DE19622270A1 - Pyrimidine-4-carboxamides - Google Patents

Abstract

Pyrimidine-4-carboxylic acid amides of formula (I) and their salts, in which R<1> is optionally substituted alkyl, aryl; n is 0, 1, or 2; R<2> is hydrogen, hydroxy, halogen, alkyl, alkyl halide, alkoxy, alkoxy halide; R<3> is hydrogen, hydroxy, halogen, alkyl, alkyl halide, alkoxy, alkoxy halide, where one of the radicals R<2> and R<3> always stands for hydrogen; Y is oxygen or sulphur; R<4> is hydrogen or optionally partially or fully halogenated alkyl, cycloalkyl; R<5> is optionally substituted alkyl, cycloalkyl, aryl; and agents containing them and their use as fungicides.

Description

The present invention relates to pyrimidine-4-carboxamides of formula I.

as well as their salts and N-oxides, in which the variables have the following meaning:
R¹ C₁-C₈-alkyl, these radicals being partially or completely halo and / or can carry one to three of the following groups: cyano, C₁-C₄-alkoxyalkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁- C₄-haloalkoxy, C₁-C₄-alkylthio, C₁-C₄-alkoxycarbonyl, C₃-C₇-cycloalkyl, C₃-C₇-cycloalkenyl, aryl, aryloxy and heteroaryl, where the cyclic radicals may in turn carry one to three of the following substituents: halogen , Cyano, C₁-C₄-alkyl, C₁-C₄-alkoxyalkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkylthio, C₁-C₄-alkoxycarbonyl, aryl, aryloxy and heteroaryl or
Aryl, this radical being able to carry one or, independently of one another, two or three of the following groups: halogen, cyano, C₁-C₄-alkyl, C₁-C₄-alkoxyalkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄ -Halogenalkoxy, C₁-C₄-alkylthio, C₁-C₄-alkoxycarbonyl, aryl, aryloxy and heteroaryl, in which the cyclic substituents in turn can carry one or, independently of one another, two or three of the following substituents: halogen, cyano, C₁-C₄- Alkyl, C₁-C₄-alkoxy alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkylthio and C₁-C₄-alkoxycarbonyl
n 0, 1 or 2;
R² is hydrogen, hydroxy, halogen, C₁-C₈ alkyl, C₁-C₈ halo alkyl, C₁-C₈ alkoxy, C₁-C₈ haloalkoxy;
R³ is hydrogen, hydroxy, halogen, C₁-C₈-alkyl, C₁-C₈-haloalkyl, C₁-C₈-alkoxy, C₁-C₈-haloalkoxy,
where one of the radicals R² and R³ is always hydrogen;
y oxygen or sulfur;
R⁴ is hydrogen or optionally partially or optionally fully halogenated C₁-C₈-alkyl or optionally partially or optionally fully halogenated C₃-C₇-cycloalkyl;
R⁵ C₁-C₈-alkyl, these radicals being partially or completely halo and / or one or, independently of one another, can carry two or three of the following groups: cyano, C₁-C₄-alkoxyalkyl, C₁-C₄-haloalkyl, C₁-C₄ -Alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkylthio, C₁-C₄-alkoxycarbonyl, C₃-C₇-cycloalkyl, C₃-C₇-cycloalkenyl, aryl, aryloxy and heteroaryl, the cyclic radicals in turn one, or independently two or can carry three of the following substituents: halogen, cyano, C₁-C₄-alkyl, C₁-C₄-alkoxyalkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkylthio, C₁ -C₄ alkoxycarbonyl, aryl, aryloxy and heteroaryl or
C₃-C₇-cycloalkyl, which radical may carry one or, independently of one another, two or three of the following groups: halogen, C₁-C₄-alkyl, C₁-C₄-haloalkyl and C₁-C₄-alkoxy or
Aryl, this radical being able to carry one or, independently of one another, two or three of the following groups: halogen, cyano, C₁-C₄-alkyl, C₁-C₄-alkoxyalkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄ -Halogenalkoxy, C₁-C₄-alkylthio, C₁-C₄-alkoxycarbonyl, aryl, aryloxy and heteroaryl, in which the cyclic substituents in turn can carry one or, independently of one another, two or three of the following substituents: halogen, cyano, C₁-C₄- Alkyl, C₁-C₄-alkoxy alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkylthio and C₁-C₄-alkoxycarbonyl.

In addition, the invention relates to those containing compounds I. Agents and the use of the compounds I and the agents for Control of harmful fungi.

Compounds of type 1 with fungicidal activity are known from EP-A 569 912 and WO-A 95/25 72.3.  

The effect of those described in the aforementioned publications However, connections against harmful fungi cannot yet satisfy.

The present invention was therefore new pyrimidine-4-carbon acid amides with improved properties, especially high ren effect and besides a broad spectrum of activity in the Be fighting harmful fungi as a task.

Accordingly, the compounds I defined at the outset were ent holding funds and their use and use of funds found to combat harmful fungi.

The compounds I can in a manner known per se or analogously to be made using known methods, as in the following three manufacturing processes is shown as an example.

Manufacturing process 1

The pyrimidine-4-carboxamides I, in which
R1 = methyl;
R² = chlorine;
R³ = hydrogen;
Y = 0 and
n = 0, 1 or 2,
is obtained, for example (see scheme 1 below), by first reacting a compound 11 with S-methylisothiourea sulfate (III) to give 4-hydroxypyrimidine-6-carboxylic acid IV (see J. Org. Chem. 26, page 2755 (1961 After chlorination of the hydroxy function, which takes place in a manner known per se and provides the compounds V, the compounds V are reacted with amines VI to give the amides T (n = 0). Compounds I, in which n is 1 or 2 is obtained from these amides by oxidation.

Scheme 1

The amines VI are known or can be easily obtained (see Houben-Weyl, Methods of Organic Chemistry, Georg Thieme Verlag, Stuttgart, Volume XI / 1, 4th edition, 1957, page 24 to Page 262 and page 360 to page 409).

The amines VI are reacted with the compounds V before preferably in a solvent such as dichloromethane, tetrahydro furan or toluene.

In particular, the amines VI themselves can serve as bases, where they are usually recovered from the raw product.

The oxidation of the amides T, where n = 0, to the corresponding Compounds I with n = 1 or 2 can in a manner known per se (see Houben-Weyl, Methods of Organic Che mie, Georg Thieme Verlag, Stuttgart, Volume EII, 4th edition, 1985, Pages 665-850, especially pages 702-718 (Volume I); ibid., Be ten 1129-1256, especially pages 1194-1204 (volume II); ibid., Vol. IX, 4th edition, 1955, p. 222 ff.)  

Suitable oxidizing agents are e.g. B. hydrogen peroxide, organic peroxides such as acetic acid peroxide, trifluoroacetic acid peroxide, m-chloroperbenzoic acid, tert-butyl hydroperoxide and tert-butyl hypochlorite, as well as inorganic compounds such as sodium metaio dat, chromic acid and nitric acid.

The complete oxidation of sulfur is particularly suitable Hydrogen peroxide, organic peroxides such as acetic acid peroxide, Trifluoroacetic acid peroxide and m-chloroperbenzoic acid, further inorganic oxidizing agents such as potassium permanganate. With Ver When using inorganic oxidizing agents, the addition of a Catalyst, e.g. B. tungstate, conducive to the course of the reaction be.

A mixture of sodium tungstate and Hydrogen peroxide.

As a rule, the implementation is carried out in an inert solution medium before, depending on the oxidizing agent z. B. organic acids such as acetic acid, trichloroacetic acid and propionic acid, chlorinated Hydrocarbons such as methylene chloride, chloroform and 1,2-dichloroethane, aromatic hydrocarbons or halogen hydrocarbons such as benzene, chlorobenzene and toluene, protic Solvents such as methanol and ethanol, or water can be used are. Mixtures of the solvents mentioned also come into Be dress.

The reaction temperature is generally from (-30) ° C to Boiling temperature of the respective reaction mixture, for partial Oxidation of the sulfur tends to be in the lower temperature range complete oxidation, however, preferably at 10 ° C to Boiling temperature. It is particularly preferred to work at 0 to 40 ° C.

Depending on the desired target product I with m = 1 or 2, one uses in approximately equimolar amounts of oxidizing agent or approximately 2-fold molar excess.

The compounds of formula I can also be known per se Can be converted into their N-oxides (cf. e.g. A. Albini et al. S. Pietra, Heterocyclic N-Oxides, CRC-Press Tnc., Boca Raton, USA 1991; H.S. Mosher et al., Org. Synth. Coll. Vol. IV 1963, page 828; E.C. Taylor et al., Org. Synth. Coll. Vol. IV 1963, Page 704; T.W. Bell et. al., Synth. 69: 226 (1990)).

Among the oxidizing agents customary for oxidation are playful peracetic acid, trifluoroperacetic acid, perbenzoic acid, m-chloroperbenzoic acid, monopermaleic acid, magnesium monoperphtha  lat, sodium perborate, Oxone® (contains peroxodisulfate), Per called tungstic acid and hydrogen peroxide.

Suitable solvents are e.g. B. water, sulfuric acid, carbon acids such as acetic acid and trifluoroacetic acid and halogenated Hydrocarbons such as dichloromethane and chloroform.

The oxidation normally takes place at temperatures from 0 ° C to Boiling temperature of the reaction mixture.

The oxidant is usually in at least equimolar Amounts based on the starting compound used. Generally but has a large excess of oxidizing agent as proven particularly advantageous.

Manufacturing process 2

The pyrimidine-4-carboxamides I, in which
R1 = methyl;
R² = hydrogen;
R³ = bromine;
Y = 0 and
n = 0, 1 or 2,
is obtained, for example (cf. scheme 2 below), by reacting mucobromic acid VII with S-methylisothiourea sulfate (III) to give 5-bromopyrimidine-6-carboxylic acids VIII (cf. J. Chem. Soc. 1953, pages 3129-3131), and then proceed as described in manufacturing method 1.

Alternatively, one works particularly in the representation of the ent speaking amides I so that the 5-bromopyrimidine-6-carboxylic acid ren VIII converted into acyl cyanides or anhydrides (cf. Tetra hedron Letters, volume 18, page 1595 to page 1598 (1973), or "Houben-Weyl", volume 15/1, page 28 to page 32). For the production the carboxy-activated acyl cyanide is suitable for. B. the reaction  with diethyl cyanophosphonate, especially in an inert Solvents such as tetrahydrofuran or toluene. For the production the carboxy-activated anhydrides is the reaction with carbonic acid rechlorides such as isobutyl chloroformate in the presence of Bases and optionally in an inert solvent such as Toluene or tetrahydrofuran preferred.

Manufacturing process 3

The pyrimidine-4-carboxamides 1, in which
R1 = methyl;
R² = hydrogen;
R³ = hydrogen;
Y = 0 and
n = 0, 1 or 2,
is obtained, for example, by compound VIII (cf. Preparation 2) according to Acta Chem. Scand. B40, pages 588-92 (1986) and J. Med. Chem. 29, pages 1374-80 (1986) enthalogenated and proceeded as described in the manufacturing process 1.

The compounds of formula I may optionally be dependent of the nature of the substituents as geometric and / or optical isomers or mixtures of isomers are present. Both the pure isomers as well as the mixtures of the isomers have the fungicidal effect on.

The salts of the acid-resistant are also part of the invention Compounds I, which are basic centers, especially basic Contain nitrogen atoms, especially with mineral acids such as Sulfuric acid and phosphoric acid or Lewis acids such as zinc chloride. Usually it depends on the type of salt not at. For the purposes of the invention, those salts are preferred which plants, areas, materia to be kept free from harmful fungi lien or rooms do not damage and the effect of the connections I don't interfere. Such are particularly important Salts which are suitable for agricultural purposes.

The salts of the compounds I are in a manner known per se common, especially by implementing the appropriate connection gen I with the acids mentioned in water or an inert orga African solvents at temperatures from (-80) to 120 preferably 0 to 60 ° C.  

In the definitions of the compounds I given at the outset, collective terms were used which are generally representative of the following groups:
Halogen: fluorine, chlorine, bromine and death;
Alkyl: straight-chain or branched alkyl groups with 1 to 8 carbon atoms, e.g. B. C₁-C₆-alkyl such as methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl, 2,2-dimethylpropyl, 1,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1- Dimethyl butyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1 , 2,2-trimethylpropyl, 1-ethyl-1-methyl propyl and 1-ethyl-2-methylpropyl;
Haloalkyl or partially or fully halogenated alkyl: straight-chain or branched alkyl groups having 1 to 4 or 8 carbon atoms (as mentioned above), in which groups the hydrogen atoms can be partially or completely replaced by halogen atoms (as mentioned above), for . B. C₁-C₂-haloalkyl such as chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2nd - chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl and pentafluoroethyl;
Alkoxy: straight-chain or branched alkoxy groups with 1 to 4 carbon atoms, e.g. B. C₁-C₃ alkoxy such as methyloxy, ethyloxy, propyloxy and 1-methylethyloxy;
Alkoxyalkyl: straight-chain or branched alkyl groups with 1 to 8 carbon atoms (as mentioned above), which in a random position bear a straight-chain or branched alkoxy group (as mentioned above) with 1 to 4 carbon atoms in the case of C₁-C₄-alkoxyalkyl, such as methoxymethyl , Ethoxymethyl, n-propoxymethyl, n-butoxymethyl, 1-methoxyethyl, 2-methoxyethyl, 1-ethoxyethyl, 2-ethoxyethyl, 2-n-propoxyethyl and 2-butoxyethyl;
Halogenalkoxy: straight-chain or branched alkoxy groups having 1 to 4 carbon atoms (as mentioned above), in which groups the hydrogen atoms can be partially or completely replaced by halogen atoms (as mentioned above), e.g. B. C₁-C₂-haloalkoxy such as chloromethyloxy, dichloromethyloxy, tri chloromethyloxy, fluoromethyloxy, difluoromethyloxy, trifluoromethyl oxy, chlorofluoromethyloxy, dichlorofluoromethyloxy, chlorodifluoromethyloxy, 1-fluoroethyloxy, 2-fluoroethyloxy, 2,2-difluoromethyloxy, 2,2,2-oxyoxy-2,2,2-trifluoromethyloxy , 2-chloro-2-fluoroethyloxy, 2-chloro-2,2-difluoroethyloxy, 2,2-dichloro-2-fluoroethyloxy, 2,2,2-trichloroethyloxy and pentafluoroethyloxy;
Alkylthio: straight-chain or branched alkyl groups with 1 to 4 carbon atoms (as mentioned above) which are bonded to the skeleton via a sulfur atom (-S-), e.g. B. C₁-C₄ alkyl thio such as methylthio, ethylthio, propylthio, 1-methylethylthio, n-butylthio and tert-butylthio;
Alkoxycarbonyl: straight-chain or branched alkoxy groups with 1 to 4 carbon atoms (as mentioned above) which are bonded to the skeleton via a carbonyl group (-CO-);
Alkenyl: straight-chain or branched alkenyl groups with 2 to 8 carbon atoms and a double bond in any position, e.g. B. 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, 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-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 and 1-ethyl-2-methyl-2-propenyl;
Alkynyl: straight-chain or branched alkynyl groups with 2 to 8 carbon atoms and a triple bond in any position, e.g. B. 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-pentinyl, 2-methyl-4-pentinyl, 3-methyl-1-pentinyl, 3-methyl-4-pentinyl, 4-methyl-1-pentinyl, 4-methyl-2-pentinyl, 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 and 1-ethyl-methyl-2-propynyl;
Cycloalkyl: monocyclic alkyl groups with 3 to 7 carbon ring members, e.g. B. C₃-C₇ cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cycloheptyl;
Cycloalkenyl: monocyclic alkyl groups with 5 to 7 carbon ring members which contain one or more double bonds z. B. C₅-C₇ cycloalkenyl such as cyclopentenyl, cyclohexenyl and cyclo heptenyl;
Aryl: monocyclic or polycyclic aromatic groups with 6 to 10 carbon atoms, such as phenyl and naphthyl;
Arylalkyl: aryl groups (as mentioned above) which, in the case of aryl (C₁-C₄) alkyl, are bonded to the skeleton via alkyl groups having 1 to 4 carbon atoms (as mentioned above), for. B. phenyl (C₁-C₄) alkyl such as benzyl, 2-phenylethyl, 3-phenylpropyl, 4-phenylbutyl, 1-phenylethyl, 1-phenylpropyl and 1-phenylbutyl;
Aryloxy: aryl groups (as mentioned above) which are bonded to the structure via an oxygen atom (-O-), such as phenoxy, 1-naphthoxy and 2-naphthoxy;
Heteroaryl: aromatic mono- or polycyclic radicals which, in addition to carbon ring members, can additionally contain 1 to 4 nitrogen atoms or 1 to 3 nitrogen atoms and one oxygen or one sulfur atom or one oxygen or one sulfur atom, e.g. B .:

• 5-membered heteroaryl containing 1 to 3 nitrogen atoms: 5-ring heteroaryl groups, which in addition to carbon atoms 1 can contain up to 3 nitrogen atoms as ring members, e.g. B. 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 heteroaryl containing 1 to 4 nitrogen atoms or 1 to 3 nitrogen atoms and 1 sulfur atom or acid substance atom or 1 oxygen or 1 sulfur atom: 5-ring Heteroaryl groups which, in addition to carbon atoms 1 to 4 Nitrogen atoms or 1 to 3 nitrogen atoms and 1 sulfur or Oxygen atom or 1 oxygen or sulfur atom as May contain ring members, for. B. 2-furyl, 3-furyl, 2-thienyl, 3-thienyl, 2-pyrrolyl, 3-pyrrolyl, 3-tsoxazolyl, 4-tsoxazolyl, 5-isoxazolyl, 3-isothiazolyl, 4-isothiazolyl, 5-isothiazolyl, 3-pyrazolyl, 4-pyrazolyl, 5-pyrazolyl, 2-oxa zolyl, 4-oxazolyl, 5-oxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 2-imidazolyl, 4-imidazolyl, 1,2,4-oxadiazole 3-yl, 1,2,4-oxadiazol-5-yl, 1,2,4-thiadiazol-3-yl, 1,2,4-thiadiazol-5-yl, 1,2,4-triazol-3-yl, 1,3,4-oxadiazol 2-yl, 1,3,4-thiadiazol-2-yl, 1,3,4-triazol-2-yl;
• - Benzo-fused 5-membered heteroaryl containing 1 to 3 nitrogen atoms or 1 nitrogen atom and / or an acid Substance or sulfur atom: 5-ring heteroaryl groups, which in addition to carbon atoms 1 to 4 nitrogen atoms or 1 to 3 nitrogen atoms and 1 sulfur or oxygen atom or 1 Contain oxygen or a sulfur atom as ring members can, and in which 2 adjacent carbon ring members or 1 nitrogen and 1 adjacent carbon ring member may be bridged by a buta-1,3-diene-1,4-diyl group nen;
• - 5-membered heteroaryl bound via nitrogen, incl tend 1 to 4 nitrogen atoms, or nitrogen bound benzo-fused 5-membered heteroaryl containing 1 to 3 nitrogen atoms: 5-ring heteroaryl groups, which next to Carbon atoms 1 to 4 nitrogen atoms or 1 to 3 stick can contain atoms of matter as ring members, and in which 2 adjacent carbon ring members or a nitrogen and an adjacent carbon ring member through a buta- 1,3-diene-1,4-diyl group can be bridged, this Rings over one of the nitrogen ring members on the frame are bound;
• - 6-membered heteroaryl containing 1 to 3 or 1 to 4 nitrogen atoms: 6-ring heteroaryl groups, which next to Carbon atoms 1 to 3 or 1 to 4 nitrogen atoms as May contain ring members, for. B. 2-pyridinyl, 3-pyridinyl, 4-pyridinyl, 3-pyridazinyl, 4-pyridazinyl, 2-pyrimidinyl,  4-pyrimidinyl, 5-pyrimidinyl, 2-pyrazinyl, 1,3,5-tri azin-2-yl, 1,2,4-triazin-3-yl and 1,2,4,5-tetrazin-3-yl;
• - Benzo-fused 6-membered heteroaryl containing 1 to 4 nitrogen atoms: 6-ring heteroaryl groups, in which 2 be neighboring carbon ring members through a buta-1,3-diene 1,4-diyl group can be bridged, e.g. B. quinoline, iso quinoline, quinazoline and quinoxaline.

The statement "partially or completely halogenated" is intended to end bring pressure that in the groups so characterized the Hydrogen atoms partially or completely by the same or various halogen atoms can be replaced as mentioned above can.

With regard to their biological action against harmful fungi, compounds I are preferred in which the residues have the following meanings, individually or in combination:
R1 methyl;
n 1, in particular 2
R² hydroxy, optionally substituted C₁-C₈ alkoxy, especially hydrogen, chlorine, methoxy;
R³ hydroxy, optionally substituted C₁-C₈ alkoxy, especially hydrogen, bromine, methoxy;
Y oxygen;
R⁴ hydrogen;
R⁵ optionally substituted C₁-C₆ alkyl, cyclohexyl, in particular special optionally substituted phenyl;
With regard to their biological action, the compounds shown in the following tables are particularly preferred

Table 1

Compounds of formula I.1

in the R⁵ for each connection one line of Table A corresponds.

Table 2

Compounds of the formula I.2

in the R⁵ for each connection one line of Table A corresponds.

Table 3

Compounds of formula I.3

in the R⁵ for each connection one line of Table A corresponds.

Table 4

Compounds of the formula I.4

in the R⁵ for each connection one line of Table A corresponds.

Table 5

Compounds of the formula I.5

in the R⁵ for each connection one line of Table A corresponds.

Table 6

Compounds of the formula I.6

in the R⁵ for each connection one line of Table A corresponds.

Table 7

Compounds of the formula I.7

in the R⁵ for each connection one line of Table A corresponds.

Table 8

Compounds of the formula I.8

in which R⁵ corresponds to one row of Table A for each connection.

Table 9

Compounds of the formula I.9

in the R⁵ for each connection one line of Table A corresponds.

Table 10

Compounds of the formula I.10

 in the R⁵ for each connection one line of Table A corresponds.

Table A

The compounds I are suitable for controlling harmful fungi.

They can vary depending on their chemical and physical properties properties with usual, i.e. familiar to the expert, Formulation aids are formulated. The products of this Operations are referred to as "means".

Suitable formulation aids are e.g. B. solid or liquid Carriers, surfactants and adhesives.

Liquid solvents such as liquid carriers Understood water and organic solvents, the latter especially when using water as a solvent the radio tion of an auxiliary solvent. As an organic solution Medium can be used: aromatics such as xylene, toluene and Alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons such as chlorobenzenes, chlorethylenes and methylene chloride, aliphatic hydrocarbons such as cyclo hexane and paraffins, e.g. B. mineral oil fractions, alcohols such as Butanol, iso-butanol, cyclohexanol and glycol and the associated gene ether and ester, ketones such as acetone, methyl ethyl ketone, methyl iso-butyl ketone and cyclohexanone, aprotic dipolar solvents such as dimethylformamide, N-methyl-2-pyrrolidone and dimethyl sulfoxide.

Examples of suitable solid carriers are: natural rock powder and mineral earth such as silicas, silicates, Kaolins, clays, bolus, loess, talc, chalk, limestone, lime, Dolomite, magnesium oxide, quartz, attapulgite, montmorillonite and Diatomaceous earth; synthetic stone powder such as highly disperse gravel silica or flours of synthetic alumina and syn theoretical silicates. Solid, particularly suitable for granules Carriers are, for example: broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite; synthe table granules made from inorganic and organic flours; Granu latex made of organic material such as sawdust, coconut shells, Corn cobs or tobacco stalks.

Suitable surfactants are nonionic and anionic emulsifiers / foam-producing agents and dispersants:

• - Fatty acid polyoxyethylene esters such as lauryl alcohol polyoxyethy lenether acetate,  
• - Alkyl polyoxyethylene or polyoxypropylene ether from about iso-tridecyl alcohol and fatty alcohol polyoxyethylene ether,
• - Alkylaryl alcohol polyoxyethylene ethers such as octylphenol poly oxyethylene ether,
• Tributylphenol polyoxyethylene ether,
• - Ethoxylated iso-octyl, octyl or nonylphenol or Rici nut oil,
• - sorbitol ester,
• Arylsulfonic acids, alkylsulfonic acids, alkylsulfuric acids,
• - alkali, alkaline earth and ammonium salts of arylsulfonic acids, e.g. B. lignin, phenol, naphthalene and dibutylnaphthalene sulfonic acid, alkyl sulfonic acids, alkylarylsulfonic acids, Alkyl, lauryl ether and fatty alcohol sulfuric acids, fatty acid ren, sulfated hexa-, hepta- and octadecanols and fat alcohol glycol ethers,
• - Condensation products of sulfonated naphthalene and its Derivatives with formaldehyde,
• - Condensation products of naphthalenesulfonic acids with phenol and formaldehyde,
• - protein hydrolyzates and
• - In particular as a dispersant: lignin sulfite liquor and Methyl cellulose.

Examples of suitable adhesives are: carboxymethyl cellulose; natural and synthetic powdery, granular or latex-shaped polymers such as gum arabic, polyvinyl alcohol, poly vinyl acetate, natural phospholipids such as cephalins and leci thine, synthetic phospholipids.

Furthermore, the funds can one or more representatives of fol The following groups of substances contain: dyes, other known agents substances, trace nutrients and other additives.

As dyes come e.g. B. inorganic pigments such as iron oxide, Titanium oxide, ferrocyan blue, also organic pigments such as Aliza rin, azo and metal phthalocyanine dyes into consideration. Under other known active ingredients include other fungicides as well Insecticides, acaricides, herbicides and growth regulators too understand. Trace nutrients are, for example, salts of iron, Manganese, boron, copper, cobalt, molybdenum and zinc. As another addi mineral and vegetable oils are also suitable.

The funds can also be of other practical importance seed mix partners such as fertilizers or other ready-made agents containing active ingredients must be mixed.  

The agents are prepared in a manner known per se, namely depending on the chemical and physical egg properties of the substances used z. B. by mixing, common with grinding, spraying, extruding, granulating or dissolving in water, the latter possibly with the help of an organic Solvent. Powders, sprinkles and dusts are e.g. B. by Mixing or grinding the compounds I together with a solid carrier available.

The means are dependent on the ones put fabrics z. B. solutions, emulsions, suspensions, Powders, foams, pastes, granules, aerosols or very fine capsules lungs in polymeric substances or in seed coating materials.

Those used for trading are usually used as concessions if available funds are dissolved as usual, diluted etc., for wettable powders, water-dispersible granules emulsifiable concentrates, dispersions and sometimes also for microgranules usually using water.

Dust-like and granulated preparations as well as sprayable Lö Before use, solutions are usually no longer combined with other solutions diluted substances.

The funds are spent in a manner known per se, for example by spraying, atomizing, dusting, scattering or To water. The plants are usually sprayed with the agents or pollinated. Alternatively or additionally, the seeds are treated the plants in a manner known per se.

Examples of such preparations are:

• I. a solution of 90 parts by weight of a Ver bond I and 10 parts by weight of N-methyl-2-pyrrolidone, which for Application in the form of tiny drops is suitable;
• II. A mixture of 20 parts by weight of an inventive Compound I, 80 parts by weight of xylene, 10 parts by weight of the An Storage product of 8 to 10 moles of ethylene oxide to 1 mole Oleic acid-N-monoethanolamide, 5 parts by weight of the calcium salt the dodecylbenzenesulfonic acid, 5 parts by weight of the plant of 40 moles of ethylene oxide and 1 mole of castor oil: by finely distributing the solution in water you get one Dispersion;
• III. an aqueous dispersion of 20 parts by weight of one Compound I according to the invention, 40 parts by weight of cyclo hexanone, 30 parts by weight of isobutanol, 20 parts by weight of the An  Storage product of 40 mol of ethylene oxide on 1 mol Castor oil;
• IV. An aqueous dispersion of 20 parts by weight of one Compound I according to the invention, 25 parts by weight of cyclo hexanol, 65 parts by weight of a mineral oil fraction from the boil point 210 to 280 ° C and 10 parts by weight of the addition pro product of 40 mol ethylene oxide with 1 mol castor oil;
• V. a mixture of 80% by weight ground in a hammer mill Parts of a compound I according to the invention, 3 parts by weight the sodium salt of diisobutylnaphthalene-1-sulfonic acid, 10 Parts by weight of the sodium salt of a lignosulfonic acid a sulfite waste liquor and 7 parts by weight of powder Silica gel: by finely distributing the mixture in what you get a spray mixture;
• VI. an intimate mixture of 3 parts by weight of a fiction according to compound I and 97 parts by weight of finely divided Kao lin; this dust contains 3% by weight of active ingredient;
• VII. An intimate mixture of 30 parts by weight of a fiction according to compound I, 92 parts by weight of powdered pebble acid gel and 8 parts by weight of paraffin oil, which on the upper surface of this silica gel was sprayed; this Aufb Riding gives the active ingredient good adhesion;
• VIII. A stable aqueous dispersion of 40 parts by weight of one Compound I according to the invention, 10 parts by weight of sodium salt of a phenolsulfonic acid-urea-formaldehyde con densates, 2 parts by weight of silica gel and 48 parts by weight of what water that can be further diluted;
• IX. a stable oily dispersion of 20 parts by weight of one Compound I according to the invention, 2 parts by weight of calcium salt of dodecylbenzenesulfonic acid, 8 parts by weight of fat alcohol polyglycol ether, 20 parts by weight of the sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate and 68 parts by weight of a paraffinic mineral oil.

If the compounds I are applied as such, it happens everything depends on their fine distribution.  

The compounds I and the agents according to the invention stand out due to its excellent effectiveness against a wide range of harmful fungi (phytopathogenic fungi), in particular from the Class of

• - Ascomycetes,
• - Basidiomycetes,
• - Deuteromycetes and
• - Phycomycetes

out. Some of them are systemically effective and can be used as leaf and Soil fungicides are used.

They are particularly important for combating a large number of mushrooms on various crops such as wheat, rye, Barley, oats, rice, corn, grass, cotton, soy, coffee, sugar pipe, wine, fruit and ornamental plants and vegetables such as cucumbers, Beans and pumpkin plants and on the seeds of these plants.

The compounds I, their salts and N-oxides and the fiction Appropriate means are applied by the harmful fungi, the Habitat or the seeds to be protected from fungal attack, Plants, surfaces, materials or spaces with a fungicidal effective amount of agents or compounds I treated. The Can be used before or after the fungus infestation.

The agents according to the invention and the compounds I are particularly suitable for controlling the following plant diseases:
Erysiphe graminis (powdery mildew) in cereals, Erysiphe cichoracearum and Sphaerotheca fuliginea on pumpkin plants, podosphaera leucotricha on apples, Uncinula necator on vines, Puccinia species on cereals, Rhizoctonia species on cotton, rice and lawn, cereals, Ustil , Venturia inaeaualis (scab) on apples, Helminthosporium species on cereals, Septoria nodorum on wheat, Botrytis cinerea (gray mushroom) on strawberries, vines, ornamental plants and vegetables, Cercospora arachidicola on peanuts, Pseudocercosporella herpotrichoides on wheat, gerste on rice, Phytophthora infestans on potatoes and tomatoes, Fusarium and Verticillium species on various plants, Plasmopara viticola on vines, Pseudoperonospora species in hops and cucumbers, Alternaria species on vegetables and fruit.

The fungicidal compositions generally contain between 0.1 and 95, preferably between 0.5 and 90,% by weight of active ingredient.  

The application rates depend on the type of effect desired between 0.01 and 2.0 kg of active ingredient per ha.

When treating seeds, amounts of active ingredient are generally used from 0.001 to 0.1 g, preferably 0.01 to 0.05 g per kilogram Seed needed.

The agents according to the invention can be used as Fungicides are also present together with other active ingredients e.g. B. with herbicides, insecticides, growth regulators, fungicides that or with fertilizers.

When mixed with fungicides you get in many cases an increase in the fungicidal spectrum of activity.

The following list of fungicides with which the compounds according to the invention can be used together is intended to explain, but not to limit, the possible combinations:
Sulfur, dithiocarbamates and their derivatives, such as Ferridimethyldi thiocarbamate, zinc dimethyldithiocarbamate, Zinkethylenbisdithio carbamate, manganese ethylenebisdithiocarbamate, manganese zinc ethylene diamine min bisdithiocarbamate, Tetramethylthiuramdisulfide, ammonia complex of zinc (N, N-ethylene-bis-dithiocarbamate), ammonia Complex of zinc (N, N'-propylene-bis-dithiocarbamate), zinc (N, N'-propylene-bis-dithiocarbamate), N, N'-polypropylene-bis- (thiocarbamoyl) disulfide;
Nitroderivatives such as dinitro- (1-methylheptyl) phenyl crotonate, 2-sec-butyl-4,6-dinitrophenyl-3,3-dimethylacrylate, 2-sec-butyl-4,6-di nitrophenyl-iso-propyl carbonate, 5- Di-isopropyl nitro-iso-phthalate;
heterocyclic substances such as 2-heptadecyl-2-imidazoline acetate, 2,4-dichloro-6- (o-chloroanilino) -s-triazine, O, O-diethyl-phthalimido dophosphonothioate, 5-amino-1- [bis- ( dimethylamino) phosphinyl] -3-phenyl-1,2,4-triazole, 2,3-dicyano-1,4-dithioanthraquinone, 2-thio-1,3-dithiolo [4,5-b] quinoxaline, 1- (butylcarbamoyl) -2-ben methyl zimidazole-carbamate, 2-methoxycarbonylamino-benzimidazole, 2- (furyl- (2)) benzimidazole, 2- (thiazolyl- (4)) benzimidazole, N- (1,1, 2,2-tetrachloroethylthio) tetrahydrophthalimide, N-trichloromethylthio-tetrahydrophthalimide, N-trichloromethylthio phthalimide,
N-dichlorofluoromethylthio-N ′, N′-dimethyl-N-phenylsulfuric acid diamide, 5-ethoxy-3-trichloromethyl-1,2,3-thiadiazole, 2-Rhodanme thylthiobenzthiazol, 1,4-dichloro-2,5- dimethoxybenzene, 4- (2-chlorophenylhydrazono) -3-methyl-5-isoxazolone, pyridine-2-thio-1-oxide, 8-hydroxyquinoline or its copper salt, 2,3-dihydro-5-carboxa nilido-6- methyl-1,4-oxathiin, 2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiin-4,4-dioxide, 2-methyl-5,6-dihydro-4H-pyran 3-carboxylic acid anilide, 2-methyl-furan-3-carboxylic acid anilide, 2,5-dimethyl-furan-3-carboxylic acid anilide, 2,4,5-trimethyl-furan-3-carboxylic acid anilide, 2,5-dimethyl-furan -3-carboxylic acid cyclohe xylamide, N-cyclohexyl-N-methoxy-2,5-dimethyl-furan-3-carboxylic acid reamide, 2-methyl-benzoic acid anilide, 2-iodo-benzoic acid anilide, N-formyl-N-morpholine -2,2,2-trichloroethyl acetal, Piperazin-1,4-diylbis- (1- (2,2,2-trichloroethyl) formamide, 1- (3,4-dichlo ranilino) -1-formylamino -2,2,2-trichloroethane, 2,6-dimethyl-N-tri-decyl-morpholine or its salts, 2,6-dimethyl-N-cy clododecyl morpholine or its salts, N- [3- (p-tert-butylphenyl) -2-methyl propyl] -cis-2,6-dimethylmorpholine, N- [3- (p-tert-butylphenyl) - 2-methylpropyl] piperidine, 1- [2- (2,4-dichlorophenyl) -4-ethyl-1,3-dioxolan-2-yl-ethyl] -1H-1,2,4-triazole, 1- [2- (2,4-dichlorophenyl) -4-n-propyl-1,3-dioxolan-2-yl-ethyl] -1H-1,2,4-triazole, N- (n-propyl) -N- (2,4,6-trichlorophenoxy thyl) -N'-imidazol-yl-urea, 1- (4-chlorophenoxy) -3,3-dimethyl-1- (1H-1,2,4-triazole- 1-yl) -2-butanone, (2-chlorophenyl) - (4-chlorophenyl) -5-pyrimidine-methanol, 5-butyl-2-dimethyla mino-4-hydroxy-6-methyl-pyrimidine, bis- ( p-chlorophenyl) -3-pyridine methanol, 1,2-bis (3-ethoxycarbonyl-2-thioureido) benzene, 1,2-bis-3-methoxycarbonyl-2-thioureido) benzene, [2- (4-chlorophe nyl) ethyl] - (1,1-dimethylethyl) -1H-1,2,4-triazole-1-ethanol and
various fungicides such as dodecylguanidine acetate, 3- [3- (3,5-dimethyl-2-oxycyclohexyl) -2-hydroxyethyl)] glutarimide, hexachlorobenzene, DL-methyl-N- (2,6-dimethyl-phenyl) -N -furoyl (2) alaninate, DL-N- (2,6-dimethyl-phenyl) -N- (2'-methoxyacetyl) alanine-methyl ester, N- (2,6-dimethylphenyl) -N-chloroacetyl-D, L-2-aminobutyrolactone, DL-N- (2,6-dimethylphenyl) -N- (phenylacetyl) alanine methyl ester, 5-methyl-5-vinyl-3- (3,5-dichlorophenyl) -2,4-dioxo- 1,3-oxazolidine, 3- [3,5-dichlorophenyl (-5-methyl-5-methoxymethyl] -1,3-oxazolino din-2,4-dione, 3- (3,5-dichlorhenyl) -1- iso-propylcarbamoylhydan toin, N- (3,5-dichlorophenyl) -1,2-dimethylcyclopropane-1,2-dicarboxylic acid imide, 2-cyano- [N- (ethylaminocarbonyl) -2-methoximino] -aceta mid, 1- [ 2- (2,4-dichlorophenyl) pentyl] -1H-1,2,4-triazole, 2,4-di fluoro-a- (1H-1,2,4-triazolyl-1-methyl) benzhydryl alcohol, N- (3-chloro-2,6-dinitro-4-trifluoromethyl-phenyl) -5-trifluoromethyl-3-chloro-2-aminopyridine, 1 - ((bis- (4-fluorophenyl) methylsilyl) methyl) -1H- 1,2,4-triazole.

Strobilurins such as methyl-E-methoximino- [a- (o-tolyloxy) -o-to lyl] acetate, methyl E-2- {2- [6- (2-cyanophenoxy) pyrimi din-4-yloxy] phenyl} -3-methoxyacrylate, methyl-E-methoxy  mino- [a- (2-phenoxyphenyl)] acetamide, methyl-E-methoxy mino- [a- (2,5-dimethylphenoxy) -o-tolyl] acetamide.

Anilinopyrimidines such as N- (4,6-dimethylpyrimidin-2-yl) aniline, N- [4-methyl-6- (1-propynyl) pyrimidin-2-yl] aniline, N- (4-Me thyl-6-cyclopropyl-pyrimidin-2-yl) aniline.

Phenylpyrroles such as 4- (2,2-difluoro-1,3-benzodioxol-4-yl) pyr rol-3-carbonitrile.

Cinnamic acid amides such as 3- (4-chlorophenyl) -3- (3,4-dimethoxyphe nyl) acrylic acid morpholide.

(2RS, 3SR) -1- [3- (2-chlorophenyl) -2- [4-fluorophenyl] oxiran-2-ylme thyl] -1H-1,2,4-triazole.

Synthesis examples

The examples given in the synthesis examples below Writings can be modified from the starting compounds Obtaining further representatives of the compounds I are used. The physical data of the products manufactured accordingly are reproduced in the following table S1.

1. 2-methylsulfonyl-5-bromopyrimidine-4-carboxy- (4-fluorophen nyl) amide (compound S1.10)

a) 2-Thiomethyl-5-bromo-pyrimidine-4-carboxylic acid was analogous to J. Chem. Soc. Vol. 1953, pages 3129-31 received: 56 g (0.217 mol) mucobromic acid were dissolved in 800 ml of water at 50 ° C. and at this temperature 60 g (0.217 mol) of S-methyli sothiourea sulfate added. After cooling to room temperature 65.8 g (0.651 mol) of triethylamine were added with stirring added dropwise, the temperature being kept at 20 ° C. After Acidify with conc. Hydrochloric acid crystallized the product as Solid from (28.0 g, mp. 168-70 ° C).

b) 2-thiomethyl-5-bromopyrimidine-4-carboxylic acid chloride

10.0 g (40 mmol) of 2-thiomethyl-5-bromo-pyrimidine-4-carboxylic acid and 50 ml of thionyl chloride were mixed with 1 ml of DMF for two hours 80 ° C stirred. After distilling off the thionyl chloride the product is fractionated at 105-110 ° C and 0.8 mbar. Off Loot: 9.3 g.

c) 2-Thiomethyl-5-bromo-pyrimidine-4-carboxy- (4-fluorophenyl) amide

1.0 g (3.7 mmol) of 2-thiomethyl-5-bromopyrimidine-4-carboxylic acid rechloride and 0.4 g (4 mmol) triethylamine were in 40 ml dissolved anhydrous toluene and 0.41 g (3.7 mmol) 4-fluorani lin added with stirring. After stirring for 16 hours 50 ml each of 2N hydrochloric acid, 5%. Sodium bicarbonate solution and water and the organic phase after drying concentrated with sodium sulfate. 1.2 g of 2-thiomas were thus obtained thyl-5-bromo-pyrimidine-4-carboxy- (4-fluorophenyl) amide (conn S1.47).

d) 2-methylsulfonyl-5-bromopyrimidine-4-carboxy- (4-fluorophen nyl) amide

To the mixture of 0.4 g 30 percent. Hydrogen peroxide and 5 ml Glacial acetic acid was added to 50 mg of sodium tungstate and 15 min. touched. Then 1.2 g (3.5 mmol) of 2-thiomas were added thyl-5-bromopyrimidine-4-carboxy- (4-fluorophenyl) amide dissolved in Glacial acetic acid and stirred at 25 ° C for 16 hours. After adding 100 ml of water precipitated the product in the form of yellow crystals and was suctioned off. This gave 1.1 g of the title ver binding (mp 169-74 ° C, verb S1.10).

2. 2-methylsulfonylpyrimidine-4-carboxy- (4-fluorophenyl) amide (ver binding S1.23)

a) 2-Thiomethylpyrimidine-4-carboxylic acid was analogous to J. Med. Chem. 29 (1986) pages 1374-80 obtained: 46.8 g (0.188 mol) 2-thiomethyl-5-bromo-pyrimidine-4-carboxylic acid were mixed with 23 g (0.41 mol) potassium hydroxide dissolved in 800 ml of methanol. After To administration of 10 g 5%. Palladium on barium sulfate became 10 bar Pressed in hydrogen and stirred for 16 hours. After Abfil trieren of the catalyst, the filtrate was ver with water thin and adjusted to pH 1 by acidification with hydrochloric acid. There the product separated in the form of light brown crystals. After recrystallization from ethanol, 28.7 g of 2-thio were obtained methylpyrimidine-4-carboxylic acid, melting point 211-215 ° C.

b) 2-thiomethyl-pyrimidine-4-carboxy- (4-fluorophenyl) amide

0.68 g (4 mmol) of 2-thiomethylpyrimidine-4-carboxylic acid and 0.44 g (4 mmol) 4-fluoroaniline were in 50 ml puriss. You lormethane suspended. After adding 0.5 g of triethylamine 0.7 g (4 mmol) of 93 percent. Diethyl cyanophosphonate added dropwise and stirred at 25 ° C for 16 hours. There were 50 ml Dichloromethane added and twice with 100 ml of 2N sodium lye, dil. hydrochloric acid, 5% Sodium bicarbonate solution and washed water. Then the organic phase  dried and concentrated. 0.9 g of 2-thiomethyl were thus obtained pyrimidine-4-carboxy- (4-fluorophenyl) amide (compound S1.48).

c) 2-methylsulfonyl-pyrimidine-4-carboxy- (4-fluorophenyl) amide

To the mixture of 0.4 g 30 percent. Hydrogen peroxide and 5 ml Glacial acetic acid was added to 50 mg of sodium tungstate and 15 min. touched. Then 0.9 g (3.4 mmol) of 2-thiomethyl was added pyrimidine-4-carboxy- (4-fluorophenyl) amide, dissolved in glacial acetic acid, added and stirred at 25 ° C for 16 hours. After adding 100 ml The product precipitated out in the form of yellow crystals and was sucked off. This gave 0.6 g of the title compound (Mp 175-78 ° C, compound S1.23).

3. 2-methylsulfonyl-6-chloro-pyrimidine-4-carboxy- (4-fluorophen nyl) amide (compound S1.43) a) 2-Thiomethyl-6-chloropyrimidine-4-carboxylic acid chloride

50 g (0.27 mol) of 2-thiomethyl-6-hydroxypyrimidine-4-carboxylic acid (see J. Org. Chem. 26, (1961), pages 2755-61) and 100 ml Phosphorus oxytrichloride were refluxed at 80 ° C for six hours xiert. After the phosphorus oxytrichloride was distilled off the product is fractionated at 100-102 ° C and 0.5 mbar. Off Loot: 36.7 g.

b) 2-Thiomethyl-6-chloropyrimidine-4-carboxy- (4-fluorophenyl) amide

2.4 g (10.8 mmol) of 2-thiomethyl-6-chloro-pyrimidine-4-carboxylic acid rechloride and 1.2 g (11.8 mmol) triethylamine were dissolved in 50 ml puriss. Dissolved dichloromethane and 1.2 g (10.8 mmol) of 4-fluora nilin added with stirring. After stirring for 16 hours with 50 ml of 2N hydrochloric acid, 5%. Sodium bicarbonate solution solution and water washed and the organic phase after Dry concentrated with sodium sulfate. After chromatography on Silica gel (eluent hexane / MTBE = 9/1) gave 1.3 g 2-thiomethyl-5-bromopyrimidine-4-carboxy- (4-fluorophenyl) amide (Mp 116-20 ° C; compound S1.34).

c) 2-Methylsulfonyl-6-chloro-pyrimidine-4-carboxy- (4-fluorophen nyl) amide

To the mixture of 2.4 g 30 percent. Hydrogen peroxide and 20 ml of glacial acetic acid were added and 100 mg of sodium tungstate Stirred for 15 min. Then 0.7 g (2.4 mmol) of 2-thio were added dissolved methyl-6-chloro-pyrimidine-4-carboxy- (4-fluorophenyl) amide in glacial acetic acid and stirred at 25 ° C for 16 hours. After addition  The product fell in the form of yellow crystals against 100 ml of water stall and was vacuumed. This gave 0.7 g of the Ti Tel connection (mp. 180-82 ° C, connection S1.43).

Table S1

Examples of use

For the following experiments on the fungicidal activity of the compounds I, an emulsion was used which consists of 10% by weight of the active ingredient and 90% by weight of a mixture of 70% by weight of cyclohexanol,
20% by weight of Nekanil® LN (Lutensol® AP6, wetting agent with emulsifying and dispersing action based on ethoxylated alkylphenols) and
10% by weight of Uniperol® EL (non-ionic emulsifier based on ethoxylated castor oil)
duration. The desired active ingredient concentrations were set by diluting this emulsion with water. The extent of the disease was determined visually.

Claims (4)

1. Pyrimidine-4-carboxamides of the formula I. and their salts and N-oxides, in which the variables have the following meaning:
R¹ C₁-C₈-alkyl, these radicals can be partially or completely halogenated and / or can carry one to three of the following groups: cyano, C₁-C₄-alkoxyalkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄ -Halogenalkoxy, C₁-C₄-alkylthio, C₁-C₄-alkoxycarbonyl, C₃-C₇-cycloalkyl, C₃-C₇-cycloalkenyl, aryl, aryloxy and heteroaryl, where the cyclic radicals can in turn carry one to three of the following substituents: halogen, Cyano, C₁-C₄-alkyl, C₁-C₄-alkoxyalkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkylthio, C₁-C₄-alkoxycarbonyl, aryl, aryloxy and heteroaryl or
Aryl, this radical can carry one or, independently of one another, the two or three of the following groups: Ha logen, cyano, C₁-C₄-alkyl, C₁-C₄-alkoxyalkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁ -C₄-haloalkoxy, C₁-C₄-alkylthio, C₁-C₄-alkoxycarbonyl, aryl, aryloxy and heteroaryl, in which the cyclic substituents may in turn carry one or two or three of the following substituents independently of one another: halogen, cyano, C₁- C₄-alkyl, C₁-C₄-alkoxyalkyl, C₁-C₄-halogeno alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkylthio and C₁-C₄-alkoxycarbonyl;
n 0, 1 or 2;
R² is hydrogen, hydroxy, halogen, C₁-C₈ alkyl, C₁-C₈ halogen alkyl, C₁-C₈ alkoxy, C₁-C₈ haloalkoxy;
R³ is hydrogen, hydroxy, halogen, C₁-C₈-alkyl, C₁-C₈-haloalkyl, C₁-C₈-alkoxy, C₁-C₈-haloalkoxy,
where one of the radicals R² and R³ is always hydrogen;
y oxygen or sulfur;
R⁴ is hydrogen or optionally partially or, if appropriate, fully halogenated C₁-C₈alkyl or, if appropriate, partially or optionally completely halogenated C₃-C₇cycloalkyl;
R⁵ C₁-C₈-alkyl, these radicals being partially or completely halogenated and / or carrying one or two of the following groups, independently of one another:
Cyano, C₁-C₄-alkoxyalkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkylthio, C₁-C₄-alkoxycarbonyl, C₃-C₇-cycloalkyl, C₃-C₇-cyclo alkenyl , Aryl, aryloxy and heteroaryl, where the cyclic radicals in turn can carry one or, independently of one another, two or three of the following substituents:
Halogen, cyano, C₁-C₄-alkyl, C₁-C₄-alkoxyalkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkylthio, C₁-C₄-alkoxycarbonyl, aryl, aryloxy and Heteroaryl or
C₃-C₇-cycloalkyl, which radical may carry one or, independently of one another, two or three of the following groups: halogen, C₁-C₄-alkyl, C₁-C₄-haloalkyl and C₁-C₄-alkoxy or
Aryl, this radical can carry one or, independently of one another, the two or three of the following groups: Ha logen, cyano, C₁-C₄-alkyl, C₁-C₄-alkoxyalkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁ -C₄-haloalkoxy, C₁-C₄-alkylthio, C₁-C₄-alkoxycarbonyl, aryl, aryloxy and heteroaryl, in which the cyclic substituents may in turn carry one or two or three of the following substituents independently of one another: halogen, cyano, C₁- C₄-alkyl, C₁-C₄-alkoxyalkyl, C₁-C₄-halogeno alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkylthio and C₁-C₄-alkoxycarbonyl. 2. Containing agents suitable for combating harmful fungi a fungicidally effective amount of a compound of formula I. or one of its salts or N-oxides according to claim 1 and min usually a common formulation aid. 3. A method of combating harmful fungi, characterized records that the harmful fungi, their habitat or the plants, surfaces, materials or Spaces with an effective amount of a compound of general my formula I or one of its salts or N-oxides according to An treated claim 1 or an agent according to claim 2. 4. Use of the compounds of general formula I, their Salts and N-oxides according to claim 1 for combating harm mushrooms.