MXPA98010135A - Pirimidin-4-carboxami - Google Patents

Abstract

The pyrimidine-4-carboxamides of the formula I (see formula) and the salts thereof, wherein: R 1 is unsubstituted or substituted: alkyl, aryl, n is 0, 1 or 2, R 2 is hydrogen, hydroxyl, halogen, alkyl , haloalkyl, alkoxy, haloalkoxy, R3 is hydrogen, hydroxyl, halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, one of the radicals R2 and R3 in each case always being hydrogen, Y is oxygen or sulfur, R4 is hydrogen or is alkyl or cycloalkyl, each of which can be paracial or completely halogenated, is substituted or unsubstituted: alkyl, cycloalkyl, aryl, compositions containing them and their use to control harmful fungi

Description

PYRIMIDIN-4-CARBOXAMIDES The present invention relates to pyrimidine-4-carboxyamines and formula I: salts and N-oxiyos? e the same,? on? e: R1 is alkyl? e Ci-Ce, it is possible that these radicals are partially or completely halogenated and / or bearing? e 1 to 3? e the following groups: cyano alkoxyalkyl of C? ~ C, haloalkyl of C? -C, alkoxy of C? ~ C, haloalkoxy of C? -C, alkylthio of C? -C4, alkoxycarbonyl of C? -C4 , C3-C7 cycloalkyl, C3-C7 cycloalkenyl, aryl, allyloxy and ethyryl, while it is possible in turn that the cyclic radicals carry one to three of the following substituents: halogen, cyano, C1-alkyl; -C4, C? -C4 alkoxyalkyl, C? -C4 haloalkyl, C1-C4 alkoxy, C? -C4 haloalkoxy, alkylthio? E C 1 -C 4 alkoxycarbonyl, aryl, aryloxy and ethanoyl, or it is aryl, it being possible for the radicals to carry 1 or 2, independently of one another, 2 or 3 the following groups: halogen, cyano, alkyl and C1- C4, alkoxyalkyl of C3.-C4, haloalkyl of C 1 -C 4, alkoxy of C 1 -C 4 haloalkoxy of C 1 -C 4, alkylthio of C 1 -C 4, alkoxycarbonyl of C 1 -C 4, aryl, aryloxy and etharyl, being in turn possible that the cyclic substituents carry one or, independently of each other, two or three? e the following substituents: halogen, cyano, alkyl? and C? -C4r alkoxyalkyl? and C1-C4, haloalkyl? and C1-C4, C1-C4 alkoxy, C 1 -C 4 haloalkoxy, C 1 -C 4 alkylthio, and C 1 -C 4 alkoxycarbonyl is 0, 1 or 2; R 2 is hydrogen, halogen hydroxyl, C 1 -C 8 alkyl, C 1 -C 8 haloalkyl, C 1 -C 8 alkoxy, haloalkoxy C 1 -C 8; RJ is hydrogen, hydroxyl, halogen, C?-C8 alkyl, C?-C8 haloalkyl, C?-C8 alkoxy, C?-C8 haloalkoxy; one of the radicals R2 and R3 in each case will always be hydrogen; And it is oxygen or sulfur; R 4 is hydrogen or C 1 -C 8 alkyl, which may be partially or completely halogenated, or C 3 -C 7 cycloalkyl, which may be partially or completely halogenated; R5 is C? -C8 alkyl, it being possible for these radicals to be partially or completely halogenated and / or carry, or independent of each other, three or three? groups: cyano alkoxyalkyl of C? -C, haloalkyl of Ci-C4, alkoxy of C1-C4, haloalkoxy? and C1-C4, alkylthio? e Cj.-C4, alkoxycarbonyl? and C1-C4, cycloalkyl of C3-C7, C3-C7 cycloalkenyl, aryl, allyloxy and ethyryl, while it is possible that the cyclic radicals bear one, or independent of each other, two or three of the following substituents: halogen, cyano, alkyl? e C 1 -C 4, C 1 -C 4 alkoxyalkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, C 1 -C 4 alkylthio, C 1 -C 4 alkoxycarbonyl, aryl, aryloxy and etaryl, or is C3-C7 cycloalkyl, it being possible for this radical to carry one or, independently of each other or three, the following groups: halogen, alkyl? and Ci-C4, haloalkyl? and C1-C4 and alkoxy? e C1-C4, or is aryl, it is possible that this radical carries one, independent of each other, two or three of the following groups: halogen, cyano, C1-C4 alkyl, C1-C4 alkoxyalkyl, haloalkyl C 1 -C 4, C 1 -C 4 alkoxy, haloalkoxy C 4 -C 4 alkylthio C 1 -C 4, C 1 -C 4 alkoxycarbonyl, aryl, aryloxy and ethyryl, while it is also possible that the cyclic substituents bear one or, in addition to each other, three or more of the following substituents : halogen, cyano, C 1 -C 4 alkyl, C 3 -C 4 alkoxyalkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, C 1 -C 4 alkylthio, C 4 -C 4 alkoxycarbonyl. In addition, the invention relates to the compositions containing the compounds I and the use of the compounds 1 and the compositions for controlling harmful fungi. Compounds of type I that have activity? fungicides are known from EP-A 569 912 and WO-A 95/25 723. However, the activity? The compounds written in the previously mentioned publications against fungal fungi is not satisfactory. It is an object of the present invention to provide novel pyrimidine-4-carboxamides which have property? Is improved, in particular a superior activity, and also a broad spectrum of activity? in the control of fungal per udiciales. We have found that this objective is achieved with the aforementioned compounds I, by the compositions containing them and by their use and use of the compositions for controlling harmful fungi. The compounds I can be prepared in a conventional manner similar to the known methods, as exemplified in the following three processes.

Process? E Preparation 1 The pyrimido-in-4-carboxyamines I,? On? E R1 = methyl; R2 = chlorine; R2 = hydrogen; Y = 0, and n = 0, 1 or 2 They can be obtained, for example, (see diagram 1 below) initially put to react a compound II with sulfate and S-methylisothiurea (III) to produce the acid. or 4-hi? roxypyrimidine-6-carboxylic (IV) see, J. Org. Chem. 26 (1961), 2755). After the chlorination of the hydroxyl function, which is carried out in a conventional manner and produces the compounds V, the compounds V are reacted with the amines VI to give the amides I (n = 0). The compounds I, don? E n is 1 or 2, are accessible from these amides by oxidation.

Scheme I O O wa NH2 H5C20- C II - C I = CH- COOC2H5 + (H2N-C It -SCH3) +2 SO42- II III I (n = 0) The amines VI are known or can be obtained in a simple form (see, Houben-Weyl, Methoden der Organischem Chemie, Georg Thieme Verlag, Stuttgart, Volume XI / l 4th edition, 1957, pages 24 to 262 and pages 360 to 409). The reaction of the amines 6 with the compounds 5 is preferably carried out in a solvent such as dichloromethane, tetrahydrpurane or toluene. The a? Ecua? As bases are, in particular, the own amines VI, being these usually recovered from? The product cru? O.

The oxidation of the amides 1, where n = 0, to give the corresponding compounds 1,? On? In = 1 or 2, can be carried out in the conventional manner (see, Houben-Weyl, Metho ? in der Organischem Chemie, Georg Thime Verlag, Stuttgart, Volume Eli 4th edition, 1985, pages 1129 to 1256 in particular pages 1195 to 1204 (Sub-volume II), ibid., Vol. IX, 4th edition, 1955, p. 222 ff.). Suitable oxygens are, for example, hydrogen peroxide, organic peroxyacids such as peracetic acid, trifluoroperacetic acid, m-chloroperbenzoic acid, hydroperoxide, tertbutyl and hypochloride, and tert-butyl, and Organic compounds such as metazo? ato? e so? io, chromic acid and nitric acid. Suitable to completely oxidize the sulfur are in particular hydrogen peroxide, organic peroxides such as peracetic acid, trifluoroperacetic acid and m-chloroperbenzoic acid, and also inorganic oxygenates such as potassium permanganate. When an inorganic oxygen agent is used, the addition of a catalyst, for example, tungstate, may favor the reaction. Particularly advantageous is a mixture of sodium tungstate and peroxygen and hydrogen. As a general rule, the reaction is carried out in an inert solvent, inert solvents, depending on the oxygenated agent, for example, organic acids as acetic acid, trichloroacetic acid, and propionic acid, chlorine hydrocarbons such as chloride, methylene, chloroform, and 1,2-? -chloroethane, aromatic hydrocarbons, or halogenated hydrocarbons such as benzene, chlorobenzene, and toluene, protic solvents such as methanol and ethanol, or Water. Mixtures of the mentioned solvents are also suitable. The reaction temperature is generally (-30) ° C to the boiling point of the mixture, the respective reaction, for the partial oxygenation, the sulfur more in the lower temperature range, for the complete oxidation preferably from 10 ° C to the boiling point. The reaction is carried out particularly preferably at 0 to 40 ° C. Depending on the desired target product, where n = 1 or 2, approximately equimolar amounts of the oxidizing agent or an approximately molar excess are used. Moreover, the compounds of the formula I can be converted into their N-oxides in a conventional manner (see, for example, A. Albini and S. Pietra, Heterocilic N-Oxyzines, CRC-Press Inc., Boca Raton, USA 1991; HS Mosher et al., Org. Synth., Coll., IV, 1963, page 828; EC Taylor et al., Org. Synth., Coll., IV, 1963, page 704; TW Bell et al., Synth 69 (1990), 226). Examples of oxidizing agents that are conventionally used for oxidation include: acid peracetic acid, trifluoroperacetic acid, perbenzoic acid, m-chloroperbenzoic acid, monopermalemal acid, magnesium monoperoxyphthalate, sodium perborate, Oxone® (contains peroxomonosulfate), pertungstic acid and hydrogen peroxide. Suitable solvents are, for example, water, sulfuric acid, carboxylic acids, such as acetic acid and trifluoroacetic acid, and halogenated hydrocarbons such as dichloromethane and chloroform. Oxidation usually proceeds at temperatures? Is 0 ° C to the boiling point? E the mixture? E reaction. The oxygenated agent is usually used at least in quantities, equimolar, based on the initial material. However, a large excess of the oxidizing agent has proved to be particularly advantageous.

Process? E preparation 2 The pirimi? In-4-carboxami? As I,? Rde • R1 = methyl; R2 = hydrogen; R2 = bromine; Y = 0, and n = 0, 1 or 2 They are obtained, for example, (see scheme 2 below), by reaction? The mucobronic acid VII with sulfate? S-methylisothiourea (III) for the 5-bromopyrimido-in-6-carboxylic acids VIII (see J. Chem. Soc. 1953, pages 3129-3131) and then proceed as described. Write in the example? e preparation 1.

H VIII Otherwise, in particular when the corresponding years are prepared, the 5-bromopyridine-6-carboxylic acids are converted into cyanides or anhydrides (acyl). see, Tetrahe? ron Letters 18 (1973), 1595-1598, or "Houen-Wely", volume 15/1, pages 28 to page 32). Active acylocarboxy cyanides are prepared, for example, by the reaction with cyanophosphonate? Etyphite, in particular in an inert solvent, such as tetrahydrofuran or toluene. Activated carboxy anhydrides are prepared by reaction with chloroformates such as chloroformate and isobutyl, in the presence of bases and, if appropriate, in an inert solvent such as toluene or tetrahydrofuran.

Preparation process 3 The pyrimidine-4-carboxamides I,? On? E R1 = methyl; R2 = hydrogen; R2 = hydrogen; Y = 0, and N = 0, 1 or 2 are obtained, for example, by the dehalogenation of compounds VIII (see process? E preparation 2) according to the Chem. Scand Act. B40 (1986), 588-592 or J. Me ?. Chem. 29 (1986), 1374-80 and then proceed as it is written in the process? E preparation 1. Depends on the nature of the substituents, the compounds? And the formula I it can, in some cases, be present as geometrical and / or optical isomers or mixtures? and isomers. Both the pure isomers and the mixtures? And isomers exhibit fungicidal action. The salts of the compounds I stable to acids containing basic centers, especially basic nitrogen atoms, in particular with mineral acids such as sulfuric acid and phosphoric acid or Lewis acids, such as zinc chloride, are also part of the invention. As usual, in this case, the nature of the salts is not important. In accordance with the invention, those salts are preferred. they do not harm plants, areas, materials or spaces that must be kept free from harmful fungi and do not affect the action of the compounds 1. Of specific importance are the salts that are suitable for agricultural purposes. The salts of the compounds 1 are accessible in a manner known per se, in particular by reaction of the corresponding compounds with the aforementioned acids, in water or an inert organic solvent of (-80) to 120 ° C, preferably? at 60 ° C. In the "definitions" of the compounds 1 that were seen at the beginning, collective terms were used which are generally representative of the following substituents: halogen: fluorine, chlorine, bromine and iodine; alkyl: straight or branched chain alkyl groups having from 1 to 8 carbon atoms, for example, Ci-Cß alkyl, such as methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methylpropyl, -methylpropyl, 1,1-dimethylethyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1- 1 -propylpropyl, 2-, 2'-imethylpropyl, 1, 2-imethylpropyl, 1-ethylpropyl, n -hexyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1, 1-imethylbutyl, 2,2-? imethylbutyl, 3, 3? -imethylbutyl, 1, 2-? imethylbutyl, 1,3 -? imethylbutyl, 2,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1, 1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl and l-ethyl-2-methylpropyl; Haloalkyl or partially or completely halogenated alkyl: or linear or branched alkyl or alkaline groups having 1 to 4 or 8 carbon atoms (as already mentioned), in these groups the atoms and hydrogen can be partially or completely substituted by atoms and halogen (as already mentioned), for example, haloalkyl? and C? ~ C2, such as chloromethyl,? -chloromethyl, trichloromethyl, fluoromethyl,? -ifluoromethyl, trifluoromethyl, chlorofluoromethyl , dichlorofluoromethyl, chlorodifluoromethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-? -fluoroethyl, 2, 2- dichloro-2-fluoroethyl, 2,2-trichloroethyl and pentafluoroethyl; alkoxy; straight or branched chain alkoxy groups having from 1 to 4 carbon atoms, for example Ci-C3 alkoxy, such as methoxy, ethoxy, propoxy and 1-methylethoxy; alkoxyalkyl: linear or branched alkyl or straight alkyl groups having 1 to 8 carbon atoms (as already mentioned), which in any desired position carry a straight or branched chain alkoxy group (as already stated) it was mentioned) that it has, in each case C 1 -C 4 alkoxyalkyl, from 1 to 4 carbon atoms, such as methoxymethyl, ethoxymethyl 'n-propoxymethyl, n-butoxymethyl, 1-methoxyethyl, 2-methoxyethyl, 1-ethoxyethyl, 2-ethoxyethyl, 2-n-propoxyethyl, and 2-butoxyethyl; haloalkoxy: straight or branched alkoxy or cationic groups having from 1 to 4 carbon atoms (as already mentioned), where in these groups the hydrogen atoms can be partially or completely replaced by halogen atoms (as already mentioned), for example, haloalkoxy? C? -C2, such as chloromethoxy,? -chloromethoxy, trichloromethoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorofluoromethoxy, dichlorofluoromethoxy, chlorodifluoromethoxy, 1-fluoroethoxy, 2-fluoroethoxy, 2, 2-difluoroethoxy, 2,2,2-trifluoroethoxy, 2-chloro-2-fluoroethoxy, 2-chloro-2,2-difluoroethoxy, 2,2-dichloro-2-fluoroethoxy, 2,2-trichloroethoxy and pentafluoroethoxy; alkylthio: straight or branched chain alkyl groups having from 1 to 4 carbon atoms (as already mentioned), which are attached to the structure via a sulfur atom (-S-), for example, alkylthio of C? ~ C4, such as methylthio, ethylthiopropylthio, 1-methylethylthio, n-butylthio and tert-butylthio; alkoxycarbonyl: linear or branched alkoxy or cationic groups having 1 to 4 carbon atoms (as already mentioned), which are bonded to the structure through a carbonyl group (-CO-); alkenyl: linear or branched chain alkenyl groups having 2 to 8 carbon atoms and a bond which can be attached at any position, eg, alkenyl, and C2-C6. 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, 2-methyl-1-propenyl, 1-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2 -methyl-1-butenyl, 3-methyl-l-butenyl, l-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, l-methyl-3-butenyl, 2-methyl -3-butenyl, 3-methyl-3-butenyl, ll-dimethyl-2-propenyl, 1, 2? -imethyl-l-propenyl, 1, 2? -imethyl-2-propenyl 1-ethyl-1-propenyl, l-ethyl-2-propenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-l-pentenyl, 2-methyl-l-pentenyl, 3-methyl-l- pentenyl, 4-methyl-1-pentenyl, l-methyl-2-pentenyl, 2-methyl-2-pentenyl, 3-methyl-2-pentenyl, 4-methyl-2-pentenyl, l-methyl-3-pentenyl, 2-methyl-3-pentenyl, 3-methyl-3-pentenyl, 4-methyl-3-pentenyl, l-methyl-4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4- methyl-4-pentenyl, 1, l-? imethyl-2-butenyl, 1, l-? imethyl- 3-Butenyl, 1, 2? -imethyl-1-butenyl, 1, 2? -imethyl-2-butenyl, 1, 2? -imethyl-3-butenyl, 1,3-? Imethyl-1-butenyl, 1, 3-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl, 2,2-dimethyl-3-butenyl, 2, 3-? Imethyl-1-butenyl, 2,3-dimethyl-2-butenyl, 2 , 3-dimethyl-3-butenyl, 3, 3-dimethyl-l-butenyl, 3,3-dimethyl-2-butenyl, 1-ethyl-l-butenyl, l-ethyl-2-butenyl, l-ethyl-3 -butenyl, 2-ethyl-l-butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl, 1, 1, 2-trimethyl-2-propenyl, 1- ethyl-l-methyl-2-propenyl, l-ethyl-2-methyl-1-propenyl and 1-ethyl-2-methyl-2-propenyl; alkynyl: straight or branched chain alkynyl groups having from 2 to 8 carbon atoms and a triple bond at any position, eg, alkynyl of C2-C6 such as ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, l-methyl-2-propynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, l-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- Hexylin, 5-hexynyl, 1-methyl-2-pentynyl, 1-methyl-3-pentynyl, 1-methyl-4-pentynyl, 2-methyl-3-pentynyl, 2-methyl-4-pentynyl, 3-methyl- l-pentynyl, 3-methyl-4-pentynyl, 4-methyl-1-pentynyl, 4-methyl-2-pentynyl, 1, 1-dimethyl-2-butynyl, 1, l-? imethyl-3-butynyl, l , 2-? Imethyl-3-butynyl, 2,2-dimethyl-3-butynyl, 3, 3-dimethyl-1-butynyl, l-ethyl-2-butynyl, l-ethyl-3-butynyl, 2-ethyl- 3-butynyl and l-ethyl-1-methyl-2-propynyl; cycloalkyl: monocyclic alkyl groups having 3 to 7 carbon members in the ring, for example, C3-C7 cycloalkyl, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cycloheptyl; cycloalkenyl: monocyclic alkyl groups having ? 5 to 7 carbon members in the ring, which contain one or more double bonds, for example, C5-C7 cycloalkenyl, such as cyclopentenyl, cyclohexenyl, and cycloheptenyl; aryl: monocyclic or polycyclic aromatic groups having from 6 to 10 carbon atoms, such as phenyl and naphthyl; arylalkyl: aryl groups (as already mentioned) that the case of arylalkyl of C? -C4, are attached to the structure through alkyl groups having from 1 to 4 carbon atoms (as already mentioned), for example , C 1 -C 4 phenylalkyl, such as benzyl, 2-phenylethyl, 3-phenylpropyl, 4-phenylbutyl, 1-phenylethyl, 1-phenylpropyl and 1-phenylbutyl; aryloxy: aryl groups (as already mentioned) that are linked to the structure through an oxygen atom (-0-), such as phenoxy, l-naphthoxy and 2-naphthoxy; hetaryl: mono- or polycyclic aromatic radicals which, in addition to the carbon members of the ring, may contain from 1 to 4 nitrogen atoms or from 1 to 3 carbon atoms and an oxygen atom or 1 sulfur atom or an oxygen atom or 1 sulfur atom: - 5-membered hetaryl, containing 1 to 3 nitrogen atoms: 5-membered hetaryl groups, in the ring which in addition to the carbon atoms may contain 1 to 3 atoms of nitrogen as members - the ring, for example, 2-pyrrolyl, 3-pyrrolyl, 3-pyrazolyl, 4-pyrazolyl, 5-pyrazolyl, 2-imidazolyl, 4-imidazolyl, 1, 2,4-triazol-3-yl and 1, 3, 4-triazol-2-yl; 5-membered hetaryl, containing 1 to 4 nitrogen atoms or 1 to 3 nitrogen atoms and one atom sulfur or atom oxygen and one atom oxygen and one atom sulfur: heteroaryl groups limbs in the ring that are still atoms and carbon can contain 1 to 4 atoms of nitrogen or 1 to 3 atoms of nitrogen and one atom of sulfur or atom of oxygen. an oxygen atom or an atom sulfur as ring members, for example, 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, -thiazolyl, 2-imi? azolyl, 4-imi? azolyl, 1, 2, 4-oxa? azazol-3-yl, 1,2,4-oxa? yol-5-yl, 1, 2, 4-tia iazol-3-yl, 1,2,4-thia-ylazol-5-yl, 1, 2,4-triazol-3-yl, 1,3,4-oxadiazol-2-yl, 1, 3, 4 -thiadiazol-2-yl, 1, 3, 4-triazol-2-yl; benzofused 5-membered heteroaryl containing from 1 to 3 nitrogen atoms or a nitrogen atom and / or a atom? or oxygen or atom? sulfur: hetaryl groups? and 5 members in the ring that? the? atoms? carbon can contain 1 to 4 nitrogen atoms or 1 to 3 nitrogen atoms and an atom of sulfur or oxygen or an oxygen atom or an atom? sulfur as members? the ring, and in which the carbon members lying in the ring or a nitrogen and a carbon member lying in the ring can To form a bridge by a group buta-1, 3-? ien-l, 4-? iilo; - 5-membered hetaryl bonded through nitrogen, containing 1 to 4 nitrogen atoms, or 5-membered benzofused or 5-membered hetaryl which is nitrogen-bonded, containing 1 to 3 nitrogen atoms: 5-membered hetaryl groups in the ring, which in addition to the carbon atoms may contain 1 to 4 atoms of nitrogen or of 1 to 3 nitrogen atoms as ring members, and in which two carbon members are attached to the ring or a nitrogen and a carbon member adjacent to the ring can form a bridge by a buta-1,3-dien-1,4-diyl group, where these rings are attached to the structure through one of the members of the nitrogen ring; - 6-membered heteroaryl, which contains from 1 to 3 or 4 atoms and nitrogen: 6-membered heteroaryl groups in the ring, which in addition to the carbon atoms can contain? 3 or? ela? 4 atoms? and nitrogen as members? the ring, for example, 2-pyridinyl, 3-pyridinyl, 4-pyridinyl, 3-pyridin-azinyl, 4- pyridin-azynyl, 2-pyrimidine ? inyl, 4-pyrimidinyl, 5-pyrimidinyl, 2-pyrazinyl, 1, 3, 5-triazin-2-yl, 1,2,4-triazin-3-yl and 1,2,4,5 - tetrazin-3-yl; - hetaril? E 6 benzofusions members containing? E 1 to 4 atoms? E nitrogen: hetaryl groups? And 6 members in the ring in which two adjacent carbon members in the ring can form a bridge with a buta-1 group , 3-dien-1,4-α-yl, for example, quinoline, isoquinoline, quinazoline and quinoxaline. The phrase "partially or completely halogenated" or "is intended to express that in the groups characterized in this way, the atoms" and hydrogen may be partially or completely substituted by identical or different halogen atoms as already mentioned. With respect to their biological action against the harmful fungi, preference is given to the compounds I? On? And the radicals have the following meanings, per se or in combination: R1 methyl; n is 1, in particular 2; R2-hydroxyl alkyl? E C? -C8, with or without substitution as claimed, in particular hydrogen, chlorine, methoxy; R is hydroxy, C? -C8 alkoxy, with or without substitution as is claimed in particular hydrogen, bromine, methoxy; And it's oxygen; R 4 is hydrogen: R 5 is C 1 -C 4 alkyl with or without substitution, cyclohexyl, in particular phenyl, with or without substitution. Regarding your activity? biological, it was very specific preference to the compounds I that are mentioned in the following tables.

Table 1 Compounds? E formula 1.1 where for each? e the compounds R5 corresponds to a row in table A.

Table 2 Compounds of formula 1.2 (1.2) ? on? e for composite fall R5 corresponds to a row in table A.

Table 3 Compounds of formula 1.3 gift for falling compound R5 corresponds to a row in table A.

Table 4 Compounds? E the formula I .4 gift for falling compound R5 corresponds to a row in table A.

Table 5 Compounds of formula 1.5 (1.5) gift for composite fall R3 corresponding to a row in table A.

Table 6 Compounds of formula 1.6 (1.6) gift for each compound R5 corresponds to a row in table A.

Table 7 Compounds of the formula I .7 where for each compound R5 corresponds to a row in table A.

Table 8 Compounds of formula I.8 where for each compound Rü corresponds to a row in table A.

Table 9 Compounds of formula 1.9 ? on? e for composite fall R5 corresponds to a row in table A.

Table 10 Compounds of the formula I. 10 (I.10) CH3 where for each compound R corresponds to a row in table A.

Table A No. Rs Table A (continued) No. R3 The compounds I are suitable for controlling harmful fungi. Depending on their chemical and physical properties, these can be formulated with conventional formulation aids, that is, auxiliary formulations known to a person skilled in the art. The products thus prepared are called "compositions". Suitable formulation auxiliaries are, for example, solid carriers or liquids, surfactants and thickeners. The liquid holders are liquid solvents such as water and organic solvents, the latter especially when water is used as a solvent, they act as auxiliary solvents. Suitable organic solvents are: aromatics such as xylene, toluene and alkylnaphthalenes, chlorine aromatic hydrocarbons or chlorinated aliphatics such as chlorobenzenes, chloroethylenes and methylene chloride, aliphatic hydrocarbons such as cyclohexane and paraffins, for example, fractions Petroleum, alcohols, such as butanol, isobutanol, cyclobutanol and glycol and also the corresponding ethers and esters, ketones, such as acetone, methyl ketone, methyl isobutyl ketone and cyclohexanone, and aprotic ipolar solvents such as? imethylformamide, N-methyl-2- pyrrolidone and dimethylsulfoxy? Suitable solid carriers are, for example, natural minerals crushed and mineral lands such as silicas, silicates, kaolins, clays, calcareoferruginosa clay, loess, talc, chalk, limestone, quicklime, dolomite, magnesium oxide, quartz, attapulgite, montmorillonite, and diatomaceous earth; crushed synthetic materials such as finely divided silicon, oxide, synthetic aluminum crushed or synthetic silicates crushed. The solid holders particularly suitable for granules are, for example: natural rock crushed and fractionated, such as calcite, marble, foot phorax and sepiolite; synthetic granules? and inorganic and organic flours; granules of organic material such as sawdust, husks, coconut, corncobs, corn or stems, and tobacco. The surfactants are non-ionic and anionic emulsifiers / foamers and dispersants: - fatty acid esters - polyoxyethylene, such as lauryl alcohol, polyoexethylene ether acetate, - polyoxyethylene alkyl ethers, oxypropylene alkyl ethers, for example , iso-tri-ethyl alcohol, and polyoxyethylene ethers? fatty alcohols, - alkylaryl alcohol polyoxyethylene ethers, such as octyl phenol polyoxyethylene ether, - tribultyl phenol polyoxyethylene ether, - isooctyl-, octyl- or nonyl or phenol or castor oil? ethoxylates, esters, sorbitol, arylsulfonic acids, alkyl sulfonic acids, alkylsulfuric acids, alkali metal salts, alkali metal salts and metals, and ammonium salts and arylsulfonic acids. , for example, ligno-, phenol-, naphthalene- and? -butylnaphthalene sulphonic acid of alkylsulfonic acids, alkylarylsulfonic acids, alkyl, lauryl ether and sulfates of fatty alcohols, fatty acids, hexa- hepta- and octa-octane sulphates Glycol ethers, fatty alcohols, naphthalene sulphonates, and their alcohols with formaldehyde, naphthalene sulphonic acid condensates with phenol or formal? ehi, hydrolysed proteins. , and - in particular as dispersants: residual liquors and lignin sulphite and methylcellulose. The added thickeners are, for example: carboxymethylcellulose; synthetic and natural polymers in the form of powders, granules or grids such as gum arabic, polyvinyl alcohol and polyvinyl acetate, natural phospholipids such as cephalins and lecithins, synthetic phospholipids.

Furthermore, the compositions may comprise one or more examples of the following groups of compounds: dyes, other known active compounds, traces of nutrients and other additives. Suitable colorants are, for example, inorganic pigments such as iron oxide, oxide, titanium, blue, Prussia, other organic coloring matters, such as alisarin coloring materials, azo dyes and coloring matters. metallic phthalocyanine. Other known active compounds are, for example, other fungici as well as insecticides, caresses, herbicides and growth regulators. Trace nutrients are, for example, salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc. Other equivalent ingredients are, for example, mineral and vegetable oils. Moreover, the compositions can be mixed with other practical mixing substances such as fertilizers and other ready-to-use compositions of active compounds. The compositions are prepared in a conventional manner, ie, depending on the chemical and physical properties of the compounds used, for example, by mixing, grinding, spraying, extruding, granulating or dissolving in water, the latter, if It is necessary, with the help of an organic solvent. Powders, granules can obtained, for example, by mixing or grinding the compounds 1 together with a solid carrier. Depending on the compounds used, the compositions are, for example, solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols or micro-encapsulations in polymeric substances or in seed coatings. For the application, the compositions that are usually available in commerce as concentrates, if necessary, are dissolved, diluted, etc., as is the common practice, in the case? powders for aspersion, granules? ispersible in water, emulsifiable concentrates, ispersions and also in the case? e some micro granules normally use? or water. Powders, granules or solutions for spray usually do not show up more with other inert substances before the application. The compositions are applied in a manner known per se, for example, by spraying, atomizing, dusting, spraying or wetting. In general, the plants are sprinkled or sprinkled with the compositions. Otherwise or in addition, the seeds of the plants are treated in a manner known per se.

Examples of these preparations are: I. A solution? E 90 parts by weight? E a compound I according to the invention, and 10 parts by weight? E N-methyl-2-pyrrolinone, which is suitable for use in the form of micro drops; II. A mixture is 20 parts by weight of a compound according to the invention, 80 parts of xylene, 10 parts by weight, the addition product is 8 to 10 moles of ethylene oxide. to 1 mol N-monoethanolamine? oleic acid, 5 parts by weight? e? o? calcium ecilbenzenesulfonate, 5 parts by weight of the addition product of 40 moles of ethylene oxide to 1 mole? Castor oil: an ispersion is obtained by disuting the solution in water; III. An aqueous dispersion of 20 parts by weight of a compound according to the invention, 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the product? Ea? Tion,? e 40 moles of ethylene oxide to 1 mole of castor oil; IV. An aqueous dispersion of 20 parts by weight of a compound I according to the invention, 25 parts by weight of cyclohexanol, 65 parts by weight of a petroleum fraction from boiling point 210 to 280 ° C and 10 parts by weight of the product of a? ición,? e 40 moles of oxyethylene, ethylene, 1 mol, castor oil; V. A mixture, comminuted in a hammer mill, of 80 parts by weight of compound compound according to the invention, 3 parts by weight? E? Isobutylnaphthalene-1-sulfonate? And so, 10 parts by weight? The only salt, the sulphonic ligneous acid, is a sulphite, and the gel is pulverulent silica: a mixture for sprinkling is obtained by finely disuting the mixture in water; SAW. An intimate mixture of 3 parts by weight of a compound I according to the invention, and 97 parts by weight of finely divided kaolin; this powder consists of 3% by weight of the active ingredient; VII. An intimate mixture of 30 parts by weight of a compound according to the invention, 92 parts by weight of the gel, powdery silica and 80 parts by weight of paraffin oil which has been sprayed. on the surface of this silica gel; this formulation imparts good adhesion to active ingre dient; VIII. A stable aqueous dispersion of 40 parts by weight of a compound I according to the invention, 10 parts by weight of the sodium salt and a con? Ess or phenolsulfonic acid / urea / formaldehyde, 2 parts by weight? silica and 48 parts by weight of water, it being possible for this dispersion to be more dilute; IX. An oily, stable dispersion of 20 parts by weight? E a compound I, according to the invention, 2 parts by weight of calcium dodecylbenzene sulfonate, 8 parts by weight of polyglycol ether of fatty alcohols, 20 parts by weight of the sodium salt and a con? ess or acid. ? or phenolsulfonic / urea / formal? ehi? o and 68 parts by weight? e a paraffin mineral oil. If the compounds I are applied as such, a fine disution is essential. The compounds I and the compositions according to the invention have an activity. outstanding against a broad spectrum of harmful fungi (phytopathogenic fungi), in particular? e classes? and the: - Ascomycetes, Basidiomycetes, - Deutoremicetos, and - Phycomycetes. Some of these act in a systemic way and can be used as fungici as they act on leaves and soil. These are especially important to control a large amount? ? e fungi in a variety? Crop plants, such as wheat, fattening, rye, oats, rice, corn, turf, cotton, soybeans, coffee, sugar cane, grapes, fruit species, ornamental species and vegetables such as cucumbers, beans and Cucurbitaceae, as well as the seeds? e these plants.

The compounds I, their salts and N-oxides and the compositions according to the invention are applied by treating the harmful fungus, its habitat or the seeds, plants, areas, materials or spaces to be protected against infection of the fungus, with a quantity? active as fungici? a • e the compositions or? e the compounds I. The application is made before or after the infection of the fungus. Specifically, the compositions according to the invention and compounds I are added to control the diseases of the following plants: Erysiphe graminis (powdery mildew) in cereals, Erysiphe cichoracearum and Sphaerotheca fuliginea in cucurbits, Po? Osphaera leucotricha in apples, Uncinula necator in vi? Es, Puccinia species in cereals, Rhizoctonia species in something? Ón, rice and céspe? Es, Ustilago species in cereals and sugar cane, Venturia inaequalis (crust or scab) in apples, Helminthosporium species in cereals, Septoria nodorum in wheat, Botrytis cinerea (gray mold) in strawberries, vines, ornamentals and vegetables, Cercospora arachidicola in peanuts, Pseudocercosporella herpotrichoides in wheat, barley, Pyricularia oryzae in rice, Phytophthora infestans in potatoes and tomatoes, Fusarium and Verticillium species in various plants, Plasmopara viticola in vi? es, Pseu? Operonospora species in hops and cucumbers and Alternating species in fruits and vegetables. In general, the fungicidal or fungal compositions comprise from 0.1 to 95, preferably from 0.5 to 90% by weight of the active compound. Depending on the nature, the desired effect, the concentrations of the application are from 0.01 to 2.0 kg, the active compound per ha. In the treatment of the seed, the quantities are from 0.001 to 0.1 g, preferably 0.01 to 0.05 g, the active compound is usually required per kg. The seed The compositions according to the invention in the form of use as fungicides may also be present together or with other active compounds, for example, with herbicides, insecticides, regulators, growth, functions or even with fertilizers. In many cases, a mixture with fungici? As will result as a result of a broader spectrum of fungicidal action. The following list of fungicides, together with which the compounds according to the invention can be used, is proposed to illustrate the possible combinations, but not to impose any limitations: sulfur, dithiocarbamates and their derivatives, as may be ? ethylene carbonate, and iron, zinc? manganese dithiocarbamate, zinc manganese ethylene diamine bis-ithiocarbamate, tetramethylthiuram disulfide, zinc ammonium complex (N, N-ethylene-bis-dithiocarbamate), ammoniacal complex of (N, N'-propylene-bis-? thiocarbamate) and zinc, (N, N-propylene-bis-ithiocarbamate) and zinc, N, N'-polypropylene bis (thiocarbamoyl) -? isulfide; Nitro, as it can be crotonated with dinitro- (1-ethylheptyl) phenyl, 2-sec-butyl-4,6-dinitrophenyl-3, 3-dimethyl acrylate, carbonate and 2-sec. butyl-4, 6-? initrofenilisopropyl, 5-nitroisophthalate? e? i-isopropyl; heterocyclic substances, such as 2-ecta-ecil-2-imi-azoline acetate, 2,4-ichloro-6- (o-chloroanilino) -s-triazine, phthaliminophosphothilate, and 0.0-? -ethyl, 5 -amino-l- [bis (γ-imethylamino) -phosphinyl] -3-phenyl-1,2,4-triazole, 2, 3-cyano-1, 4-ithio-anthraquinone, 2-thio-1, 3 -? itiolo [4, 5-b] quinoxaline, 1- (butylcarbamoyl) -2-benzimido? azole carbamate, methyl, 2-methoxycarbonyl-aminobenzimido? azole, 2- (furyl- (2)) benzimidozole, 2 - (thiazolyl- (4)) benzimidozol, N- (1,1, 2,2-tetrachloroethylthio) tetrahydrophthalimide, N-trichloromethylthiotetrahi? roftalimi? a, N-trichloromethylthioftali? a, diamide N-dichlorofluoromethylthio-N ', N '-? Imethyl-N-phenylsulfuric acid, 5-ethoxy-3-trichloromethyl-1,2,3-thiazole, 2-thiocyanatomethylthiobenzothiazole, 1,4-dichloro-2,5-dimethoxybenzene, 4- (2 -chlorofenilhi? razono) -3-methyl-5-isoxazolone, pyri-in-2-thio-l-oxy, 8-hydroxyquinoline or its copper salt, 2,3-dihydro-5-carboxanilido-6-methyl-l, 4-oxathiaine, 2, 3-? ihi? ro-5-carboxanyl-o-6-methyl-l, 4-oxathiain-4, 4-oleyoxy, 2-methyl-5,6-dihydro-4H-pyran-3-carboxanilyl, 2 -methylfuran-3-carboxanyl? a, 2, 5-? imethylfuran-3-carboxanyl? a, 2,4,5-trimethyl furan-3-carboxanilide, N-cyclohexyl-2, 5-dimethyl-furan-3-carboxy? a, N- cyclohexyl-N-methoxy-2, 5-? imethylfuran-3-carboxyamy, 2-methylbenzanyl? a, 2-yo? obenzanili? a, N-formyl-N-morpholine 2, 2, 2-trichloroethyl acetal, piperazine -1, 4-? Iilbis (1- (2, 2, 2-trichloroethyl) formami? A, l- (3,4-? Icloroanilino) l-formylamino-2, 2, 2-trichloroethane, 2,6-dimethyl-N-tphidecylmorpholine or its salts, 2,6-imetyl-N-cyclododecylmorpholine or its salts, N- [3- (p-tert-butylphenyl) -2-methylpropyl ] -cis-2, 6-dimethylmorpholine, N- [3- (p-tert-butylphenyl) -2-methylpropyl] piperi? ina, l- [2- (2,4-dichlorophenyl) -4-ethyl-1, 3-dioxolan-2-ylethyl] -1H-1,2,4-triazole, 1- [2- (2,4-dichloro-phenyl) -4-n-propyl-l, 3-yxoxolan-2-ylethyl ] -1H-1, 2,4-triazole, N- (n-propyl) -N- (2,4,6-trichlorophenoxyethyl) -N-f-yl) azolylurea, 1- (4-chlorophenoxy) -3,3- ? imethyl-l- (1H-1,2,4-triazol-1-yl) 2-butanone, (2-chlorophenyl) - (4-chlorophenyl) -5-pyrimidine-methanol, 5-butyl-2-dimethylamino- 4-hydroxy-6-methylpyrimidine, bis (p-chlorophenyl) -3-pyrimethanol, 1,2-bis (3-ethoxycarbonyl-2-thioureidyl) benzene, 1,2-bis (3-methoxycarbonyl) -2-thioureido) benzene, [2- (4-chlorophenyl) ethyl] - (1,1-dimethylethyl) - 1H, 1, 2, 4-triazole-1-ethanol, and Various functions such as acetate, dodecylguanine, 3- [3- (3, 5-? imethyl-2-oxycyclohexyl) -2-hydroxyethyl] glutarimic acid, hexachlorobenzene, methyl N- (2, 6) -? imethylphenyl) -N- (2-furoyl) DL-alaninate, DL-N- (2, 6-? imethylphenyl) -N- (2'-methoxyacetyl) -alanine methyl ester, N- (2, 6? imethylphenyl) -N-chloroacetyl-D, L-2-aminobutyrolactone, DL-N- (2, 6-? imethylphenyl) -N- (phenylacetyl) alanine methyl ester, 5-methyl-5-vinyl-3- (3, 5-? - chlorophenyl) -2,4-? -ioxo-l, 3-oxazolidine, 3- (3,5-dichlorophenyl) 5-methyl-5-methoxymethyl-l, 3-oxazoli? Ina-2,4-dione, 3- (3,5-dichlorophenyl) -1-iso-propylcarbamoylhydantoin, N- (3,5-dichlorophenyl) -1,2-? Imethylcyclopropan-1, 2-dicarboximide, 2-cyano- [N- (ethylaminocarbonyl) - 2-methoximino] -acetamide, 1- [2- (2, 4? -chlorophenyl) pentyl] -1H-1, 2,4-triazole, 2, 4-? Ifluoro-a- (1H-1, 2, 4 -triazolyl-l-methyl) benzhi? ryl alcohol, N- (3-chloro-2, 6-? initro-4-trifluoromethylphenyl) -5-trifluoro-methyl-3-chloro-2-aminopyridine, 1- ( (bis- (4-fluorophenyl) methyl-silyl) methyl) -1H-1, 2 , 4-triazole.

Strobilurins, such as methyl E-methoximino- [a- (o-tolyloxy) o-tolyl] acetate, methyl E-2-. { 2- [6- (2-cyanophenoxy) pyri? Imin-4-yloxy] phenyl} -3-methoxyacrylate, N-methyl-E-methoximino- [a- (2-phenoxyphenyl)] acetam- ine, N-methyl-E-methoximino- [a- (2, 5? Imetilphenoxy) -o-tolyl] acetami? Anilinopyrimetics, such as N- (4,6-dimethylpyrimidin-2-yl) -aniline, N- [4-methyl-6- (1-propynyl) pyrimidin-2-yl] aniline, N- (4-methyl- 6-cyclopropyl-pyrimidin-2-yl) aniline.

Phenylpyrroles, 4- (2, 2-difluoro-1,3-benzodioxol-4-yl) pyrrole-3-carbonitrile Cinnamines, such as 3- (4-chlorophenyl) -3- (3, 4-? Imethoxyphenyl) acryloylmorpholide. (2RS, 3SR) -1- [3- (2-chlorophenyl) -2- [4-fluorophenyl] oxiran-2-ylmethyl] -1H-1,2,4-triazole.

Preparation Examples The following procedures and examples can be used to prepare other representatives of the compounds I modify or the initial materials. Physical processes and products are prepared in this way and are mentioned in the table below. 1. 2-Methylsulfonyl-5-bromopyrimido-4-carboxy (4-fluorophenyl) amide (compound S1.10) a) The 2-thiomethyl-5-bromopyrimidine-4-carboxylic acid was obtained by the method of J. Chem. Soc. 1953, 3129-21: 56 g (0.217 mol)? and mucobronic acid were dissolved in 800 ml of water at 50 ° C, and 60 g (0.217 mol)? sulfate? and S-methylisothiourea were added at this temperature. After cooling to room temperature, 65.8 g (0.651 mol) of triethylamine were added dropwise with stirring, the temperature was maintained at 20 ° C. After acidification with concentrated hydrochloric acid, the product crystallized as a solid (28.0 g, mp 168-170 ° C). b) 2-thiomethyl-5-bromopyrimido-in-4-carbonyl chloride 10.1 g (40 mmol)? 2-thiomethyl-5-bromopyrimido-4-carboxylic acid and 50 ml? thionyl were stirred with 1 ml of DMF for two hours at 80 ° C. The thionyl chloride was distilled and the product was fractionated at 105-110 ° C and 0.8 mbar. Ren? I iento: 9.3 g. C) 2-thiomethyl-5-bromopyrimido-in-4-carboxy (4- fluorophenyl) ami? A 1.0 g (3.7 mmol)? And chloride? E 2-thiomethyl-5-bromopyrimidine-4-carbonyl and 0.4 g ( 4 mmol) of triethylamine were dissolved in 40 ml of anhydrous toluene, and 0.41 g (3.7 mmol) and 4-fluoroaniline were added with stirring. The mixture was stirred for 16 hours and washed with 50 ml each time 2 N hydrochloric acid, a 5% sodium bicarbonate solution and water, and the organic phase was dried with sodium sulfate. so? io and concentrated. This pro? Ujo 1.2 g? E 2-thiomethyl-5-bromopyrimido? In-4-carboxy- (4-fluorophenyl) ami? A (Compound S1.47). ?) 2-methylsulfonyl-5-bromopyrimido? In-4-carboxy (4-fluorophenyl) ami? A 50 mg? Tungstate? Were added to a mixture of 0.4 g of peroxide? And hi? 30% nitrogen and 5 ml glacial acetic acid, and the mixture was stirred for 15 min. 1.2 g (3.5 mmol) of 2-thiomethyl-5-bromopyrimidine-4-carboxy (4-fluorophenyl) amide dissolved in glacial acetic acid were then added, and the mixture was stirred for 16 hours at 25 ° C. With the addition of 100 milliliters of water, the product precipitated in the form of yellow crystals and was filtered with suction. This yielded 1.1 g of the title compound (mp 169-174 ° C, compound S1.10). 2. 2-Methylsulfonylpyrimidine-4-carboxy (4-fluorophenyl) amide (compound S1.23) a) The 2-thiomethylpyrimido-4-carboxylic acid was prepared by the E.? Chem. 29 (1986), 1374-80: 46.8 g (0.188 mol) of 2-thiomethyl-5-bromopyrimido-in-4-carboxylic acid together with 23 g (0.41 mol)? And hydroxy potassium were dissolved in 800 ml of methanol. After the addition of 10 g of 5% palladium. on barium sulfate, a pressure of 10 bar? and hi? ogen was applied and the mixture was stirred for 16 hours. The catalyst was filtered and the filter was diluted with water and acidified to pH 1 using chlorine acid. The product precipitated in the form of light brown crystals. Recrystallization from ethanol produced 28.7 g of 2-thiomethylpyrimido-4-carboxylic acid at 211-215 ° C. b) 2-thiomethylpyrimido-4-carboxy (4-fluorophenyl) ami? a 0.68 g (4 mmol)? and 2-thiomethylpyrimidine-4-carboxylic acid and 0.44 g (4 mmol) of 4-fluoroaniline were suspended in 50 ml of ichloromethane (puriss). After the addition of 0.5 g of triethylamine, 0.7 g (4 mmol) of 93% diethyl cyanophosphonate were dropwise and the mixture was stirred at 25 ° C for 16 hours. 50 ml of dichloromethane were added, and the mixture was washed 2 times with 100 ml of an aqueous solution of 2 N soya hydroxide, hydrochloric acid, sodium bicarbonate solution. at 5% and water each time.

The organic phase was then dried and concentrated. This procedure 0.9 g 2-thiomethylpyrimidine-4-carboxy (4-fluorophenyl) -amide (compound S1.48) c) 2-methylsulfonylpyrimidine-4-carboxy (4-fluorophenyl) amine mg tungstate sodium were added to a mixture of 0.4% peroxygen and 30% hydrogenated and 5 ml glacial acetic acid, and the mixture was stirred? during 15 minutes. 0.9 g (3.4 mmol) of 2-thiomethylpyrimido-4-carboxy (4-fluorophenyl) amide dissolved in glacial acetic acid were then added, and the mixture was stirred at 25 ° C for 16 hours. With the addition of 100 ml of water, the product precipitated in the form of yellow crystals and was filtered with suction. This yielded 0.6 g? The compound? The title (mp 175-178 ° C, compound S1.23) 3. 2-methylsulfonyl-6-chloropyrimido-in-4-carboxy (4-fluoro-phenyl) ami? A ( compound S1.43) a) 2-thiomethyl-6-chloropyrimidine-4-carbonyl chloride 50 g (0.27 mol) of 2-thiomethyl-6-hydroxypyrimidine-4-carboxylic acid (see J. Org. Chem. 26 (1961 ), 2755-61) and 100 ml of phosphorous oxytrichloride were heated to reflux at 80 ° C for 6 hours. Phosphorous oxytrichloride was distilled and the product was fractionated at 100-102 ° C and 0.5 mbar. Renning: 36.7 gb) 2-thiomethyl-6-chloropyrimido-4-carboxy (4-fluorophenyl) -amino 2.4, g (10.8 mmol)? And chloride? E 2-thiomethyl-6-chloropyrim? in-4-carbonyl and 1.2 g (11.8 mmol)? triethylamine were dissolved in 50 ml? -chloromethane (puriss.), and 1.2 g (10.8 mmol)? and fluoroaniline were added with stirring. The mixture was stirred for 16 hours and washed with 50 ml of acid each time. 2 N hydrochloric acid, 5% sodium bicarbonate solution and water, and the organic phase was dried with sodium sulfate and concentrated. Chromatography on silica gel (eluent hexane / MTBE = 9/1) gave 1.3 g of 2-thiomethyl-5-bromopyrimidine-4-carboxy (4-fluorophenyl) amide (mp 116-120 ° C; compound S1.34 ) 2-Methylsulfonyl-6-chloropyrimidine-4-carboxy (4-fluorophenyl) ami? A 100 mg? Tungstate was added to a mixture of 2.4 g? Peroxy? E and hi? 30% and 20 ml glacial acetic acid, and the mixture was stirred for 15 minutes. 0.7 g (2.4 mmol) and 2-thiomethyl-6-chloropyrimido-4-carboxy (4-fluorophenyl) amide dissolved in glacial acetic acid were then added, and the mixture was stirred at 25 ° C? uring 16 hours. With the addition of 100 ml of water, the product precipitated in the form of yellow crystals and was filtered with suction. This produced 0.7 g? The compound? The title (mp 180-182 ° C, compound S1.43).

Table Sl R3 O Table Sl (continued) Examples? E use For the following experimental investigations? E the activity? fungici a of the compounds I, an emulsion consisting of 10% by weight of the active compound and 90% by weight of a mixture? e: 70% by weight? and cyclohexanol, 20% by weight? and Nekanil® LN (Lutensol® AP6, wetting agent) was used. which has emulsifying and dispersing action, based on ethoxylated alkylphenols) and 10% by weight of Uniperon® EL (non-ionic emulsifier based on oil? and ricino ethoxylate?) The concentration? the active compound? esa? or was established by dilution of this emulsion with water. The degree of infection was determined visually.

Claims (1)

CLAIMS Pyrimido-4-carboxamides of the formula I salts and N-oxides thereof, wherein: it is Ci-Cs alkyl, it being possible for these radicals to be partially or completely halogenated and / or to carry from 1 to 3 [mu] e the following groups: cyano alkoxyalkyl and C1-C4 , haloalkyl? C? ~ C4, C? -C4 alkoxy, C? -C4 haloalkoxy, C? -C alkylthio, alkoxycarbonyl? C? C, cycloalkyl? C3-C7, cycloalkenyl? e C3- C7,. aryl, allyloxy and etaryl, it being possible in turn that the cyclic radicals carry one to three of the following substituents: halogen, cyano, C1-C4 alkyl, C1-C4 alkoxyalkyl, C? -C haloalkyl, alkoxy of C3.-C4, haloalkoxy of C1-C4, alkylthio of C1-C4, alkoxycarbonyl of C1-C4, aryl, aryloxy and etharil, or is aryl, while it is possible for the radicals to carry 1 or, independents between yes, 2 or 3? e the following groups: halogen, cyano, C3-C4 alkoyl, C? -C4 alkoxyalkyl, C1-C4 haloalkyl, C1-C4 alkoxy, haloalkoxy? C? -C4, C1-C4 alkylthio, C1-C4 alkoxycarbonyl, aryl, aryloxy and ethanoyl, while it is also possible that the cyclic substituents bear one or, interpense with each other, The following substituents are halogen, cyano, C1-C4 alkyl, C1-C4 alkoxyalkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, and alkylthio. C 1 -C 4, and C 1 -C 4 alkoxycarbonyl, "n is 0, 1 or 2; R 2 is hydrogen, halogen hydroxyl, C 1 -C 8 alkyl, C 1 -C 8 haloalkyl, C 1 -C 8 alkoxy; , haloalkoxy? C- C8; R3 is hydrogen, hydroxy, halogen, C? -C8 alkyl, C? -C8 haloalkyl, C? -C8 alkoxy, C? C8 haloalkoxy; the R2 and R3 radicals in case will always be hydrogen, and is oxygen or sulfur, R4 is hydrogen or alkyl? and C? -C8, which can be partially or completely halogenated, or cycloalkyl C3-C7, which can be partially or completely halogenated, R5 is alkyl? e C? -8, it is possible that these radicals are partially or completely h allogenates and / or carry, or interpense with each other, three or three of the following groups: C1-C4 cyano alkoxyalkyl, C1-C4 haloalkyl, C, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, d-C 4 alkylthio, C 1 -C 4 alkoxycarbonyl, C 3 -C 7 cycloalkyl, C 3 -C 7 cycloalkenyl, aryl, allyloxy and ethynyl, In turn, it is possible for the cyclic radicals to carry one or more of one or more of the following substituents: halogen, cyano, C1-C4 alkyl, C1-C4 alkoxyalkyl, haloalkyl C1-C4, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylthio, C1-C4 alkoxycarbonyl, aryl, aryloxy and ethanoyl, or is C3-C7 cycloalkyl, if possible for this ra? Any one or two independent of the following groups: halogen, Ci-C4 alkyl, haloalkyl of C? -C4 and C1-C4 alkoxy, or is aryl, it being possible for this radical to carry one , independent of each other, two or three of the following groups: halogen, cyano, C 1 -C 4 alkyl, C 1 -C 4 alkoxyalkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy, haloalkoxy → C 1 -C 4, alkylthio? e C1-C4, alkoxycarbonyl and C1-C4, aryl, aryloxy and eta It is also possible that the cyclic substituents bear one or more of the following substituents: halogen, cyano, C1-C4 alkyl, C1-C4 alkoxyalkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, C 1 -C 4 alkylthio, C

1 -C 4 alkoxycarbonyl. The fungici? As, which comprise a quantity? activates as a fungicide a compound of the formula I or a salt or N-oxy or the same as claimed in claim 1 and at least one auxiliary of the conventional formulation. The method to control the harmful fungi, which they buy in treating the harmful fungi, their habitat or the plants, areas, materials or spaces that must be kept free? And these, with an active amount of a compound of the general formula I or a salt or N-oxide thereof as claimed in claim 1, or a fungicide as claimed in claim 2. The use of the compounds of the general formula I and the salts and N -oxides are the same as claimed in claim 1, to control fungal fungi.