp., Gloeophyllum spp., Lentinus spp., Pleurotus spp., Poria spp., Serpula spp. and Tyromyces spp., Deuteromycetes, such as Aspergillus spp., Cladosporium spp., Penicillium spp., Trichoderma spp., Alternaria spp., Paecilomyces spp. and Zygomycetes, such as Mucor spp., additionally in the protection of materials the following yeasts: Candida spp. and Saccharomyces cerevisae.
In addition, the compounds of the formula (I) can also be used in crops which, owing to breeding including genetical engineering, are tolerant to attack by insects or fungi.
The compounds I are employed by treating the fungi or the plants, seeds, materials or soil to be protected from fungal attack with a fungicidally effective amount of the active compounds. The application can be carried out both before and after the infection of the materials, plants or seeds by the fungi.
The fungicidal compositions generally comprise between 0.1 and 95%, preferably between 0.5 and 90%, by weight of active compound.
When employed in plant protection, the amounts applied are, depending on the kind of effect desired, between 0.01 and 2.0 kg of active compound per ha.
Seed can be treated by methods known to the person skilled in the art, such as, for example, seed dressing, seed coating, seed dusting, seed soaking and seed pelleting.
In seed treatment, amounts of active compound of from 1 to 1000 g, preferably from 1 to 200 g, in particular from 5 to 100 g, per 100 kg of seed are generally required.
Accordingly, the present invention furthermore provides seed comprising a compound of the formula (I) according to the invention in an amount of from 1 to 1000 g per 100 kg.
When used in the protection of materials or stored products, the amount of active compound applied depends on the kind of application area and on the desired effect. Amounts customarily applied in the protection of materials are, for example, 0.001 g to 2 kg, preferably 0.005 g to 1 kg, of active compound per cubic meter of treated material.
The compounds I can be converted into the customary formulations, for example solutions, emulsions, suspensions, dusts, powders, pastes and granules. The application form depends on the particular purpose; in each case, it should ensure a fine and uniform distribution of the compound according to the invention.
The formulations are prepared in a known manner, for example by extending the active compound with solvents and/or carriers, if desired using emulsifiers and dispersants. Solvents/auxiliaries which are suitable are essentially:
Suitable surfactants are alkali metal, alkaline earth metal and ammonium salts of lignosulfonic acid, naphthalenesulfonic acid, phenolsulfonic acid, dibutylnaphthalenesulfonic acid, alkylarylsulfonates, alkyl sulfates, alkylsulfonates, fatty alcohol sulfates, fatty acids and sulfated fatty alcohol glycol ethers, furthermore condensates of sulfonated naphthalene and naphthalene derivatives with formaldehyde, condensates of naphthalene or of naphthalenesulfonic acid with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctylphenol, octylphenol, nonylphenol, alkylphenol polyglycol ethers, tributylphenyl polyglycol ether, tristearylphenyl polyglycol ether, alkylaryl polyether alcohols, alcohol and fatty alcohol/ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitol esters, lignosulfite waste liquors and methylcellulose.
Suitable for the preparation of directly sprayable solutions, emulsions, pastes or oil dispersions are mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, furthermore coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, for example toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, methanol, ethanol, propanol, butanol, cyclohexanol, cyclohexanone, isophorone, strongly polar solvents, for example dimethyl sulfoxide, N-methylpyrrolidone and water.
Powders, materials for spreading and dustable products can be prepared by mixing or concomitantly grinding the active substances with a solid carrier.
Granules, for example coated granules, impregnated granules and homogeneous granules, can be prepared by binding the active compounds to solid carriers. Examples of solid carriers are mineral earths such as silica gels, silicates, talc, kaolin, attaclay, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground synthetic materials, fertilizers, such as, for example, ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas, and products of vegetable origin, such as cereal meal, tree bark meal, wood meal and nutshell meal, cellulose powders and other solid carriers.
Formulations for seed treatment may further comprise binders and/or gelants and if appropriate dyes.
Binders can be added to increase the adhesion of the active compounds to the seed after the treatment. Suitable binders are for example EO/PO block copolymer surfactants, but also polyvinyl alcohols, polyvinylpyrrolidones, polyacrylates, polymethacrylates, polybutenes, polyisobutylenes, polystyrenes, polyethyleneamines, polyethyleneamides, polyethyleneimines (Lupasol®, Polymin®), polyethers, polyurethanes, polyvinyl acetates, Tylose and copolymers of these polymers. A suitable gelant is for example carrageen (Satiagel®).
In general, the formulations comprise from 0.01 to 95% by weight, preferably from 0.1 to 90% by weight, of the active compound. The active compounds are employed in a purity of from 90% to 100%, preferably 95% to 100% (according to NMR spectrum).
Examples of Formulations are:
1. products for dilution with water
A Water-soluble concentrates (SL)
Seed treatment typically utilizes water-soluble concentrates, suspensions, dusts, water-dispersible and water-soluble powders, emulsions, emulsifiable concentrates and gel formulations. These formulations can be applied neat or preferably diluted to the seed. The application can take place prior to sowing.
Preference is given to using suspension formulations for seed treatment. Such formulations typically comprise from 1 to 800 g/l of active compound, from 1 to 200 g/l of surfactants, from 0 to 200 g/l of antifreeze, from 0 to 400 g/l of binder, from 0 to 200 g/l of dyes and solvent, preferably water.
The active compounds can be used as such, in the form of their formulations or the use forms prepared therefrom, for example in the form of directly sprayable solutions, powders, suspensions or dispersions, emulsions, oil dispersions, pastes, dustable products, materials for spreading, or granules, by means of spraying, atomizing, dusting, spreading or pouring. The use forms depend entirely on the intended purposes; the intention is to ensure in each case the finest possible distribution of the active compounds according to the invention.
Aqueous use forms can be prepared from emulsion concentrates, pastes or wettable powders (sprayable powders, oil dispersions) by adding water. To prepare emulsions, pastes or oil dispersions, the substances, as such or dissolved in an oil or solvent, can be homogenized in water by means of a wetter, tackifier, dispersant or emulsifier. Alternatively, it is possible to prepare concentrates composed of active substance, wetter, tackifier, dispersant or emulsifier and, if appropriate, solvent or oil, and such concentrates are suitable for dilution with water.
The active compound concentrations in the ready-to-use preparations can be varied within relatively wide ranges. In general, they are from 0.0001 to 10%, preferably from 0.01 to 1%.
The active compounds may also be used successfully in the ultra-low-volume process (ULV), by which it is possible to apply formulations comprising over 95% by weight of active compound, or even to apply the active compound without additives.
For the treatment of seed, the formulations in question may be diluted two- to ten-fold, resulting in active compound concentrations of from 0.01 to 60% by weight, preferably from 0.1 to 40% by weight, in the finished ready-to-use preparations.
Various types of oils, wetters, adjuvants, herbicides, fungicides, other pesticides, or bactericides may be added to the active compounds, if appropriate not until immediately prior to use (tank mix). These agents can be admixed with the agents according to the invention in a weight ratio of 1:100 to 100:1, preferably 1:10 to 10:1.
Suitable adjuvants in this sense are in particular: organically modified polysiloxanes, for example Break Thru S 240®; alcohol alkoxylates, for example Atplus 245®, Atplus MBA 1303®, Plurafac LF 300® and Lutensol ON 30®; EO/PO block polymers, for example Pluronic RPE 2035® and Genapol B®; alcohol ethoxylates, for example Lutensol XP 80®; and sodium dioctylsulfosuccinate, for example Leophen RA®.
The compositions according to the invention can, in the use form as fungicides, also be present together with other active compounds, e.g. with herbicides, pesticides (such as insecticides and acaricides), growth regulators, fungicides or else with fertilizers. Mixing the compounds I or the compositions comprising them in the application form as fungicides with one or more active substances, in particular other fungicides results in many cases in a broadening of the spectrum of activity being obtained or resistance development can be prevented thereby. In many cases synergistic effects are achieved.
The following list of fungicides, in conjunction with which the compounds according to the invention can be used, is intended to illustrate the possible combinations but does not limit them:
The present invention furthermore relates to the pharmaceutical use of the compounds of the formula (I) according to the invention and/or the pharmaceutically acceptable salts thereof, in particular their use for treating tumors in mammals such as, for example, humans.
The procedures described in the synthesis examples below were used to prepare further compounds I by appropriate modification of the starting compounds. The compounds thus obtained are listed in the table C below, together with physical data.
The malonates of the formula VI listed in table B (malonates VI.4 to VI.64) were prepared in an analogous manner:
The compounds of the general formulae I, II and III where Y=H listed in tables C, D and E below were prepared according to the given procedures.
All products were characterized by HPLC, mass spectrometry, by combined HPLC/mass spectrometry (High Performance Liquid Chromatography Mass Spectrometry) or by their melting point. For HPLC, an analytical RP-18 column (Chromolith Speed ROD from Merck KGaA, Germany), which was operated at 40° C., was used. The mobile phase used was acetonitrile with 0.1% by volume of a trifluoroacetic acid water mixture and 0.1% by volume of trifluoroacetic acid. (The ratio of trifluoroacetic acid/water was changed from 5:95 to 95:5 over a period of 5 minutes). Mass spectrometry was carried out using a quadrupole mass spectrometer with electrospray ionization at 80 V in the positive mode.
1)melting point in ° C.
2)m/z of the M+ or the [M + H]+ peak
3)HPLC analysis retention time in minutes
1)melting point in ° C.
2)m/z of the M+ or the [M + H]+ peak
3)HPLC analysis retention time in minutes
1)melting point in ° C.
2)m/z of the M+ or the [M + H]+ peak
3)HPLC analysis retention time in minutes
The fungicidal action of the compounds of formula I was demonstrated by the following tests:
The respective active compound was prepared as a stock solution with 25 mg of active compound which was made up to 10 ml with a mixture of acetone and/or dimethyl sulfoxide (DMSO) and the emulsifier Uniperol® EL (wetting agent having emulsifying and dispersing action based on ethoxylated alkylphenols) in a volume ratio solvent/emulsifier of 99 to 1. The solution was then made up to 100 ml with water. This stock solution was diluted to the active compound concentration stated below using the solvent/emulsifier/water mixture described.
Leaves of potted plants of the cultivar “Goldene Konigin” were sprayed to runoff point with an aqueous suspension having the concentration of active compounds stated below. The next day, the leaves were infected with an aqueous spore suspension of Alternaria solani in 2% biomalt solution having a density of 0.17×106 spores/ml. The plants were then placed in a water-vapor-saturated chamber at temperatures of between 20 and 22° C.
After 5 days, the infection on the untreated, but infected control plants had developed to such an extent that the infection could be determined visually in %.
In this test, the plants which had been treated with 250 ppm (concentration of active compound) of the compound from example 1, 8, 9, 21, 26, 28, 38, 30, 31, 43, 47, 51, 52, 58, 60, 61, 62, 66, 67, 68, 69, 71, 72, 73, 74, 76, 77, 75, 78, 79, 80, 81, 83, 86, 88, 89, 90, 91, 95, 96, 97, 101 showed an infection of at most 30%, whereas the untreated plants were 90% infected.
Bell pepper seedlings of the cultivar “Neusiedler Ideal Elite” were, after 2-3 leaves were well developed, sprayed to runoff point with an aqueous suspension having the concentration of active compound stated below. The next day, the treated plants were inoculated with a spore suspension of Botrytis cinerea which contained 1.7×106 spores/ml in a 2% strength aqueous biomalt solution. The test plants were then placed in a dark climatized chamber at 22-24° C. and high atmospheric humidity. After 5 days, the extent of the fungal infection on the leaves could be determined visually in %.
In this test, the plants which had been treated with 250 ppm of the compound from example 3, 5, 21, 22, 28, 30, 31, 43, 47, 51, 52, 56, 58, 66, 67, 71, 72, 73, 76, 78, 79, 81, 83, 86, 88, 89, 90, 91, 95, 96, 97 or 101 showed an infection of at most 20%, whereas the untreated plants were 70% infected.
Leaves of potted barley seedlings of the cultivar “Hanna” were sprayed to runoff point with an aqueous suspension having the concentration of active compound stated below. 24 h after the spray coating had dried on, the test plants were inoculated with an aqueous spore suspension of Pyrenophora [syn. Drechslera] teres, the net blotch pathogen. The test plants were then placed in a greenhouse at temperatures of from 20 to 24° C. and 95 to 100% relative atmospheric humidity. After 6 days, the extent of the fungal infection on the leaves was determined visually in %.
In this test, the plants which had been treated with 250 ppm of the compound from example 2, 5, 8, 19, 26, 41, 46, 50, 62, 64, 69, 74 or 80 showed an infection of at most 20%, whereas the untreated plants were 90% infected.
Leaves of potted wheat seedlings of the cultivar “Kanzler” were inoculated with a spore suspension of brown rust (Puccinia recondita). The pots were then placed in a chamber with high atmospheric humidity (90 to 95%) and 20 to 22° C. for 24 hours. During this time, the spores germinated and the germ tubes penetrated into the leaf tissue. The next day, the infected plants were sprayed to runoff point with the active compound solution described above at the active compound concentration stated below. After the spray coating had dried on, the test plants were cultivated in a greenhouse at temperatures between 20 and 22° C. and 65 to 70% relative atmospheric humidity for 7 days. The extent of the rust fungus development on the leaves was then determined.
In this test, the plants which had been treated with 250 ppm of the compound from example 40, 60 or 64 showed an infection of at most 5%, whereas the untreated plants were 90% infected.
Leaves of potted wheat seedlings of the cultivar “Kanzler” were sprayed to runoff point with an aqueous suspension having the active compound concentration stated below. The next day, the treated plants were inoculated with a spore suspension of brown rust of wheat (Puccinia recondita). The plants were then placed in a chamber with high atmospheric humidity (90 to 95%) at 20 to 22° C. for 24 hours. During this time, the spores germinated and the germ tubes penetrated into the leaf tissue. The next day, the test plants were returned to the greenhouse and cultivated at temperatures between 20 and 22° C. and 65 to 70% relative atmospheric humidity for a further 7 days. The extent of the rust fungal development on the leaves was then determined visually.
In this test, the plants which had been treated with 250 ppm of the compound from example 59 showed no infection, whereas the untreated plants were 90% infected.
| Number | Date | Country | Kind |
|---|---|---|---|
| 102004060958.6 | Dec 2004 | DE | national |
| 102004062199.3 | Dec 2004 | DE | national |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/EP05/13577 | 12/16/2005 | WO | 00 | 6/14/2007 |
