DE19620392A1 - New (2-(pyrimidinyl-oxy-methyl)phenyl)-acetic acid derivatives - Google Patents

Abstract

2-(pyrimidin-4-yloxy)methyl)phenylacetic acid derivatives of formula (I) and their salts and N-oxides are new. R1 = H or 1-4C alkyl; R2 = halo, CH3, CH2CH3, halomethyl or haloethyl; R3 = phenyl, phenoxy, phenoxymethyl, benzyloxy or heteroaryl, (all optionally ring-substituted), H, amino, OH, SH, halo, 1-8C alkyl (optionally substituted by Ar or halo), alkoxy-(1-4C alkyl), alkoxy, mono- or di- alkylamino, alkylthio, alkylsulphoxy, alkylsulphonyl, 3-8C cycloalkyl, trialkylsilyloxy; Ar = phenyl (optionally mono- or di-substituted by halo, CN, NO2, 1-4C alkyl, 1-4C haloalkyl or 1-4C alkoxy); R4 = H, CN, halo, 1-4C alkyl, 1-4C haloalkyl or 1-4C alkoxy; Q = C(=NOCH3)CONHCH3, C(=NOCH3)COOCH3 or N(OCH3)COOCH3; alkyl, alkoxy have 1-8 C unless specified otherwise.

Description

The present invention relates to 2- (O- [pyrimidin-4-yl] methylene oxy) phenylacetic acid derivatives of the general formula I

and their salts and N-oxides, in which the radicals R¹ to R⁴ and Q have the following meanings:
R¹ is hydrogen or C₁-C₄ alkyl;
R² is halogen, C₁-C₂ alkyl or C₁-C₂ haloalkyl;
R³ is hydrogen; Amino; Hydroxy; Mercapto; Halogen; C₁-C₈-alkyl, where the alkyl radicals can carry a phenyl group, which in turn can carry one or, independently of one another, two of the following substituents: halogen, cyano, nitro, C₁-C₄-alkyl, C₁-C₄-haloalkyl and C₁- C₄ alkoxy; C₁-C₈ haloalkyl; C₁-C₈ alkoxy-C₁-C₄ alkyl; C₁-C₈ alkoxy; C₁-C₈ monoalkylamino; Di-C₁-C₈ alkylamino; C₁-C₈ alkylthio; C₁-C₈ alkyl sulfoxyl; C₁-C₈ alkylsulfonyl; C₃-C₈ cycloalkyl; Tri-C₁-C₈-alkylsilyloxy or optionally substituted in the aromatic ring: phenyl, phenoxy, phenoxymethyl, benzyloxy or heteroaryl;
R⁴ hydrogen; Cyano; Halogen; C₁-C₄ alkyl; C₁-C₄ haloalkyl or C₁-C₄ alkoxy;
QC (= NOCH₃) -CONHCH₃,
C (= NOCH₃) -COOCH₃ or
N (OCH₃) -COOCH₃.

The invention also relates to compounds I containing Agents and their use for controlling harmful fungi and animal pests.  

α- [2- (Hetaryloxymethylene) phenyl] -α-methoxyiminoacetic acid methyl mide with fungicidal and / or insecticidal and acaricidal activity are known (EP-A 398 629; EP-A 477 631; JP-A 04/182 461; Deut cal patent application Az. 195 26 661.7).

Furthermore, α- [2-hetaryloxymethylene) phenyl] -α-methoxyiminoes methyl acetate with fungicidal and / or insecticidal and aka ricidal effect known (cf. EP-A 254 426, EP-A 363 818, EP-A 407 873.

In addition, N- [2- (hetaryloxymethylene) phenyl] -N-methoxy carbamic acid methyl ester with fungicidal and / or insecticidal and Acaricidal effect known (see WO-A 93/15046).

The effect of those described in the aforementioned publications Links against harmful fungi and animal pests can still be made not satisfy.

The present invention was therefore new compounds with ver improved properties in the control of harmful fungi and animal pests as a task.

Accordingly, the compounds I defined at the outset were found as well as compositions containing them and their use for combating of harmful fungi and animal pests.

The compounds I are prepared in analogy to those in of the methods described in the introduction.

It is generally unimportant in the synthesis of compounds I. significant whether the group Q first or the 2- (O- [pyrimidin-4-yl] methyleneoxy) group is built up.

Compounds I are obtained, for example, by adding a Pyrimidin-4-ol of the formula II in a manner known per se in one inert organic solvents in the presence of a base a benzyl derivative of the formula III.

(Q = C (= NOCH₃) -CONHCH₃), C (= NOCH₃) -COOCH₃ or N (OCH₃) -COOCH₃).

In formula III, X stands for a nucleophilically exchangeable Leaving group such as halogen (e.g. chlorine, bromine or iodine), alkyl sulfonyl (e.g. methylsulfonyl or trifluoromethylsulfonyl) or Arylsulfonyl (e.g. phenylsulfonyl or 4-methylphenylsulfonyl).

The reaction is usually carried out at temperatures from 0 to 80 preferably carried out at 20 to 60 ° C.

Suitable solvents are aromatic hydrocarbons such as Toluene, o-, m- and p-xylene, halogenated hydrocarbons such as Methylene chloride, chloroform and chlorobenzene, ethers such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, dioxane, anisole and tetrahydrofuran, nitriles such as acetonitrile and propionitrile, Alcohols such as methanol, ethanol, n-propanol, isopropanol, n-buta nol and tert-butanol, ketones such as acetone and methyl ethyl ketone such as dimethyl sulfoxide, dimethylformamide, dimethylacetamide, 1,3-dimethylimidazolidin-2-one and 1,3-dimethyltetrahydro-2 (1H) pyrimidinone. Methylene chloride, Ace are particularly preferred clay and dimethylformamide.

Mixtures of the solvents mentioned can also be used will.

In general, inorganic compounds with basi come as bases character such as alkali metal and alkaline earth metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, alkali metal and alkaline earth metal oxides such as lithium oxide, Sodium oxide, calcium oxide and magnesium oxide, alkali metal and  Alkaline earth metal hydrides such as lithium hydride, sodium hydride, potassium hydride and calcium hydride, alkali metal amides such as lithium amide, Sodium amide and potassium amide, alkali metal and alkaline earth metal carbonates such as potassium carbonates and calcium carbonate and alkali metal hydrogen carbonates such as potassium carbonate and calcium carbonate and alkali metal bicarbonates such as sodium bicarbonate, organometallic compounds, especially alkali metal alkyls such as methyl lithium, butyllithium and phenyllithium, alkyl magnesium halides such as methyl magnesium chloride and alkali tall and alkaline earth metal alcoholates such as sodium methoxide, Sodium methoxide, potassium ethoxide, potassium tert-butoxide and Dimethoxymagnesium.

Also suitable as bases are organic bases, e.g. B. tertiary Amines such as trimethylamine, triethylamine, diisopropylethylamine and N-methylpiperidine, pyridine, substituted pyridines such as collidine, Lutidine and 4-dimethylaminopyridine and bicyclic amines.

Sodium hydroxide, sodium hydride, potassium carbonate and potassium tert-butanolate are particularly preferred.

The bases are generally equimolar or in excess, ge optionally also used as a solvent.

It may be advantageous to implement a catalytic one Amount of a crown ether such as B. 18-crown-6 or 15-crown-5 clog.

The implementation can also consist of two-phase systems for example from a solution of alkali or alkaline earth hydroxides or alkali or alkaline earth carbonates in water and an organic phase such as B. halogenated hydrocarbon fen be carried out. Can be used as phase transfer catalysts Ammonium halides and tetrafluoroborates such as. B. Benzyltri ethylammonium chloride, benzyltributylammonium bromide, tetrabutyl ammonium chloride, hexadecyltrimethylammonium bromide or tetra butylammonium tetrafluoroborate and phosphonium halides such as Te trabutylphosphonium chloride or tetraphenylphosphonium bromide be set.

It can be advantageous for the implementation, first the Treat compounds II with base and the resulting salt implement with the compounds III.  

The compounds II can by condensation of β-keto esters VI with amidines, guanidines, ureas or thioureas VII in Analogy to known methods can be obtained [cf. J. Chem. Soc. (1946), page 5].

R in the formula VI primarily represents a C₁-C₄ alkyl group, especially methyl or ethyl.

The reaction is usually carried out at temperatures from 0 to 120 preferably 20 to 80 ° C and especially at the boiling temperature of the solvent. Find as a solvent usually alcohols, especially methanol or ethanol, Use.

The compounds VII can also in the form of their salts, ins especially as hydrohalides (e.g. hydrochloride or hydrobro mid) can be used. Recommended when using salts it is possible to carry out the reaction in the presence of a base (e.g. alkaline earth metal or alkali metal alcoholates or hydro xides such as sodium methoxide, sodium ethoxide, potassium tert-buty lat, sodium hydroxide, potassium hydroxide and calcium hydroxide).

The starting compounds of type II and their syntheses are all commonly known, in particular from the following publication NEN:

Justus Liebigs Ann. Chem. 758, (1972), pages 125, 127, 130;
Chem. Pharm. Bull. 22, (1974), pages 1239, 1240, 1245-1247;
J. Amer. Chem. Soc. 79 (1957) page 2230;
Bull. Soc. Chim. Fr. (1965), pages 2301-2306;
Bull. Soc. Chim. Fr. (1963), page 673;
BE-A 645062;
Recl. Trav. Chim. Pays-Bas 87, 10, (1968), page 1089;
Chem. Pharm. Bull. 36, 5, (1988), pages 1669-1675;
Tetrahedron 25, (1969), pages 5989, 5992;
J. Org. Chem. 35, (1970), pages 3786, 3790, 3791;
Z. Chem., GE 25, 9, (1985), pages 328-329;
J. Chem. Soc. (1950), pages 452, 456, 458;
At the. Chem. J. 29 (1903), page 487;
Bull. Soc. Chim. Belg. 68 (1959), pages 30, 40;
J. Biol. Chem. 3 (1907), page 303;
Arch. Pharm. (Weinheim Ger.) GE, 317, 5, (1984), pages 425-430;
At the. Chem. J. 31 (1904), page 595;
At the. Chem. J. 43 (1910), page 23;
J. Amer. Chem. Soc. 51 (1929), page 1240;
At the. Chem. J. 42 (1909), page 368;
Rocz. Chem. 51, (1977), pages 1227, 1228, 1230;
Pole. J. Chem. EN, 55, 7/8, (1981), pages 1673-1676;
Org. Mass Spectrom. 14, (1979), pages 405, 409, 412;
Aust. J. Chem. 41, 8, 1988, 1209-1219;
Pole. J. Chem. 57, 7-9, (1983), pages 1027-1031;

CS-A 107166;
BE-A 627342;
US-A 3954759;
US-A 3954758;
CS-A 108806;
SU-A 232975;
BE-A 860309;
JP-A 50150936;
Gazz. Chim. Italian 93 (1963) pages 1268, 1272;
Collect. Czech. Chem. Commun. 27 (1962) pages 2250-2560;
J. Med. Chem. 8 (1965), pages 253;
J. Org. Chem. 27 (1962), page 2580;
J. Chem. Soc. C. (1967), page 1822;
J. Chem. Soc. C. (1967), pages 2206-2207;
J. Med. Chem. 36, 18 (1993), pages 2627-2638;
J. Chem. Soc. (1959), pages 3278, 3284;
J. Am. Chem. Soc. 79 (1957), page 4559;
Acta Chem. Scand. 23 (1969), page 294.

BE-A 645062;
GB-A 1174165;
Collect. Czech. Chem. Commun. 27 (1962), pages 2250-2560;
J. Org. Chem. 27 (1962), pages 3507, 3510;
J. Med. Chem. 6 (1963), pages 688-693;
J. Med. Chem. 36, 18 (1993), pages 2627-2638;

Heterocycles 31, 3 (1990), pages 569-574.

The preparation of the starting compounds III.1 (X = Cl) and III.2 (X = Br), in which Q represents C (= NOCH₃) -CONHCH₃, - cf. EP-A 477 631, Tab. 1, No. 332 and 333 - from the corresponding Alkoxy or aryloxy compounds VII

R ′ = possibly subst. Alkyl or
if necessary subst. Aryl

succeeds by splitting with z. B. boron trichloride (for III.1) or with hydrogen bromide (for III.2) in inert solvents such as ha logenated hydrocarbons at temperatures from (-30) to 40 ° C. An advantageous representation from the corresponding Ver bond VII with R ′ = 2-tolyl (see EP-A 477 631, Tab. 1, No. 94) is described in Examples 1 to 3.

The preparation of the compounds III, in which Q for C (= NOCH₃) -COOCH₃ is known from EP-A 363 818.

The preparation of the compounds III, in which Q for N (OCH₃) -COOCH₃ is known from WO-A 93/15046.

The compounds I can in the preparation due to their C = N double bonds in group Q as E / Z isomer mixtures fall, the z. B. by crystallization or chromatography in can be separated into the individual connections in the usual way.

If isomer mixtures are obtained in the synthesis, in general However, a separation of the isomers is not absolutely necessary This is because the individual isomers partly change during the preparation for use or during use (e.g. under Light, acid or base exposure) can convert into each other. Corresponding conversions can also be made after application for example in the treatment of plants, in the treated Plant or in the harmful fungus or animal damage to be controlled ling done.

Regarding the C = N double bond in group Q, there are visibly their effectiveness the E-isomers of the compounds I be preferred (configuration based on the OCH₃ group in the ratio to -CONHCH₃- or -COOCH₃ group).

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 those to be kept free from harmful fungi or animal pests Do not damage plants, surfaces, materials or spaces and that Do not impair the action of the compounds I. Especially be such salts are significant, which are for agricultural Purposes.  

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

The compounds of formula I can also by known methods or converted into their N-oxides analogously to these {cf. e.g. B. A. Albini and S. Pietra, Heterocyclic N-Oxides, CRC-Press Inc., 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 oxidations customary for the oxidation of the pyridine ring Examples include peracetic acid, trifluoroperacetic acid, Perbenzoic acid, m-chloroperbenzoic acid, monopermaleic acid, Magnesium monoperphthalate, sodium perborate, Oxone® (contains Per oxodisulfate), tungsten 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.

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 iodine;
Alkyl: straight-chain or branched alkyl groups with 1 to 4, 6 or 8 carbon atoms, e.g. B. C₁-C₆-alkyl such as methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methyl-propyl, 2-methylpropyl, 1,1-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1 , 2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2 Trimethylpropyl, 1-ethyl-1-methylpropyl and 1-ethyl-2-methylpropyl;
Alkylamino: an amino group which carries a straight-chain or branched alkyl group having 1 to 6 carbon atoms as mentioned above;
Dialkylamino: an amino group which carries two independent, straight-chain or branched alkyl groups each having 1 to 6 carbon atoms as mentioned above;
Alkylsulfoxyl: e.g. B. C₁-C₈ alkyl sulfoxyl:
Alkyl groups as defined above which are bonded to the skeleton via a sulfo xyl group (-SO₂-);
Alkylsulfonyl: e.g. B. C₁-C₈ alkyl sulfoxyl:
Alkyl groups as defined above which are attached to the skeleton via a sulfoyl group (-SO-);
Trialkylsilyloxy: e.g. B. Tri-C₁-C₈-alkylsilyloxy:
Silyloxy groups

which carry three alkyl groups as defined above on the silicon atom and are bonded to the structure via the oxygen atom;
Haloalkyl: straight-chain or branched alkyl groups with 1 to 6 carbon atoms, in which groups the hydrogen atoms in these groups can be partially or completely replaced by halogen atoms as mentioned above, e.g. 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, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl and penta fluoroethyl;
Alkoxy: straight-chain or branched alkyl groups with 1 to 4, 6 or 8 carbon atoms as mentioned above, which are bonded to the skeleton via an oxygen atom (-O-), for. B. C₁-C₆ alkoxy such as methyloxy, ethyloxy, propyloxy, 1-methylethyloxy, butyloxy, 1-methyl-propyloxy, 2-methylpropyloxy, 1,1-dimethylethyloxy, pentyloxy, 1-methylbutyloxy, 2-methylbutyloxy, 3-methylbutyloxy , 2,2-dimethylpropyloxy, 1-ethylpropyloxy, hexyloxy, 1,1-dimethylpropyloxy, 1,2-dimethylpropyloxy, 1-methylpentyloxy, 2-methylpentyloxy, 3-methylpentyloxy, 4-methylpentyloxy, 1,1-dimethylbutyloxy , 1,2-dimethylbutyloxy, 1,3-dimethylbutyloxy, 2,2-dimethylbutyloxy, 2,3-dimethylbutyloxy, 3,3-dimethylbutyloxy, 1-ethylbutyloxy, 2-ethylbutyloxy, 1,1,2-trimethylpropyloxy, 1,2,2-trimethylpropyloxy, 1-ethyl-1-methylpropyloxy and 1-ethyl-2-methylpropyloxy;
Alkoxyalkyl: e.g. B. C₁-C₈-alkoxy-C₁-C₄-alkyl: alkyl groups having 1 to 4 carbon atoms as defined above, which carry an alkoxy group having 1 to 8 carbon atoms as mentioned above;
Alkylenedioxy: e.g. B. C₁-C₂-alkylenedioxy: straight-chain or ver branched alkylene groups with 1 to 2 carbon atoms, which are bound in two places via an oxygen atom (-O-) in the structure or are bound to the structure such as methylenedioxy (-O-CH₂ -O-) or ethylenedioxy (-O-CH₂CH₂-O-);
Alkylthio: straight-chain or branched alkyl groups with 1 to 4 or 6 carbon atoms as mentioned above, which are bonded to the skeleton via a sulfur atom (-S-), e.g. B. C₁-C₆-alkylthio such as methylthio, ethylthio, propylthio, 1-methylethylthio, butylthio, 1-methylpropylthio, 2-methylpropylthio, 1,1-dimethylethylthio, pentylthio, 1-methylbutylthio, 2-methyl butylthio, 3-methylbutylthio, 2,2-dimethylpropylthio, 1-ethylpropylthio, hexylthio, 1,1-dimethylpropylthio, 1,2-dimethylpropylthio, 1-methylpentylthio, 2-methylpentylthio, 3-methylpentylthio, 4-methylpentylthio, 1,1-dimethylbutylthio , 1,2-dimethylbutylthio, 1,3-dimethylbutylthio, 2,2-dimethylbutylthio, 2,3-dimethylbutylthio, 3,3-dimethylbutylthio, 1-ethylbutylthio, 2-ethylbutylthio, 1,1,2-trimethylpropylthio, 1 , 2,2-tri methylpropylthio, 1-ethyl-1-methylpropylthio and 1-ethyl-2-methylpropylthio;
Cycloalkyl: e.g. B. C₃-C₈-cycloalkyl: monocyclic alkyl groups with 3 to 8 carbon ring members, for. B. cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl;
Heteroaryl: aromatic mono- or polycyclic radicals which, in addition to carbon ring members, can additionally contain one to four nitrogen atoms or one to three nitrogen atoms and one oxygen or one sulfur atom or one oxygen or one sulfur atom, e.g. B.

• - 5-membered heteroaryl containing one to three nitrogen atoms: 5-ring heteroaryl groups, which in addition to carbon atoms contain one to three nitrogen atoms as ring members can, 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 one to four nitrogen atoms or one to three nitrogen atoms and one sulfur or Oxygen atom or an oxygen or a sulfur atom: 5-ring heteroaryl groups, which in addition to carbon atoms one to four nitrogen atoms or one to three stick atoms of matter and a sulfur or oxygen atom or a Contain oxygen or sulfur atom as ring members can, e.g. B. 2-furyl, 3-furyl, 2-thienyl, 3-thienyl, 2-pyrrolyl, 3-pyrrolyl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 3-isothiazolyl, 4-isothiazolyl, 5-isothiazolyl, 3-pyrazolyl, 4-pyrazolyl, 5-pyrazolyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 2-imidazolyl, 4-imidazolyl, 1,2,4-oxadiazol-3-yl, 1,2,4-oxadiazol-5-yl, 1,2,4-thiadiazol-3-yl, 1,2,4-thiadiazol-5-yl, 1,2,4-triazol-3-yl, 1,3,4-oxadiazol-2-yl, 1,3,4-thiadiazol-2-yl, 1,3,4-triazol-2-yl;
• - Benzo-condensed 5-membered heteroaryl containing one up to three nitrogen atoms or one nitrogen atom and / or one Oxygen or sulfur atom: 5-ring heteroaryl groups, which besides carbon atoms one to four nitrogen atoms or one to three nitrogen atoms and one sulfur or Oxygen atom or an oxygen or a sulfur atom as Ring members can contain, and in which two adjacent Carbon ring members or a nitrogen and an adj beard carbon ring member through a buta-1,3-diene-1,4-diyl group can be bridged;
• - 5-membered heteroaryl bound via nitrogen, ent holding one to four nitrogen atoms, or over nitrogen bound benzo-fused 5-membered heteroaryl, ent holding one to three nitrogen atoms: 5-ring heteroaryl groups which, in addition to carbon atoms, contain one to four sticks atoms or one to three nitrogen atoms as ring members can contain, and in which two adjacent coals fabric ring links or a nitrogen and an adjacent one Carbon ring member through a buta-1,3-diene-1,4-diyl group can be bridged, these rings over one of the Nitrogen ring members are bound to the scaffold;
• - 6-membered heteroaryl containing one to three or one to four nitrogen atoms: 6-ring heteroaryl groups, which next to Carbon atoms one to three or one to four nitrogen  may contain atoms as 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-triazin-2-yl, 1,2,4-triazin-3-yl and 1,2,4,5-tetrazin-3-yl;
• - Benzo-condensed 6-membered heteroaryl containing one up to four nitrogen atoms: 6-ring heteroaryl groups in which two adjacent carbon ring members by one Buta-1,3-diene-1,4-diyl group may be bridged, e.g. B. Quinoline, isoquinoline, 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 as mentioned above can be replaced can.

The expression "optionally substituted" is intended to express brin gene that in the groups characterized in this way the hydrogen atoms partially or completely by the same or different For example, those groups can be replaced that under the collective terms set out above.

With regard to their biological action against harmful fungi and animal pests, preference is given to compounds I in which the radicals have the following meanings, on their own or in combination;
R1 hydrogen;
R1 methyl;
R² halogen, especially fluorine and chlorine;
R² is methyl;
R2 trifluoromethyl;
R³ C₁-C₈-alkyl, which radical can be partially or completely halo geniert;
R³ C₃-C₆ cycloalkyl;
R³ C₁-C₈ alkoxy;
R³ C₁-C₈ alkylthio;
R³ di-C₁-C₈ alkylamino;
R³ C₁-C₈ alkyl sulfoxyl;
R³ C₁-C₈ alkylsulfonyl;
R³ chlorine;
R³ phenyl, which radical can carry one to three of the following groups: halogen, C₁-C₄-alkyl, cyano, C₁-C₄-alkoxy, nitro, optionally partially or completely halogenated C₁-C₂-alkylenedioxy;
R³ is C₁-C₄-alkyl substituted by phenyl, where the alkyl part is otherwise unsubstituted and the phenyl part can carry one or two of the following groups: halogen, cyano, nitro, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄- Alkoxy;
R⁴ hydrogen.

With regard to the biological effect mentioned especially before are listed in the following tables Connections I.

Table 1
Compounds of formula I.1, with
R1 = hydrogen;
R² = methyl;
R³ = one row each from Table A

Table 2
Compounds of formula I.1, with
R1 = hydrogen;
R² = fluorine;
R³ = one row each from Table A

Table 3
Compounds of formula I.1, with
R1 = hydrogen;
R² = chlorine;
R³ = one row each from Table A

Table 4
Compounds of formula I.1, with
R1 = hydrogen;
R² = trifluoromethyl;
R³ = one row each from Table A, except row No. 1

Table 5
Compounds of formula I.1, with
R1 = methyl;
R² = chlorine;
R³ = one row each from Table A

Table 6
Compounds of formula I.2, with
R1 = hydrogen;
R² = methyl;
R³ = one row each from Table A

Table 7
Compounds of formula I.2, with
R1 = hydrogen;
R² = fluorine;
R³ = one row each from Table A

Table 8
Compounds of formula I.2, with
R1 = hydrogen;
R² = chlorine;
R³ = one row each from Table A

Table 9
Compounds of formula I.2, with
R1 = hydrogen;
R² = trifluoromethyl;
R³ = one row each from Table A, except row No. 1

Table 10
Compounds of formula I.2, with
R1 = methyl;
R² = chlorine;
R³ = one row each from Table A

Table 11
Compounds of formula I.3, with
R1 = hydrogen;
R² = methyl;
R³ = one row each from Table A

Table 12
Compounds of formula I.3, with
R1 = hydrogen;
R² = fluorine;
R³ = one row each from Table A

Table 13
Compounds of formula I.3, with
R1 = hydrogen;
R² = chlorine;
R³ = one row each from Table A

Table 14
Compounds of formula I.3, with
R1 = hydrogen;
R² = trifluoromethyl;
R³ = one row each from Table A, except row No. 1

Table 15
Compounds of formula I.3, with
R1 = methyl;
R² = chlorine;
R³ = one row each from Table A

Table A

Among the particularly preferred ones compiled above Compounds I are particularly preferred in those R³ does not mean hydrogen.

The compounds I are suitable for combating harmful fungi and animal pests.

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 Rizi 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 of dodecylbenzenesulfonic acid, 5 parts by weight of the addition product of 40 moles of ethylene oxide with 1 mole of castor oil: through A fine distribution of the solution in water gives a dis persion;
• 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 moles of ethylene oxide to 1 mole 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 parts by weight ground in a hammer mill a compound I, 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 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 and sugar cane, Ustilago , Venturia inaequalis (scab) on apples, Helminthosporium species on cereals, Septoria nodorum on wheat, Botrytis cinerea (gray mushrooms) on strawberries, vines, ornamental plants and vegetables, Cercospora arachidicola on peanuts, Pseudocercosporella herpotrichoides on wheat, barley 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 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 (dithiocarbamate N-ethylene-bis-N,) of zinc, 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 -Nitro-iso-phthalic acid di-iso-propyl ester;
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-trichloromethylthiophthalimide, N-dichlorofluoromethylthio-N ', N'-dimethyl-N-phenylsulfuric acid diami-d, 5-ethoxy-3-trichloromethyl 1,2,3-thiadiazole, 2-rhodane methyl thiobenzothiazole, 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-oxathiine, 2,3-dihydro-5-carboxanilido-6-methyl-1,4- oxathiin-4,4-dioxide, 2-Me thyl-5,6-dihydro-4H-py ran-3-carboxylic acid anilide, 2-methyl-furan-3-carboxylic acid anilide, 2,5-dimethyl-furan-3-carboxylic acid anilide, 2,4,5-trimethyl-fu ran-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- Iodobenzoic 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-cyclododecyl 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-triazol-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-chlorophenyl) 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-dimethoxyphenyl) acrylic acid morpholide.

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

The compounds of formula I are also suitable, animal Pests, especially from the class of insects, arachnids and effectively combat nematodes. You can in crop protection  as well as in the hygiene, stock protection and veterinary sector as Pesticides are used.

The harmful insects belong to the order of the Shmet terlings (Lepidoptera) for example Agrotis ypsilon, Agrotis segetum, Alabama argillacea, Anticarsia gemmatalis, Argyresthia conjugella, Autographa gamma, Bupalus piniarius, Cacoecia murinana, Capua reticulana, Cheimatobia brumata, Choristoneura fumiferana, Choristoneura occidentalis, Cirphis unipuncta, Cydia pomonella, Dendrolimus pini, Diaphania nitidalis, Diatraea grandiosella, Earias insulana, Elasmopalpus lignosellus, Eupoecilia ambiguella, Evetria bouliana, Feltia subterranea, Galleria mellonella, Grapholitha funebrana, Grapholitha molesta, Heliothis armigera, Heliothis virescens, Heliothis zea, Hellula undalis, Hibernia defoliaria, Hyphantria cunea, Hyponomeuta malinellus, Keiferia lycopersicella, Lambdina fiscellaria, Laphygma exigua, Leucoptera coffeella, Leucoptera scitella, Lithocolletis blancardella, Lobesia botrana, Loxostege sticticalis, Lymantria dispar, Lymantria monacha, Lyonetia clerkella, Malacosoma neustria, Mamestra brassicae, Orgyia pseudotsugata, Ostrinia nubilalis, Panolis flammea, Pectinophora gossypiella, Peridroma saucia, Phalera bucephala, Phthorimaea operculella, Phyllocnistis citrella, Pieris brassicae, Plathypena scabra, Plutella xylostella, Pseudoplusia includens, Rhyacionia frustrana, Scrobipalpula absoluta, Sitotroga cerealella, Sparga nothis pilleriana, Spodoptera frugiperda, Spodoptera littoralis, Spodoptera litura, Thaumatopoea pityocampa, Tortrix viridana, Trichoplusia ni, Zeiraphera canadensis.

From the order of the beetles (Coleoptera), for example Agrilus sinuatus, Agriotes lineatus, Agriotes obscurus, Amphimallus solstitialis, Anisandrus dispar, Anthonomus grandis, Anthonomus pomorum, Atomaria linearis, Blastophagus piniperda, Blitophaga undata, Bruchus rufimanus, Bruchus pisorum, Bruchus lentis, Byctiscus betulae, Cassida nebulosa, Cerotoma trifurcata, Ceuthorrhynchus assimilis, Ceuthorrhynchus napi, Chaetocnema tibialis, Conoderus vespertinus, Crioceris asparagi, Diabrotica longicornis, Diabrotica 12-punctata, Diabrotica virgifera, Epilachna varivestis, Epitrix hirtipennis, Eutinobothrus brasiliensis, Hylobius abietis, Hypera brunneipennis, Hypera postica, Ips typographus, Lema bilineata, Lema melanopus, Leptinotarsa decemlineata, Limonius californicus, Lissorhoptrus oryzophilus, Melanotus communis, Meligethes aeneus, Melolontha hippocastani, Melolontha melolontha, Oulema oryzae, Ortiorrhynchus sulcatus, Otiorrhynchus ovatus, Phaedon cochleariae, Phyllotreta chrysocephala, Phyllophaga sp., Phyllopertha horticola, Phyllotreta nemorum, Phyllotreta  striolata, Popillia japonica, Sitona lineatus, Sitophilus granaria.

From the order of the two-winged birds (Diptera), for example, Aedes aegypti, Aedes vexans, Anastrepha ludens, Anopheles maculipennis, Ceratitis capitata, Chrysomya bezziana, Chrysomya hominivorax, Chrysomya macellaria, Contarinia sorghicola, Cordylobia anthro pophaga, Culex pipiens, Dacus cucurbitae, Dacus oleae, Dasineura brassicae, Fannia canicularis, Gasterophilus intestinalis, Glossina morsitans, Haematobia irritans, Haplodiplosis equestris, Hylemyia platura, Hypoderma lineata, Liriomyza sativae, Liriomyza trifolii, Lucilia caprina, Lucilia cuprina, Lucilia sericata, Lycoria pectoralis, Mayetiola destructor, Musca domestica, Muscina stabulans, Oestrus ovis, Oscinella frit, Pegomya hysocyami, Phorbia antiqua, Phorbia brassicae, Phorbia coarctata, Rhagoletis cerasi, Rhagoletis pomonella, Tabanus bovinus, Tipula oleracea, tipula paludosa.

From the order of the thrips (Thysanoptera) for example Frankliniella fusca, Frankliniella occidentalis, Frankliniella tritici, Scirtothrips citri, Thrips oryzae, Thrips palmi, Thrips tabaci.

From the order of the hymenoptera, for example Athalia rosae, Atta cephalotes, Atta sexdens, Atta texana, Hoplocampa minuta, Hoplocampa testudinea, Monomorium pharaonis, Solenopsis geminata, Solenopsis invicta.

From the order of the bugs (Heteroptera), for example, Acroster num hilare, Blissus leucopterus, Cyrtopeltis notatus, Dysdercus cingulatus, Dysdercus intermedius, Eurygaster integriceps, Euschistus impictiventris, Leptoglossus phyllopus, Lygus lineolaris, Lygus pratensis, Nezara viridula, Piesma quadrata, Solubea insularis, Thyanta perditor.

From the order of the plant suckers (Homoptera), for example Acyrthosiphon onobrychis, Adelges laricis, Aphidula nasturtii, Aphis fabae, Aphis pomi, Aphis sambuci, Brachycaudus cardui, Brevicoryne brassicae, Cerosipha gossypii, Dreyfusia nord mannianae, Dreyfusia piceae, Dysaphis radicola, Dysaulacorthum pseudosolani, Empoasca fabae, Macrosiphum avenae, Macrosiphum euphorbiae, Macrosiphon rosae, Megoura viciae, Metopolophium dirhodum, Myzodes persicae, Myzus cerasi, Nilaparvata lugens, Pemphigus bursarius, Perkinsiella saccharicida, Phorodon humuli, Psylla mali, Psylla piri, Rhopalomyzus ascalonicus, Rhopalosiphum maidis, Sappaphis mala, Sappaphis mali, Schizaphis graminum,  Schizoneura lanuginosa, Trialeurodes vaporariorum, Viteus vitifolii.

From the order of the termites (Isoptera), for example, Calotermes flavicollis, Leucotermes flavipes, Reticulitermes lucifugus, Termes natalensis.

From the order of the straight wing aircraft (Orthoptera) for example Acheta domestica, Blatta orientalis, Blattella germanica, Forficula auricularia, Gryllotalpa gryllotalpa, Locusta migrato ria, Melanoplus bivittatus, Melanoplus femur-rubrum, Melanoplus mexicanus, Melanoplus sanguinipes, Melanoplus spretus, Nomadacris septemfasciata, Periplaneta americana, Schistocerca americana, Schistocerca peregrina, Stauronotus maroccanus, Tachycines asynamorus.

Arachnoid, for example, arachnids (Acarina) such as Amblyomma americanum, Amblyomma variegatum, Argas persicus, Boophilus annulatus, Boophilus decoloratus, Boophilus microplus, Brevipalpus phoenicis, Bryobia praetiosa, Dermacentor silvarum, Eotetranychus carpini, Eriophyes sheldoni, Hyalomma truncatum, Ixodes ricinus, Ixodes rubicundus, Ornithodorus moubata, Otobius megnini, Paratetranychus pilosus, Dermanyssus gallinae, Phyllocoptruta oleivora, Polyphagotarsonemus latus, Psoroptes ovis, Rhipicephalus appendiculatus, Rhipicephalus evertsi, Sarcoptes scabiei, Tetranychus cinnabarinus, Tetranychus kanzawai, Tetranychus pacificus, Tetranychus telarius, Tetra nychus urticae.

From the class of nematodes, for example, root gall nematodes, e.g. B. Meloidogyne hapla, Meloidogyne incognita, Meloidogyne javanica, cyst-forming nematodes, e.g. B. Globodera rostochiensis, heterodera avenae, heterodera glycines, heterodera schachtii, Heterodera trifolii, stick and leaf whale, e.g. B. Belonolaimus longicaudatus, Ditylenchus destructor, Ditylenchus dipsaci, Heliocotylenchus multicinctus, Longidorus elongatus, Radopholus similis, Rotylenchus robustus, Trichodorus primitivus, Tylenchorhynchus claytoni, Tylenchorhynchus dubius, Pratylenchus neglectus, Pratylenchus penetrans, Pratylenchus curvitatus, Pratylenchus goodeyi.

The drug concentrations in the ready-to-use Preparations can be varied in larger areas.

Generally they are between 0.0001 and 10%, preferably between 0.01 and 1%.  

The active ingredients can also be used with great success in the ultra-low-volume process (ULV) can be used, it is possible to use form stungen with more than 95 wt .-% active ingredient or even the active ingredient without applying additives.

The amount of active ingredient used to control pests is 0.1 to 2.0, preferably in the field 0.2 to 1.0 kg / ha.

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 and III used will. The physical data of the Pro Products are shown in the following tables.

The chemical shifts (in ppm) of the 1 H NMR spectra were measured against tetramethylsilane (br = broad signal, s = Singu lett, d = doublet, m = multiplet).

I) Preparation of compounds I in which Q is for C (= NOCH₃) -CONHCH₃ stands

The preparation of the starting compounds III can, for example, as described below (Examples 1 to 3) from the easily accessible E-2-methoxyimino-2 - [(2-methylphenyloxymethyl) phenyl] acetic acid methyl ester (cf. EP-A 493 711) by aminolysis with methylamine and subsequent cleavage with boron trichloride or bromine water fabric.

example 1 E-2-methoxyimino-2 - [(2-methylphenyloxymethyl) phenyl] acetic acid methylamide

250 g of E-2-methoxyimino-2 - [(2-methylphenyloxymethyl) phenyl] acetic acid methyl ester were suspended in 1 l of 40% strength aqueous methylamine solution and heated to 40 ° C. for 4 hours. After cooling to room temperature (20 ° C), the solid was suction filtered, washed several times with water and dried at 50 ° C. 229.8 g of the title compound were obtained as colorless crystals.
M.p .: 109-112 ° C; 1 H NMR (CDCl₃): 2.20 (s, 3H); 2.85 (d, 3H); 3.95 (s, 3H); 4.90 (s, 2H); 6.7 (NH); 6.8-7.6 (m, 8H).

Example 2 E-2-methoxyimino-2 - [(2-chloromethyl) phenyl] acetic acid methyl amide

2 g of E-2-methoxyimino-2 - [(2-methylphenyloxymethyl) phenyl] acetic acid methylamide from Example 1 were placed in 30 ml of anhydrous dichloromethane at 10 ° C. 9.4 g of boron trichloride (as a 1 molar solution in n-hexane) were added dropwise, the mixture was heated under reflux for 1.5 h, cooled to 10 ° C., another 9.4 g of boron trichloride were added and the mixture was left overnight at room temperature Stir (20 ° C). After 8.2 g of methanol had been added dropwise, the mixture was spun in. The residue was taken up in 100 ml dichloromethane, lye with 5% sodium hydroxide and then washed with water. The organ. Phase was then dried over sodium sulfate. After stripping off the solvent, 1.2 g of the title compound remained as an oil.
1 H NMR (CDCl₃): 2.95 (d, 3H); 3.90 (s, 3H); 4.45 (s, 2H); 6.8 (NH) 7.1-7.6 (m, 4H).

Example 3 E-2-methoxyimino-2 - [(2-bromomethyl) phenyl] acetic acid methyl amide

10 g of E-2-methoxyimino-2 - [(2-methylphenyloxymethyl) phenyl] acetic acid methylamide from Example 1 were placed in 50 ml of anhydrous dichloromethane. Hydrogen bromide was introduced into the solution up to the saturation concentration (approx. 9 g HBr). After stirring for 68 h at room temperature, the starting material was completely converted. After adding a further 50 ml of dichloromethane, the procedure was as in Example 2. There remained 7.0 g of the title compound as an oil, which crystallized on standing.
Mp: 128-129 ° C; 1 H NMR (CDCl₃): 2.95 (d, 3H); 3.95 (s, 3H); 4.35 (s. 2H); 6.85 (NH); 7.1-7.5 (m. 4H).

Example 4 E-2-methoxyimino-2 - [(2- [2-n-propyl-5-methylpyrimidin-4-yl)] oxy methyl) phenyl] acetic acid methyl amide

1.52 g of 2-n-propyl-5-methyl-4-hydroxypyrimidine was dissolved in 25 ml of dimethylformamide. 1.38 g of finely powdered potassium carbonate and 2.85 g of E-2-methoxyimino-2 - [(2-bromomethyl) phenyl] acetic acid methyl amide were added. The mixture was stirred at 50 ° C. for 4 hours and concentrated. The residue was taken up in 300 ml of semi-concentrated aqueous sodium chloride solution and extracted three times with 100 ml each of methyl tert-butyl ether. Then the combined organic phases were washed with water and dried over sodium sulfate. After the solvent had been stripped off, the remaining residue was chromatographed on silica gel using cyclohexane / ethyl acetate 1: 2. 0.6 g of the title compound was obtained as a colorless solid.
Mp .: 60-62 ° C.

II) Preparation of compounds I in which Q is for C (= NOCH₃) -COOCH₃ is Example 5 E-2-methoxyimino-2 - [(2- [2-ethyl-5-methylpyrimidin-4-yl)] oxy methyl) phenyl] methyl acetate (Table No. 2)

2.17 g of 2-ethyl-5-methyl-4-hydroxypyrimidine were dissolved in 40 ml of dimethylformamide. 3.1 g of finely powdered potassium carbonate and 4.29 g of E-2-methoxyimino-2 - [(2-bromomethyl) phenyl] acetic acid methyl ester were added. The mixture was stirred at 50 ° C. for four hours, then at room temperature overnight and concentrated. The residue was taken up in 300 ml of dilute sodium chloride solution and extracted three times with methyl tert-butyl ether. The combined organic phases were washed first with sodium hydrogen carbonate solution, then with water. Then the combined organic phases were dried over sodium sulfate. After the solvent had been stripped off, the remaining residue was recrystallized from n-hexane / methyl tert-butyl ether. 1.3 g of the title compound were obtained as a colorless solid.
Mp .: 75-77 ° C.

Examples of use 1. Example of the action against harmful fungi

For the following experiments on the fungicidal activity of Compounds I an emulsion was used which 10% by weight from the active ingredient and 90% by weight from a mixture

70% by weight 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 drug concentrations were determined by Dilute this emulsion with water.

Efficacy against Pyricularia oryzae (protective)

Leaves of rice seedlings of the variety grown in pots "Tai-Nong 67" were made with aqueous emulsions that were 80% active and contained 20% emulsifier in the dry substance, drip sprayed wet and 24 hours later with an aqueous spore suspension of Pyricularia oryzae inoculated. Then were the test plants in climatic chambers at 22-24 ° C and 95-99% relative humidity set up. After 6 days it was The extent of the disease was determined visually.

The following compounds according to the invention were each individually in Form of an aqueous containing 63 ppm of the respective active ingredient Preparation tested: No. 1, 3, 5, 6, 7, 8, 9, 10 and 11 from Ta belle S1. The visual assessment resulted when using this Connections a fungal attack on 0 to 5% of the leaf areas. Untreated plants were 80% infected.

2. Examples of the action against animal pests

The activity of the compounds of the general formula I against animal pests was demonstrated by the following tests:
The active ingredients were

• a) as a 0.1% solution in acetone or  
• b) as a 10% emulsion in a mixture of 70% by weight cyclo hexanone, 20% by weight Nekanil® LN (Lutensol® AP6, wetting agent with emulsifying and dispersing action based on ethoxy gated alkylphenols) and 10% by weight Uniperol® EL (non-ionic shear emulsifier based on ethoxylated castor oil)

processed and in accordance with the desired concentration Dilute acetone in the case of a) or with water in the case of b).

After the end of the tests, the lowest concentration was obtained tration determined in which the connections compared to unbe control attempts were still 80-100% inhibition or Cause mortality (threshold of action or minimum concentration).

Claims (7)

1. 2- (O- [pyrimidin-4-yl] methyleneoxy) phenylacetic acid derivatives of the general formula I and their salts and N-oxides, in which the radicals R¹ to R⁴ and Q have the following meanings: R¹ is hydrogen or C₁-C₄ alkyl;
R² is halogen, C₁-C₂ alkyl or C₁-C₂ haloalkyl;
R³ is hydrogen; Amino; Hydroxy; Mercapto; Halogen; C₁-C₈-alkyl, where the alkyl radicals can carry a phenyl group, which in turn can carry one or, independently of one another, two of the following substituents: halogen, cyano, nitro, C₁-C₄-alkyl, C₁-C₄-haloalkyl and C₁ -C₄ alkoxy; C₁-C₈ haloalkyl; C₁-C₈-Alko xy-C₁-C₄-alkyl; C₁-C₈ alkoxy; C₁-C₈ monoalkylamino; Di-C₁-C₈ alkylamino; C₁-C₈ alkylthio; C₁-C₈ alkyl sulfoxyl; C₁-C₈ alkylsulfonyl; C₃-C₈ cycloalkyl; Tri-C₁-C₈-alkyl silyloxy or optionally substituted in the aromatic ring: phenyl, phenoxy, phenoxymethyl, benzyloxy or heteroaryl;
R⁴ hydrogen; Cyano; Halogen; C₁-C₄ alkyl; C₁-C₄ halogen alkyl or C₁-C₄ alkoxy;
QC (= NOCH₃) -CONHCH _3,
C (= NOCH₃) -COOCH₃ or
N (OCH₃) -COOCH₃. 2. To combat harmful fungi and animal pests suitable means containing an effective amount of ver bond of the general formula I or one of its salts or N-oxides according to claim 1 and at least one formulation tools.   3. Use of the compounds I, their salts or N-oxides according to Claim 1 for the production of agents against harmful fungi and animal pests. 4. A process for the preparation of the agent according to claim 2, because characterized in that a compound of general Process formula I with at least one formulation aid works. 5. Use of the compounds I, their salts and N-oxides according to Claim 1 or the agent according to claim 2, for combating of harmful fungi and animal pests. 6. Procedures to control harmful fungi and animal Pests, characterized in that the harmful fungi or the animal pests, their habitat or that of Plants, seeds, areas, materia to be kept free lien or rooms with an effective amount of a compound of formula I or one of its salts or N-oxides according to An treated claim 1 or an agent according to claim 2.