DE10339360A1 - New 7-amino-5-halo-pyrazolo-(1,5-a)-pyrimidine derivatives, useful as microbicides, especially fungicides or bactericides for protecting plants or materials such as wood - Google Patents

Abstract

3-Substituted 7-amino-5-halo-pyrazolo-(1,5-a)-pyrimidine derivatives (I) are new. Pyrazolo-pyrimidines of formula (I) and their salts are new. [Image] R 1>alkyl, alkenyl, alkynyl, cycloalkyl or heterocyclyl (all optionally substituted); R 2>H or alkyl; or NR 1>R 2>optionally substituted heterocycle; R 3>optionally substituted heterocyclyl; R 4>H or alkyl; Hal : halogen; and X : halo, CN, NO 2, alkyl, optionally substituted alkenyl, optionally substituted alkynyl, hydroxyalkyl, alkylcarbonyl, alkoxyalkyl, haloalkyl, cycloalkyl, CHO, CSNH 2, alkoxycarbonyl, hydroxyiminoalkyl, alkoxyiminoalkyl, alkylthio, alkylsulfinyl, alkylsulfonyl or alkylaminocarbonyl. Independent claims are included for: (a) A method of preparation of (I); (b) Interconversion of (I); (c) New pyrazolo-pyrimidine derivative intermediates of formulae (II) and (X); (d) New pyridyl- or pyrimidinyl-malonate ester derivative intermediates of formulae (XII-a) and (XII-b); and (e) A method of preparation of (II), (X), (XII-a) and (XII-b). [Image] X 1>halo, CN, NO 2, alkyl, haloalkyl, cycloalkyl, CHO, CSNH 2, alkoxycarbonyl, alkylcarbonyl, alkylthio, alkylsulfinyl, alkylsulfonyl or alkylaminocarbonyl; Y 1>halo; R : halo, CN, NO 2, alkyl, haloalkyl, cycloalkyl, CSNH 2, alkoxycarbonyl, alkylthio, alkylsulfinyl, alkylsulfonyl or alkylaminocarbonyl; R 1> 2>1-4C alkyl; R 1> 3>, R 1> 4>halo or haloalkyl; and R 15>, R 1> 6>H, F, CL, Br, Me, Et or OMe. ACTIVITY : Fungicide; antibacterial; algicide; cytostatic; herbicide; plant growth regulator. In tests against Venturia inaequalis in apple tree seedlings, 3-cyano-5-chloro-6-(3-trifluoromethyl-pyridin-2-yl)-pyrazolo-(1,5-a)-pyrimidin-7-yl-N-((1S)-2,2,2-trifluoro-1-methylethyl)-amine (Ia) at an application rate of 100 g/ha gave more than 90% prevention of infection. MECHANISM OF ACTION : None given.

Description

The The present invention relates to novel pyrazolopyrimidines, several Process for their preparation and their use for controlling undesirable Microorganisms. The invention also relates to novel intermediates and process for their preparation.

It has already become known that certain pyrazolopyrimidines have fungicidal properties (cf. DE-A 3,130,633 or FR-A 2 794 745 ). The effect of these substances is good, but leaves at low application rates in some cases to be desired.

in welcher
R¹ für gegebenenfalls substituiertes Alkyl, gegebenenfalls substituiertes Alkenyl, gegebenenfalls substituiertes Alkinyl, gegebenenfalls substituiertes Cylcoalkyl oder für gegebenenfalls substituiertes Heterocyclyl steht,
R² für Wasserstoff oder Alkyl, steht, oder
R¹ und R² gemeinsam mit dem Stickstoffatom, an das sie gebunden sind, für einen gegebenenfalls substituierten heterocyclischen Ring stehen,
R³ für gegebenenfalls substituiertes Heterocyclyl steht,
Hal für Halogen steht und
X für Halogen, Cyano, Nitro, Alkyl, Alkenyl, Hydroxyalkyl, Alkoxyalkyl, Halogenalkyl, Cycloalkyl, Formyl, Thiocarbamoyl, Alkoxycarbonyl, Alkylcarbonyl, Hydroxyiminoalkyl, Alkoximinoalkyl, Alkylthio, Alkylsulfinyl, Alkylsulfonyl oder Alkylaminocarbonyl steht,
gefunden.There have now been new pyrazolopyrimidines of the formula

in which
R ^{1 is} optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted cycloalkyl or optionally substituted heterocyclyl,
R ^{2 is} hydrogen or alkyl, or
R ¹ and R ² together with the nitrogen atom to which they are attached represent an optionally substituted heterocyclic ring,
R ^{3 is} optionally substituted heterocyclyl,
Hal stands for halogen and
X is halogen, cyano, nitro, alkyl, alkenyl, hydroxyalkyl, alkoxyalkyl, haloalkyl, cycloalkyl, formyl, thiocarbamoyl, alkoxycarbonyl, alkylcarbonyl, hydroxyiminoalkyl, alkoximinoalkyl, alkylthio, alkylsulfinyl, alkylsulfonyl or alkylaminocarbonyl,
found.

Depending on the substitution pattern, the compounds according to the invention may optionally be present as mixtures of various possible isomeric forms, in particular of stereoisomers, such as E and Z, threo and erythro, and also optical isomers, but optionally also in the form of tautomers. If R ^{3 is} unequivocally substituted at both atoms adjacent to the binding site, the compounds in question may be in a particular form of stereoisomerism, as atropisomers.

• a) Halogen-pyrazolopyrimidine der Formel
  
  in welcher R³ und Hal die oben angegebenen Bedeutungen haben, X¹ für Halogen, Cyano, Nitro, Alkyl, Halogenalkyl, Cycloalkyl, Thiocarbamoyl, Alkoxycarbonyl, Alkylcarbonyl, Alkylthio, Alkylsulfinyl, Alkylsulfonyl oder Alkylaminocarbonyl steht und Y¹ für Halogen steht, mit Aminen der Formel
  
  in welcher R¹ und R² die oben angegebenen Bedeutungen haben, gegebenenfalls in Gegenwart eines Verdünnungsmittels, gegebenenfalls in Gegenwart eines Katalysators und gegebenenfalls in Gegenwart eines Säureakzeptors, umsetzt, oder
• b) Pyrazolopyrimidine der Formel
  
  in welcher R¹, R², R³ und Hal die oben angegebenen Bedeutungen haben, entweder α) mit Diisobutyl-aluminiumhydrid in Gegenwart von wässriger Ammoniumchlorid-Lösung sowie in Gegenwart eines organischen Verdünnungsmittels umsetzt, oder β) mit Grignard-Verbindungen der Formel R⁴-Mg-X² (IV) in welcher R⁴ für Alkyl steht und X² für Chlor oder Brom steht, in Gegenwart eines Verdünnungsmittels und gegebenenfalls in Gegenwart eines Katalysator umsetzt, oder
• c) Pyrazolopyrimidine der Formel
  
  in welcher R¹, R², R³ und Hal die oben angegebenen Bedeutungen haben und R⁵ für Wasserstoff oder Alkyl steht, entweder α) mit Amino-Verbindungen der Formel H₂N-OR⁶ (V)in welcher R⁶ für Wasserstoff oder Alkyl steht, in Gegenwart eines Verdünnungsmittels und gegebenenfalls in Gegenwart eines Katalysators umsetzt, wobei die Amino-Verbindungen der Formel (V) auch in Form ihrer Säureadditions-Salze eingesetzt werden können, oder β) mit Triphenylphosphonium-Salzen der Formel
  
  in welcher Ph für Phenyl steht und R⁷ für Wasserstoff oder Alkyl steht, in Gegenwart einer Base sowie in Gegenwart eines Verdünnungsmittels umsetzt, oder γ) mit Diisobutyl-aluminiumhydrid in Gegenwart von wässriger Ammoniumchlorid-Lösung sowie in Gegenwart eines organischen Verdünnungsmittels umsetzt, oder mit Natriumborhydrid in Gegenwart eines Verdünnungsmittels umsetzt, und gegebenenfalls die dabei entstehenden Pyrazolopyrimidine der Formel
  
  in welcher R¹, R², R³, R⁷ und Hal die oben angegebenen Bedeutungen haben, mit Alkylierungsmitteln der Formel R⁸-X³ (VII)in welcher R⁸ für Alkyl steht und X³ für Chlor, Brom, Iod oder den Rest R⁸O-SO₂-O- steht,

gegebenenfalls in Gegenwart einer Base und in Gegenwart eines Verdünnungsmittels umsetzt.Furthermore, it has been found that pyrazolopyrimidines of the formula (I) can be prepared by

• a) halo-pyrazolopyrimidines of the formula
  
  in which R ³ and Hal have the meanings given above, X ^{1 is} halogen, cyano, nitro, alkyl, haloalkyl, cycloalkyl, thiocarbamoyl, alkoxycarbonyl, alkylcarbonyl, alkylthio, alkylsulfinyl, alkylsulfonyl or alkylaminocarbonyl and Y ^{1 is} halogen, with amines the formula
  
  in which R ¹ and R ^{2 have} the meanings given above, if appropriate in the presence of a diluent, if appropriate in the presence of a catalyst and optionally in the presence of an acid acceptor, or
• b) pyrazolopyrimidines of the formula
  
  in which R ¹ , R ² , R ³ and Hal have the meanings given above, either α) with diisobutyl aluminum hydride in the presence of aqueous ammonium chloride solution and in the presence of an organic diluent, or β) with Grignard compounds of the formula R ⁴ -Mg-X ² (IV) in which R ^{4 is} alkyl and X ^{2 is} chlorine or bromine, in the presence of a diluent and optionally in the presence of a catalyst, or
• c) pyrazolopyrimidines of the formula
  
  in which R ¹ , R ² , R ³ and Hal have the meanings given above and R ^{5 is} hydrogen or alkyl, either α) with amino compounds of the formula H ₂ N-OR ⁶ (V) in which R ^{6 is} hydrogen or alkyl, in the presence of a diluent and optionally in the presence of a catalyst, wherein the amino compounds of the formula (V) are also used in the form of their acid addition salts can, or β) with triphenylphosphonium salts of the formula
  
  in which Ph is phenyl and R ^{7 is} hydrogen or alkyl, in the presence of a base and in the presence of a diluent, or γ) with diisobutyl aluminum hydride in the presence of aqueous ammonium chloride solution and in the presence of an organic diluent, or with Sodium borohydride in the presence of a diluent, and optionally the resulting pyrazolopyrimidines of the formula
  
  in which R ¹ , R ² , R ³ , R ⁷ and Hal have the meanings given above, with alkylating agents of the formula R ⁸ -X ³ (VII) in which R ^{8 is} alkyl and X ^{3 is} chlorine, bromine, iodine or the radical R ⁸ O-SO ₂ -O-,

if appropriate in the presence of a base and in the presence of a diluent.

Finally became found that the pyrazolopyrimidines of the formula (I) are very good to combat undesirable Microorganisms are suitable. Above all, they show a strong fungicidal Efficacy and can be both in crop protection and in the Use material protection.

Surprisingly have the pyrazolopyrimidines of the invention of the formula (I) a significantly better microbicidal activity than the most constitutionally similar, previously known substances of the same direction of action.

heterocyclyl in the present case stands for saturated or unsaturated, aromatic or non-aromatic, annular compounds having 3 to 8 ring members, in which at least one ring member is a heteroatom is therefore an atom different from carbon. Contains the ring several heteroatoms, so can these may be the same or different. Heteroatoms are preferably oxygen, Nitrogen or sulfur. contains the ring has several oxygen atoms, so they are not directly adjacent. Optionally, the annular form Compounds with other carbocyclic or heterocyclic, fused or bridged rings together a polycyclic ring system. Preference is mono- or Bicyclic ring systems, in particular mono- or bicyclic, aromatic Ring systems.

The triazolopyrimidines according to the invention are generally defined by the formula (I). Preference is given to those substances of the formula (I) in which
R ^{1 is} alkyl having 1 to 6 carbon atoms, which may be monosubstituted, monosubstituted or differently substituted by halogen, cyano, hydroxy, alkoxy having 1 to 4 carbon atoms and / or cycloalkyl with 3 to 6 carbon atoms, or
R ^{1 is} alkenyl of 2 to 6 carbon atoms which may be monosubstituted to trisubstituted, identically or differently substituted by halogen, cyano, hydroxy, alkoxy of 1 to 4 carbon atoms and / or cycloalkyl of 3 to 6 carbon atoms, or
R ^{1 is} alkynyl of 3 to 6 carbon atoms, which may be monosubstituted to trisubstituted, identically or differently substituted by halogen, cyano, alkoxy of 1 to 4 carbon atoms and / or cycloalkyl of 3 to 6 carbon atoms, or
R ^{1 is} cycloalkyl of 3 to 6 carbon atoms which may be monosubstituted to trisubstituted, identically or differently substituted by halogen and / or alkyl of 1 to 4 carbon atoms, or
R ^{1 is} saturated or unsaturated heterocyclyl having 5 or 6 ring members and 1 to 3 heteroatoms, such as nitrogen, oxygen and / or sulfur, where the heterocyclyl may be monosubstituted or disubstituted by halogen, alkyl having 1 to 4 carbon atoms, cyano, Nitro and / or cycloalkyl having 3 to 6 carbon atoms,
R ^{2 is} hydrogen or alkyl of 1 to 4 carbon atoms, or
R ¹ and R ² together with the nitrogen atom to which they are attached represent a saturated or unsaturated heterocyclic ring having 3 to 6 ring members, which heterocycle may contain another nitrogen, oxygen or sulfur atom as ring member and wherein the heterocycle may be substituted up to three times by fluorine, chlorine, bromine, alkyl having 1 to 4 carbon atoms and / or halogenoalkyl having 1 to 4 carbon atoms and 1 to 9 fluorine and / or chlorine atoms,
R ^{3 is} saturated or unsaturated heterocyclyl having 5 or 6 ring members and 1 to 4 heteroatoms, such as oxygen, nitrogen and / or sulfur, wherein the heterocyclyl can be monosubstituted, monosubstituted or differently substituted by one to four times
Fluorine, chlorine, bromine, cyano, nitro, alkyl, alkoxy, hydroximinoalkyl or alkoximinoalkyl having in each case 1 to 3 carbon atoms per alkyl part,
Haloalkyl or haloalkoxy having in each case 1 to 3 carbon atoms and 1 to 7 halogen atoms,
Hal is fluorine, chlorine or bromine and
X is cyano, fluorine, chlorine, bromine, iodine, nitro, formyl, haloalkyl of 1 to 4 carbon atoms and 1 to 9 fluorine, chlorine and / or bromine atoms, alkyl of 1 to 4 carbon atoms, alkenyl of 2 to 4 carbon atoms, hydroxyalkyl with 1 to 4 carbon atoms, alkoxyalkyl of 1 to 4 carbon atoms in the alkoxy moiety and 1 to 4 carbon atoms in the alkyl moiety, cycloalkyl of 3 to 6 carbon atoms, thiocarbamoyl, alkoxycarbonyl of 1 to 4 carbon atoms in the alkoxy moiety, alkylcarbonyl of 1 to 4 carbon atoms in the alkyl moiety, hydroximinoalkyl with 1 to 4 carbon atoms in the alkyl part, alkoximinoalkyl with 1 to 4 carbon atoms in the alkoxy part and 1 to 4 carbon atoms in the alkyl part, alkylthio with 1 to 4 carbon atoms, alkylsulfinyl with 1 to 4 carbon atoms, alkylsulfonyl with 1 to 4 carbon atoms or for alkylaminocarbonyl with 1 to 4 carbon atoms in the alkyl moiety.

wobei # die Anknüpfungsstelle markiert,
R² für Wasserstoff, Methyl, Ethyl oder Propyl steht, oder
R¹ und R² gemeinsam mit dem Stickstoffatom, an das sie gebunden sind, für Pyrrolidinyl, Piperidinyl, Morpholinyl, Thiomorpholinyl, Piperazinyl, 3,6-Dihydro-1(2H)-piperidinyl oder Tetrahydro-1(2H)-pyridazinyl stehen, wobei diese Reste durch 1 bis 3 Fluoratome, 1 bis 3 Methylgruppen und/oder Trifluormethyl substituiert sein können,
oder
R¹ und R² gemeinsam mit dem Stickstoffatom, an das sie gebunden sind, für einen Rest der Formel

worin
R' für Wasserstoff oder Methyl steht,
R'' für Methyl, Ethyl, Fluor, Chlor oder Trifluormethyl steht,
m für die Zahlen 0, 1, 2 oder 3 steht, wobei R'' für gleiche oder verschiedene Reste steht, wenn m für 2 oder 3 steht,
R''' für Methyl, Ethyl, Fluor, Chlor oder Trifluormethyl steht
und
n für die Zahlen 0, 1, 2 oder 3 steht, wobei R''' für gleiche oder verschiedene Reste steht, wenn n für 2 oder 3 steht,
R³ für Pyridyl steht, das in 2- oder 4-Stellung verknüpft ist und einfach bis vierfach, gleichartig oder verschieden substituiert sein kann durch Fluor, Chlor, Brom, Cyano, Nitro, Methyl, Ethyl, Methoxy, Methylthio, Hydroximinomethyl, Hydroximinoethyl, Methoximinomethyl, Methoximinoethyl und/oder Trifluormethyl, oder
R³ für Pyrimidyl steht, das in 2- oder 4-Stellung verknüpft ist und einfach bis dreifach, gleichartig oder verschieden substituiert sein kann durch Fluor, Chlor, Brom, Cyano, Nitro, Methyl, Ethyl, Methoxy, Methylthio, Hydroximinomethyl, Hydroximinoethyl, Methoximinomethyl, Methoximinoethyl und/oder Trifluormethyl, oder
R³ für Thienyl steht, das in 2- oder 3-Stellung verknüpft ist und einfach bis dreifach, gleichartig oder verschieden substituiert sein kann durch Fluor, Chlor, Brom, Cyano, Nitro, Methyl, Ethyl, Methoxy, Methylthio, Hydroximinomethyl, Hydroximinoethyl, Methoximinimethyl, Methoximinoethyl und/oder Trifluormethyl, oder
R³ für Thiazolyl steht, das in 2-, 4- oder 5-Stellung verknüpft ist und einfach bis zweifach, gleichartig oder verschieden substituiert sein kann durch Fluor, Chlor, Brom, Cyano, Nitro, Methyl, Ethyl, Methoxy, Methylthio, Hydroximinomethyl, Hydroximinoethyl, Methoximinimethyl, Methoximinoethyl und/oder Trifluormethyl,
Hal für Fluor oder Chlor steht und
X für Cyano, Fluor, Chlor, Brom, Jod, Nitro, Formyl, Trifluormethyl, Difluormethyl, Methyl, Ethyl, Cyclopropyl, Thiocarbamoyl, Methoxycarbonyl, Methylcarbonyl, Ethylcarbonyl, Hydroximinomethyl, Methoximinomethyl, Methylthio, Methylsulfinyl Methylsulfonyl, Methylaminocarbonyl, Ethenyl, Propenyl, Hydroxymethyl, Hydroxyeth-1-yl, Methoxymethyl, Ethoxymethyl oder 1-Methoxy-ethyl steht.Particularly preferred are those pyrazolopyrimidines of the formula (I) in which
R ^{1 is} a radical of the formula

where # marks the point of attachment,
R ^{2 is} hydrogen, methyl, ethyl or propyl, or
R ¹ and R ² together with the nitrogen atom to which they are attached represent pyrrolidinyl, piperidinyl, morpholinyl, thiomorpholinyl, piperazinyl, 3,6-dihydro-1 (2H) -piperidinyl or tetrahydro-1 (2H) -pyridazinyl, these radicals may be substituted by 1 to 3 fluorine atoms, 1 to 3 methyl groups and / or trifluoromethyl,
or
R ¹ and R ² together with the nitrogen atom to which they are attached, represent a radical of the formula

wherein
R 'is hydrogen or methyl,
R '' is methyl, ethyl, fluorine, chlorine or trifluoromethyl,
m is the numbers 0, 1, 2 or 3, where R '' is identical or different radicals, when m is 2 or 3,
R '''is methyl, ethyl, fluorine, chlorine or trifluoromethyl
and
n is the numbers 0, 1, 2 or 3, where R '''is identical or different radicals, when n is 2 or 3,
R ^{3 is} pyridyl which is linked in the 2- or 4-position and may be monosubstituted, monosubstituted or differently substituted by fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, methoxy, methylthio, hydroximinomethyl, hydroximinoethyl, Methoximinomethyl, methoximinoethyl and / or trifluoromethyl, or
R ^{3 is} pyrimidyl which is linked in the 2- or 4-position and may be monosubstituted to trisubstituted by identical or different substituents by fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, methoxy, methylthio, hydroximinomethyl, hydroximinoethyl, Methoximinomethyl, methoximinoethyl and / or trifluoromethyl, or
R ^{3 is} thienyl which is linked in the 2- or 3-position and monosubstituted to trisubstituted, identical or different which may be substituted by fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, methoxy, methylthio, hydroximinomethyl, hydroximinoethyl, methoximinimethyl, methoximinoethyl and / or trifluoromethyl, or
R ^{3 is} thiazolyl which is linked in the 2-, 4- or 5-position and may be mono- to disubstituted by identical or different substituents by fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, methoxy, methylthio, hydroximinomethyl , Hydroximinoethyl, methoximinimethyl, methoximinoethyl and / or trifluoromethyl,
Hal is fluorine or chlorine and
X is cyano, fluoro, chloro, bromo, iodo, nitro, formyl, trifluoromethyl, difluoromethyl, methyl, ethyl, cyclopropyl, thiocarbamoyl, methoxycarbonyl, methylcarbonyl, ethylcarbonyl, hydroximinomethyl, methoximinomethyl, methylthio, methylsulfinyl, methylsulfonyl, methylaminocarbonyl, ethenyl, propenyl, hydroxymethyl , Hydroxyeth-1-yl, methoxymethyl, ethoxymethyl or 1-methoxy-ethyl.

The previously mentioned residue definitions can be used among each other in any Way combined. Furthermore can individual definitions are omitted.

used 3-Cyano-5,7-dichloro-6- (3-trifluoromethylpyridin-2-yl) -pyrazolo [1,5-a] pyrimidine and 2,2,2-trifluoroisopropylamine as starting materials, so can the course of the process according to the invention (a) are illustrated by the following formula scheme.

used 3-cyano-5-chloro-6- (3-trifluoromethylpyridin-2-yl) -7- (2,2,2-trifluoroisopropylamino) pyrazolo [1,5-a] pyrimidine as starting material and di-isobutyl aluminum hydride as reaction component, Thus, the course of the process according to the invention (b, variant a) are illustrated by the following formula scheme.

used 3-cyano-5-chloro-6- (3-trifluoromethylpyridin-2-yl) -7- (2,2,2-trifluoroisopropylamino) pyrazolo [1,5-a] pyrimidine as starting material and methyl magnesium bromide as reaction component, Thus, the course of the process according to the invention (b, variant β) by the the following formula schema are shown.

used 3-Formyl-5-chloro-6- (3-trifluoromethyl-pyridin-2-yl) -7- (2,2,2-trifluoroisopropylamino) -pyrazolo [1,5a] pyrimidine and methoxyamine hydrochloride as starting materials, so may the course the method according to the invention (c, variant α) are illustrated by the following equation scheme.

used 3-methylcarbonyl-5-chloro-6- (3-trifluoromethyl-pyridin-2-yl) -7- (2,2,2-trifluoroisopropylamino) -pyrazolo [1,5a] pyrimidine as starting material and triphenylmethylphosphonium bromide as reaction component, Thus, the course of the process according to the invention (c, variant β) by the the following formula schema are shown.

used 3-methylcarbonyl-5-chloro-6- (3-trifluoromethyl-pyridin-2-yl) -7- (2,2,2-trifluoroisopropylamino) -pyrazolo [1,5a] pyrimidine as starting material, diisobutylaluminum hydride as the reaction component in the first stage and methyl iodide as the reaction component in the second stage, so can the course of the process according to the invention (c, variant γ) are illustrated by the following equation scheme.

For carrying out the process (a) required as starting materials Halogenpyrazolopyrimidine are generally defined by the formula (II). In this formula (II), R ³ and Hal preferably have those meanings which have already been mentioned as preferred for these radicals in connection with the description of the compounds of the formula (I) according to the invention.

Y ¹ is preferably fluorine, chlorine or bromine, more preferably fluorine or chlorine.

X ¹ preferably represents cyano, fluorine, chlorine, bromine, iodine, nitro, haloalkyl having 1 to 4 carbon atoms and 1 to 9 fluorine, chlorine and / or bromine atoms, alkyl having 1 to 4 carbon atoms, cycloalkyl having 3 to 6 carbon atoms , Thiocarbamoyl, alkoxycarbonyl having 1 to 4 carbon atoms in the alkoxy part, alkylcarbonyl having 1 to 4 carbon atoms in the alkyl part, alkylthio having 1 to 4 carbon atoms, alkylsulfinyl having 1 to 4 carbon atoms, alkylsulfonyl having 1 to 4 carbon atoms or alkylaminocarbonyl having 1 to 4 carbon atoms in the alkyl moiety.

X ¹ particularly preferably represents cyano, fluorine, chlorine, bromine, iodine, nitro, trifluoromethyl, difluoromethyl, methyl, ethyl, cyclopropyl, thiocarbamoyl, methoxycarbonyl, methylcarbonyl, methylthio, ethylcarbonyl, methylsulfinyl, methylsulfonyl or methylaminocarbonyl.

The Halo-pyrazolopyrimidines of the formula (II) are novel. These too Substances are suitable for combat of unwanted Microorganisms.

• d) Hydroxy-pyrazolopyrimidine der Formel
  
  in welcher R³ und X¹ die oben angegebenen Bedeutungen haben, mit Halogenierungsmitteln, gegebenenfalls in Gegenwart eines Verdünnungsmittels umsetzt.

The halogenopyrazolopyrimidines of the formula (II) can be prepared
by

• d) hydroxy-pyrazolopyrimidines of the formula
  
  in which R ³ and X ^{1 have} the meanings given above, with halogenating agents, if appropriate in the presence of a diluent.

If 3-cyano-6- (3-trifluoromethyl-pyridin-2-yl) -pyrazolo [1,5-a] pyrimidine-5,7-diol is used as starting material and phosphorus oxychloride mixed with phosphorus pentachloride as halogenating agent, the course of the process (d) according to the invention by the following equation Scheme illustrates who the.

The hydroxy-pyrazolopyrimidines required as starting materials for carrying out the process (d) according to the invention are generally defined by the formula (VIII). In this formula, R ³ and X ¹ preferably have those meanings which have already been mentioned as preferred in connection with the description of the compounds of the formulas (I) and (II) according to the invention.

• (e) Heterocyclylmalonester der Formel
  
  in welcher R³ die oben angegebene Bedeutung hat und R⁹ für Alkyl mit 1 bis 4 Kohlenstoffatomen steht, mit Aminopyrazolen der Formel
  
  in welcher X¹ die oben angegebene Bedeutung hat, gegebenenfalls in Gegenwart eines Verdünnungsmittels und gegebenenfalls in Gegenwart eines Säurebindemittels umsetzt.

Also, the hydroxy-pyrazolopyrimidines of the formula (VIII) are not yet known. They can be produced by one

• (e) heterocyclylmalonic esters of the formula
  
  in which R ^{3 has} the abovementioned meaning and R ^{9 is} alkyl having 1 to 4 carbon atoms, with aminopyrazoles of the formula
  
  in which X ^{1 has} the abovementioned meaning, if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder.

used 2- (3-trifluoromethyl-2-pyridyl) -malonate and 3-amino-4-cyano-pyrazole as starting materials, so can the course of the process according to the invention (e) be illustrated by the following formula scheme.

The heterocyclylmalonic esters required as starting materials for carrying out the process (e) according to the invention are generally defined by the formula (IX). In this formula, R ³ preferably has those meanings which have already been mentioned as preferred in connection with the description of the substances of the formula (I) according to the invention for this radical. R ⁹ is preferably methyl or ethyl.

The heterocyclylmalonic esters of the formula (IX) are known in some cases (cf. DE 38 20 538-A WO 01-11965 and WO 99-32464).

in welcher
R⁹ die oben angegebene Bedeutung hat und
R¹⁰ für Halogen oder Halogenalkyl steht.New are pyridylmalonic esters of the formula

in which
R ^{9 has} the abovementioned meaning and
R ^{10 is} halogen or haloalkyl.

in welcher
R9 die oben angegebene Bedeutung hat,
R¹¹ für Halogen oder Halogenalkyl steht, und
R¹² und R¹³ unabhängig voneinander für Wasserstoff, Fluor, Chlor, Brom, Methyl, Ethyl oder Methoxy stehen.Also new are pyrimidylmalonic esters of the formula

in which
R9 has the meaning given above,
R ^{11 is} halogen or haloalkyl, and
R ¹² and R ¹³ independently represent hydrogen, fluorine, chlorine, bromine, methyl, ethyl or methoxy.

• (f) Halogenpyridine der Formel
  
  in welcher R¹⁰ die oben angegebene Bedeutung hat und Y² für Halogen steht, mit Malonestern der Formel
  
  in welcher R⁹ die oben angegebene Bedeutung hat, gegebenenfalls in Gegenwart eines Verdünnungsmittels, gegebenenfalls in Gegenwart eines Kupfersalzes und gegebenenfalls in Gegenwart eines Säureakzeptors umsetzt.

The Pyridylmalonester of formula (IX-a) can be prepared by

• (f) halopyridines of the formula
  
  in which R ^{10 has} the abovementioned meaning and Y ^{2 is} halogen, with malonic esters of the formula
  
  in which R ^{9 has} the abovementioned meaning, if appropriate in the presence of a diluent, if appropriate in the presence of a copper salt and if appropriate in the presence of an acid acceptor.

used 2-chloro-3-trifluoromethylpyridine and dimethyl malonate as starting materials, Thus, the course of the process (f) by the the following formula schema are shown.

The halopyridines required as starting materials for carrying out the process (f) according to the invention are generally defined by the formula (XI). In this formula, R ^{10 is} preferably fluorine, chlorine or trifluoromethyl. Y ² is preferably chlorine or bromine.

The Halogenopyridines of the formula (XI) are known synthetic chemicals.

The to carry out the method according to the invention (f) further required as starting materials malonic acid ester of formula (XII) are also known synthetic chemicals.

• (g) Halogenpyrimidine der Formel
  
  in welcher R¹¹, R¹² und R¹³ die oben angegebenen Bedeutungen haben und Y³ für Halogen steht, mit Malonestern der Formel
  
  in welcher R⁹ die oben angegebene Bedeutung hat, gegebenenfalls in Gegenwart eines Verdünnungsmittels, gegebenenfalls in Gegenwart eines Kupfersalzes und gegebenenfalls in Gegenwart eines Säureakzeptors umsetzt.

The Pyrimidylmalonester of formula (IX-b) can be prepared by

• (g) halopyrimidines of the formula
  
  in which R ¹¹ , R ¹² and R ^{13 have} the meanings given above and Y ^{3 is} halogen, with malonic esters of the formula
  
  in which R ^{9 has} the abovementioned meaning, if appropriate in the presence of a diluent, if appropriate in the presence of a copper salt and if appropriate in the presence of an acid acceptor.

used 4,5-dichloropyrimidine and dimethyl malonate as starting materials, Thus, the course of the process (g) by the the following formula schema are shown.

The halopyrimidines required as starting materials for carrying out the process (g) according to the invention are generally defined by the formula (XIII). In this formula, R ^{11 is} preferably fluorine, chlorine or trifluoromethyl. R ¹² and R ¹³ are also preferably independently of one another hydrogen, fluorine, chlorine, bromine, methyl, ethyl or methoxy. Y ³ is preferably chlorine or bromine.

The Halogenopyrimidines of the formula (XIII) are known and can after known methods (see J. Chem. Soc. 1955, 3478, 3481).

The aminopyrazoles required for carrying out the process (e) according to the invention as reaction components are generally defined by the formula (X). In this formula, X ¹ preferably has the meanings which have already been mentioned as preferred in connection with the description of the substances of the formula (II) according to the invention for this radical.

The Aminopyrazoles of the formula (X) are known or can be prepared by known methods getting produced.

When Halogenating agents are all used in the practice of process (d) for the Replacement of hydroxyl groups by halogen customary components into consideration. Preferably usable are phosphorus trichloride, phosphorus tribromide, Phosphorus pentachloride, phosphorus oxychloride, thionyl chloride, thionyl bromide or their mixtures. The corresponding fluoro compounds of the formula (II) can be prepared from the chlorine or bromine compounds by reaction make with potassium fluoride.

The mentioned halogenating agents are known.

The amines furthermore required for carrying out the process (a) according to the invention as starting materials are generally defined by the formula (III). In this formula, R ¹ and R ² preferably have those meanings which have already been mentioned as preferred in connection with the description of the compounds of the formula (I) according to the invention for R ¹ and R ² .

The Amines of the formula (III) are known or can be known by known Establish methods.

When thinner come in the implementation the method according to the invention (a) all usual inert organic solvents into consideration. Preferably usable are halogenated hydrocarbons, such as chlorobenzene, Dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, dichloroethane or trichloroethane; Ethers, such as diethyl ether, diisopropyl ether, methyl t-butyl ether, methyl t-amyl ether, Dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane or anisole; nitrites, such as acetonitrile, propionitrile, n- or i-butyronitrile or benzonitrile; Amides, such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylformanilide, N-methylpyrrolidone or hexamethylphosphoric triamide; Esters such as methyl acetate or ethyl acetate; Sulfoxides, such as dimethylsulfoxide; Sulfones, such as sulfolane.

When Acid acceptors come in the implementation the method according to the invention (a) all for such Implementations usual inorganic or organic bases in question. Preferably usable Alkaline earth metal or alkali metal hydrides, hydroxides, amides, alkoxides, acetates, carbonates or bicarbonates, such as Sodium hydride, sodium amide, lithium diisopropylamide, sodium methoxide, sodium ethoxide, Potassium tert-butoxide, sodium hydroxide, potassium hydroxide, sodium acetate, Potassium acetate, calcium acetate, sodium carbonate, potassium carbonate, potassium bicarbonate and sodium bicarbonate, and also ammonium compounds such as ammonium hydroxide, ammonium acetate and ammonium carbonate, as well as tertiary amines, such as trimethylamine, triethylamine, tributylamine, N, N-dimethylaniline, N, N-dimethylbenzylamine, pyridine, N-methylpiperidine, N-methylmorpholine, N, N-dimethylaminopyridine, diazabicyclooctane (DABCO), diazabicyclononene (DBN) or diazabicycloundecene (DBU).

When Catalysts come in carrying out the method according to the invention (a) all for Such reactions usual Reaction accelerator into consideration.

Preferably usable are fluorides such as sodium fluoride, potassium fluoride or Ammonium fluoride.

The Reaction temperatures can during execution the method according to the invention (a) in a wider area be varied. In general, one works at temperatures between 0 ° C and 150 ° C, preferably at temperatures between 0 ° C and 80 ° C.

at the implementation the method according to the invention (A) is used to 1 mol of halogen-pyrazolo-pyrimidine of the formula (II) is generally 0.5 to 10 mol, preferably 0.8 to 2 mol Amine of formula (III). The workup is carried out according to customary Methods.

The Py required as starting materials in carrying out the process (b) according to the invention Razolopyrimidines are generally defined by the formula (Ia). In this formula, R ¹ , R ² , R ³ and Hal preferably have those meanings which have already been mentioned as preferred in connection with the description of the substances of the formula (I) according to the invention for these radicals.

at the pyrazolopyrimidines of the formula (Ia) are substances according to the invention, which is the method according to the invention (a) make.

When thinner come in the implementation the method according to the invention (b, variant α) all usual inert, organic solvents in question. Preferably usable are aliphatic or aromatic, optionally halogenated Hydrocarbons, such as toluene, dichloromethane, chloroform or carbon tetrachloride.

The Reaction temperatures can during execution the method according to the invention (b, variant α) be varied within a certain range. In general one works at temperatures between -80 ° C and + 20 ° C, preferably between -60 ° C and + 10 ° C.

at the implementation the method according to the invention (b, variant α) it is based on 1 mol of pyrazolopyrimidine of the formula (Ia) in general an equivalent Amount or even a surplus, preferably 1.1 to 1.2 moles of di-isobutylaluminum hydride and adds subsequently a surplus at watery Ammonium chloride solution added. The workup is carried out by conventional methods. In general moves one in such a way that one acidifies the reaction mixture, the organic phase separates, the aqueous Phase with a water-immiscible organic solvent extracted, the combined organic phases were washed, dried and concentrated Pressure narrows.

The Grignard compounds required as reaction components in carrying out the process (b, variant β) according to the invention are generally defined by the formula (IV). In this formula, R ^{4 is} preferably alkyl having 1 to 4 carbon atoms, particularly preferably methyl or ethyl. X ² is preferably bromine.

When Catalysts come in carrying out the method according to the invention (b, variant β) all for such Grignard reactions usual Reaction accelerator into consideration. For example, be mentioned Potassium iodide and iodine.

When thinner come in the implementation the inventive method (b, variant β) all for such reactions usual, inert organic solvents in question. Preferably usable are ethers, such as diethyl ether, dioxane or tetrahydrofuran, also aromatic Hydrocarbons, such as toluene, and also mixtures of ethers and aromatic hydrocarbons, such as toluene / tetrahydrofuran.

The Reaction temperatures can during execution the method according to the invention (b, variant β) be varied in a particular area. In general works at temperatures between -20 ° C and + 100 ° C, preferably between 0 ° C and 80 ° C.

at the implementation the method according to the invention (b, variant β) it is based on 1 mol of pyrazolopyrimidine of the formula (Ia) in general 2 to 3 moles of Grignard compound of formula (IV). Subsequently, will an aqueous one Work-up according to usual Methods performed.

The pyrazolopyrimidines required as starting materials in carrying out the process (c) according to the invention are generally defined by the formula (Ib). In this formula, R ¹ , R ² , R ³ and Hal preferably have those meanings which have already been mentioned as preferred in connection with the description of the substances of the formula (I) according to the invention for these radicals. R ⁵ is preferably hydrogen or alkyl of 1 to 4 carbon atoms, more preferably hydrogen, methyl or ethyl.

at the pyrazolopyrimidines of the formula (Ib) are substances according to the invention, which is the method according to the invention (b).

The amino compounds required as reaction components in carrying out the process (c, variant .alpha.) According to the invention are generally defined by the formula (V). In this formula, R ^{6 is} preferably hydrogen or alkyl of 1 to 4 carbon atoms, more preferably hydrogen, methyl or ethyl.

When Reaction components also come acid addition salts, preferably Hydrogen chloride addition salts of amino compounds of the formula (V).

Either the amino compounds of the formula (V) and also their acid addition salts are known or can be prepared by known methods.

When thinner come in the implementation the method according to the invention (c, variant α) all usual inert, organic solvents in question. Preferably usable are alcohols, such as methanol, ethanol, n-propanol or isopropanol.

Suitable catalysts in carrying out the process (c, variant α) are all customary for such reactions reaction accelerator into consideration. Preferably used are acidic or basic catalysts, for example under the name Amberlyst A-21 ^® which is available commercially, weakly basic ion exchanger.

The Reaction temperatures can during execution the method according to the invention (c, variant α) be varied within a certain range. In general one works at temperatures between 0 ° C and 80 ° C, preferably between 10 ° C and 60 ° C.

at the implementation the method according to the invention (c, variant α) it is based on 1 mol of pyrazolopyrimidine of the formula (Ib) in general an equivalent Quantity or surplus, preferably between 1.1 and 1.5 moles of amino compound of formula (V) or a Acid addition salt one of them. The workup is carried out by conventional methods. In general if you proceed so that you filtered the reaction mixture optionally, then narrow and clean.

When carrying out the process (c, variant β) required as reaction components Triphenylphosphonium salts are generally defined by the formula (VI). In this formula, Ph is phenyl. R ⁷ is preferably hydrogen or alkyl of 1 to 4 carbon atoms, more preferably hydrogen, methyl or ethyl.

The Triphenylphosphonium salts of the formula (VI) are known or are allowed to produce by known methods.

When Bases come in the implementation the method according to the invention (c, variant β) all for such Wittig reactions usual Deprotonating agent into consideration. Preferably used is butyl-lithium.

When thinner come in the implementation the method according to the invention (c, variant β) all for such Wittig reactions usual organic solvents in question. Preferably usable are ethers, such as dioxane or tetrahydrofuran.

The Reaction temperatures can during execution the method according to the invention (c, variant β) be varied within a certain range. In general it works at temperatures between -78 ° C and + 30 ° C.

at the implementation the method according to the invention (c, variant β) is set to 1 mol of pyrazolopyrimidine of the formula (Ib) an equivalent Quantity or even a surplus Triphenylphosphonium salt of the formula (VI) and an equivalent Quantity or even a surplus at base. The workup is carried out by conventional methods.

In carrying out the process (c, variant γ) required as reactants alkylating agents are generally defined by the formula (VII). In this formula, R ^{8 is} preferably alkyl having 1 to 4 carbon atoms, more preferably methyl or ethyl. X ³ is preferably chlorine, bromine, iodine or the radical R ⁸ -O-SO ₂ -O-, wherein R ^{8 has} the meanings given above.

The Alkylating agents of the formula (VII) are known or can be produce by known methods.

If, in carrying out the process (c, variant γ) in the first stage, di-isobutylaluminum hydride is used as the reducing agent, then it is expedient to work under the condition tions that have already been mentioned in connection with the description of the method (b, variant α).

used one in the implementation the method according to the invention (c, variant γ) In the first stage sodium borohydride as a reducing agent, so used as a diluent in general, alcohols, preferably methanol, ethanol or isopropanol.

at the reduction with sodium borohydride can the reaction temperatures be varied within a certain range. In general one works at temperatures between 0 ° C and 70 ° C, preferably between 0 ° C and 50 ° C.

at the implementation the reduction with sodium borohydride is based on 1 mol, pyrazolopyrimidine the Formula (Ib) is an equivalent Quantity or even a surplus of sodium borohydride. The work-up is again according to usual Methods.

at the implementation the second stage of the process (c, variant γ) come as Bases all usual acid binder in question. Preferably used are alkali metal hydrides, alcoholates and carbonates, such as sodium hydride, sodium methoxide, potassium tert-butoxide, Sodium carbonate, potassium carbonate or lithium carbonate.

When thinner come in the implementation the second step of the process (c, variant γ) all customary, inert organic solvents into consideration. Preferably usable Ethers, such as dioxane or tetrahydrofuran, and also nitriles, such as acetonitrile.

The Temperatures can during execution the second stage of the process according to the invention (c, variant γ) within a larger area be varied. In general, one works at temperatures between 0 ° C and 100 ° C, preferably between 20 ° C and 80 ° C.

at the implementation the second stage of the process (c, variant γ) is set up 1 mol of pyrazolopyrimidine of the formula (Ic) in general 1 to 2 mol, preferably 1 to 1.5 mol of alkylating agent. The Workup is again by conventional methods.

When dilution Mitel come in the implementation the method according to the invention (d) all for such Halogenations usual Solvents in question. Preferably used are halogenated aliphatic or aromatic hydrocarbons, such as chlorobenzene. As a diluent however, the halogenating agent itself, e.g. phosphorus oxychloride or a mixture of halogenating agents.

The Temperatures can also in the implementation of the method (d) varies within a substantial range become. In general, one works at temperatures between 0 ° C and 150 ° C, preferably between 10 ° C and 120 ° C.

at the implementation of process (d) is hydroxy-pyrazolo-pyrimidine of the formula (VIII) generally with a surplus to halogenating agent. The workup is carried out according to customary Methods.

When thinner come in the implementation of the method (e) all for such reactions usual, inert organic solvents in question. Preference as usable are alcohols such as methanol, ethanol, n-propanol, i-propanol, n-butanol and tert-butanol.

When acid binder come in the implementation of the method (e) all for Such reactions usual inorganic and organic bases into consideration.

Preferably can be used tertiary Amines, such as tributylamine or pyridine. Excess amine used Can also be used as a diluent act.

The Temperatures can during execution of process (e) in a wider range be varied. In general, one works at temperatures between 20 ° C and 200 ° C, preferably between 50 ° C and 180 ° C.

In carrying out the process (e) is set Heterocyclylmalonester of formula (IX) and Ami nopyrazole of formula (X) generally in equivalent amounts. But it is also possible to use one or the other component in excess. The workup is carried out by conventional methods.

When thinner come in the implementation the invention. method (f) and (g) all usual, inert organic solvents in question. Preferably usable are halogenated hydrocarbons, such as chlorobenzene, Dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, dichloroethane or trichloroethane; Ethers, such as diethyl ether, diisopropyl ether, methyl t-butyl ether, methyl t-amyl ether, Dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane or anisole; Nitriles, such as acetonitrile, propionitrile, n- or i-butyronitrile or benzonitrile; Amides, such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylformanilide, N-methylpyrrolidone or hexamethylphosphoric triamide; Sulfoxides, such as dimethylsulfoxide; Sulfones, such as sulfolane; alcohols, such as methanol, ethanol, n- or i-propanol, n-, i-, sec- or tert-butanol, Ethanediol, propane-1,2-diol, ethoxyethanol, methoxyethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, their mixtures with water or pure water.

When Copper salts come in carrying out the method according to the invention (f) and (g) each usual Copper salts into consideration. Preferably usable are copper (I) chloride or copper (I) bromide.

When Acid acceptors come in the implementation the inventive method (f) and (g) all usual inorganic or organic bases in question. Preferably usable are alkaline earth metal or alkali metal hydrides, hydroxides, amides, alcoholates, acetates, carbonates or bicarbonates, such as Sodium hydride, sodium amide, lithium diisopropylamide, sodium methoxide, Sodium ethoxide, potassium tert-butoxide, sodium hydroxide, potassium hydroxide, Sodium acetate, potassium acetate, calcium acetate, sodium carbonate, potassium carbonate, Kaliumhydrogencarbonat and sodium bicarbonate and also ammonium compounds such as Ammonium hydroxide, ammonium acetate and ammonium carbonate, and tertiary amines, such as trimethylamine, triethylamine, tributylamine, N, N-dimethylaniline, N, N-dimethylbenzylamine, pyridine, N-methylpiperidine, N-methylmorpholine, N, N-dimethylaminopyridine, diazabicyclooctane (DABCO), diazabicyclononene (DBN) or diazabicycloundecene (DBU).

The Reaction temperatures can also in the implementation the inventive method (f) and (g) in a wider range be varied. In general, one works at temperatures between 0 ° C and 150 ° C, preferably at temperatures between 0 ° C and 80 ° C.

at the implementation the method according to the invention (f) is used for 1 mole of halopyridine of the formula (XI) in general 1 to 15 mol, preferably 1.3 to 8 mol of malonic ester of the formula (XII). The workup is carried out by conventional methods.

at the implementation the method according to the invention (g) is used for 1 mol of halopyrimidine of the formula (XIII) im Generally 1 to 15 moles, preferably 1.3 to 8 moles of malonic ester of the formula (XII). The work-up is again according to usual Methods.

The inventive method are generally carried out under atmospheric pressure. It is but also possible under increased Pressure to work.

The Inventive substances have a strong microbicidal action and can be used to combat undesirable Microorganisms, such as fungi and bacteria, in crop protection and be used in the protection of materials.

fungicides can plant protection be used to combat Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes and Deuteromycetes.

bactericidal can be used in crop protection to control Pseudomonadaceae, Rhizobiaceae, Enterobacteriaceae, Corynebacteriaceae and Streptomycetaceae deploy.

By way of example but not limitation, some pathogens of fungal and bacterial diseases, which fall under the above-enumerated generic terms, are named:
Xanthomonas species, such as Xanthomonas campestris pv. Oryzae;
Pseudomonas species, such as Pseudomonas syringae pv. Lachrymans;
Erwinia species, such as Erwinia amylovora;
Pythium species such as Pythium ultimum;
Phytophthora species, such as Phytophthora infestans;
Pseudoperonospora species, such as, for example, Pseudoperonospora humuli or Pseudoperonospora cubensis;
Plasmopara species, such as Plasmopara viticola;
Bremia species, such as Bremia lactucae;
Peronospora species such as Peronospora pisi or P. brassicae;
Erysiphe species, such as Erysiphe graminis;
Sphaerotheca species, such as Sphaerotheca fuliginea;
Podosphaera species, such as Podosphaera leucotricha;
Venturia species, such as Venturia inaequalis;
Pyrenophora species, such as, for example, Pyrenophora teres or P. graminea (conidia form: Drechslera, Syn: Helminthosporium);
Cochliobolus species, such as Cochliobolus sativus (conidia form: Drechslera, Syn: Helminthosporium);
Uromyces species, such as Uromyces appendiculatus;
Puccinia species, such as Puccinia recondita;
Sclerotinia species, such as Sclerotinia sclerotiorum;
Tilletia species, such as Tilletia caries;
Ustilago species such as Ustilago nuda or Ustilago avenge;
Pellicularia species, such as, for example, Pellicularia sasakii;
Pyricularia species, such as Pyricularia oryzae;
Fusarium species such as Fusarium culmorum;
Botrytis species, such as Botrytis cinerea;
Septoria species such as Septoria nodorum;
Leptosphaeria species, such as Leptosphaeria nodorum;
Cercospora species, such as Cercospora canescens;
Alternaria species, such as Alternaria brassicae;
Pseudocercosporella species, such as Pseudocercosporella herpotrichoides.

The active ingredients according to the invention also have a very good restorative Effect in plants. They are therefore suitable for mobilization plant's own defenses against infestation by unwanted Microorganisms.

Under plant-strengthening (resistance-inducing) substances are in the present context to understand such substances that are capable of the immune system of plants to stimulate so that the treated plants at subsequent inoculation with unwanted microorganisms extensive resistance unfold against these microorganisms.

Under undesirable Microorganisms in the present case are phytopathogenic fungi, To understand bacteria and viruses. The substances according to the invention can So be used to plants within a period of time after the treatment against the infestation by the mentioned pathogens to protect. The period within which protection is provided extends in the general from 1 to 10 days, preferably 1 to 7 days after Treatment of plants with the active ingredients.

The good plant tolerance the active ingredients in the fight of plant diseases necessary concentrations allows one Treatment of above-ground parts of plants, planting and seed, and the soil.

there can be the active compounds of the invention with particular success in combating cereal diseases, such as against Erysiphe species, diseases in wine, Fruit and vegetable cultivation, such as against Botrytis, Venturia, Sphaerotheca- and Podosphaera species, use.

The active ingredients according to the invention are also suitable for increasing crop yield. They are also less toxic and have good plant tolerance.

The active ingredients according to the invention can optionally in certain concentrations and application rates also as herbicides, for influencing plant growth, as well as for fight of animal pests be used. Where appropriate, they may also be considered as intermediate and precursors for use the synthesis of other drugs.

According to the invention, all plants and parts of plants can be treated. Being under plants understood here all plants and plant populations, such as desirable and undesirable wild plants or crops (including naturally occurring crops). Crop plants can be plants which can be obtained by conventional breeding and optimization methods or by biotechnological and genetic engineering methods or combinations of these methods, including the transgenic plants and including plant varieties which can or can not be estimated by plant variety protection rights. Plant parts are to be understood as meaning all aboveground and subterranean parts and organs of the plants, such as shoot, leaf, flower and root, examples of which include leaves, needles, stems, stems, flowers, fruiting bodies, fruits and seeds, and roots, tubers and rhizomes. The plant parts also include crops and vegetative and generative propagation material, such as cuttings, tubers, rhizomes, offshoots and seeds.

The Treatment according to the invention the plants and plant parts with the active ingredients are made directly or by affecting their environment, habitat or storage space the usual Treatment methods, e.g. by dipping, spraying, evaporating, misting, Sprinkle, spread and propagate material, in particular in seeds, further by single or multi-layer wrapping.

in the Material protection can be the substances of the invention for the protection of technical Materials against infestation and destruction by unwanted microorganisms deploy.

Under technical materials are non-living in the present context Understand materials for the use has been prepared in the art. For example can technical materials, by the active compounds according to the invention before microbial change or destruction protected adhesives, glues, paper and board, textiles, Leather, wood, paints and plastics, coolants and other materials that are infested by microorganisms or can be decomposed. As part of the protected Materials are also parts of production plants, such as cooling water circuits, called, which can be affected by the proliferation of microorganisms. As part of of the present invention are preferred as engineering materials Adhesives, glues, papers and cartons, leather, wood, paints, coolant and heat transfer fluids called, more preferably wood.

When Microorganisms that cause degradation or alteration of engineering materials can cause are for example bacteria, fungi, yeasts, algae and slime organisms called. The active compounds according to the invention preferably act against fungi, especially molds, wood-discolouring and wood-destroying fungi (Basidiomycetes) and against slime organisms and algae.

There may be mentioned, for example, microorganisms of the following genera:
Alternaria, such as Alternaria tenuis,
Aspergillus, such as Aspergillus niger,
Chaetomium, such as Chaetomium globosum,
Coniophora, like Coniophora puetana,
Lentinus, like Lentinus tigrinus,
Penicillium, such as Penicillium glaucum,
Polyporus, such as Polyporus versicolor,
Aureobasidium, such as Aureobasidium pullulans,
Sclerophoma, such as Sclerophoma pityophila,
Trichoderma, like Trichoderma viride,
Escherichia, like Escherichia coli,
Pseudomonas, such as Pseudomonas aeruginosa,
Staphylococcus, such as Staphylococcus aureus.

The Active ingredients can dependent on from their respective physical and / or chemical properties in the usual Formulations are transferred, like solutions, Emulsions, suspensions, powders, foams, pastes, granules, aerosols, Very fine encapsulation in polymeric substances and in encapsulants for seeds, as well as ULV cold and warm mist formulations.

These formulations are prepared in a known manner, for example by mixing the active compounds with extenders, ie liquid solvents, liquefied gases under pressure and / or solid carriers, optionally with the use of surface-active agents, ie emulsifiers and / or dispersants and / or foam-forming agents , In the case of using water as extender, for example, organic solvents can also be used as auxiliary solvents. As liquid Solvents are essentially in question: aromatics such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons such as cyclohexane or paraffins, eg petroleum fractions, alcohols such as butanol or glycol and their ethers and Esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide and dimethyl sulfoxide, and water. By liquefied gaseous diluents or carriers are meant those liquids which are gaseous at normal temperature and under normal pressure, for example aerosol propellants, such as halogenated hydrocarbons as well as butane, propane, nitrogen and carbon dioxide. Suitable solid carriers are: for example ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as finely divided silica, alumina and silicates. As solid carriers for granules are: for example, broken and fractionated natural rocks such as calcite, pumice, marble, sepiolite, dolomite and synthetic granules of inorganic and organic flours and granules of organic material such as sawdust, coconut shells, corn cobs and tobacco stalks. Suitable emulsifiers and / or foam-formers are: for example nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulfonates, alkyl sulfates, arylsulfonates and protein hydrolysates. Suitable dispersants are: for example lignin-sulphite liquors and methylcellulose.

It can in the formulations adhesives such as carboxymethylcellulose, natural and synthetic powdery, granular or latex-shaped Polymers such as gum arabic, polyvinyl alcohol, Polyvinyl acetate, as well as natural Phospholipids, such as cephalins and lecithins, and synthetic phospholipids. Further Additives can mineral and vegetable oils be.

It can Dyes such as inorganic pigments, e.g. Iron oxide, titanium oxide, Ferrocyan blue and organic dyes such as alizarin, azo and Metal phthalocyanine dyes and trace nutrients, such as salts of iron, Manganese, boron, copper, cobalt, molybdenum and zinc are used.

The Formulations generally contain between 0.1 and 95 weight percent Active ingredient, preferably between 0.5 and 90%.

The active ingredients according to the invention can as such or in their formulations also in mixture with known Fungicides, bactericides, acaricides, nematicides or insecticides used, e.g. to widen the spectrum of action or to prevent development of resistance. In many cases you get it synergistic effects, i. the effectiveness of the mixture is greater than the effectiveness of the individual components.

When Mischpartner come, for example, the following compounds in question:

fungicides:

• 2-phenylphenol; 8-hydroxyquinoline sulfate;
• Acibenzolar-S-methyl; aldimorph; amidoflumet; Ampropylfos; Ampropylfos-potassium; andoprim; anilazine; azaconazole; azoxystrobin;
• benalaxyl; Benodanil; benomyl; Benthiavalicarb-isopropyl; Benzamacril; Benzamacril-isobutyl; bilanafos; binapacryl; biphenyl; bitertanol; Blasticidin-S; bromuconazole; Bupirimate; Buthiobate; butylamine;
• Calcium polysulfides; capsimycin; captafol; captan; carbendazim; carboxin; carpropamid; carvones; chinomethionat; Chlobenthiazone; Chlorfenazole; chloroneb; chlorothalonil; chlozolinate; Clozylacon; cyazofamid; cyflufenamid; cymoxanil; cyproconazole; cyprodinil; cyprofuram;
• Dagger G; debacarb; dichlofluanid; dichlone; dichlorophen; diclocymet; Diclomezine; dicloran; diethofencarb; Difenoconazole; diflumetorim; dimethirimol; dimethomorph; dimoxystrobin; diniconazole; Diniconazole-M; dinocap; diphenylamines; Dipyrithione; Ditalimfos; dithianon; dodine; Drazoxolon;
• edifenphos; epoxiconazole; ethaboxam; ethirimol; etridiazole;
• famoxadone; fenamidone; Fenapanil; fenarimol; Fenbuconazole; fenfuram; fenhexamid; Fenitropan; fenoxanil; fenpiclonil; fenpropidin; fenpropimorph; ferbam; fluazinam; Flubenzimine; fludioxonil; flumetover; flumorph; fluoromides; fluoxastrobin; fluquinconazole; flurprimidol; flusilazole; flusulfamide; flutolanil; flutriafol; folpet; Fosetyl-Al; Fosetyl-sodium; fuberidazole; furalaxyl; furametpyr; Furcarbanil; Furmecyclox;
• guazatine;
• Hexachlorobenzene; hexaconazole; hymexazol;
• imazalil; Imibenconazole; Iminoctadine triacetate; iminoctadine tris (albesil; iodocarb; ipconazole; Iprobenfos; iprodione; iprovalicarb; Irumamycin; isoprothiolane; Isovaledione;
• kasugamycin; Kresoxim-methyl;
• mancozeb; maneb; Meferimzone; mepanipyrim; mepronil; metalaxyl; Metalaxyl-M; metconazole; methasulfocarb; Methfuroxam; metiram; metominostrobin; Metsulfovax; mildiomycin; myclobutanil; myclozoline;
• natamycin; nicobifen; Nitro Thal-isopropyl; Noviflumuron; nuarimol;
• ofurace; orysastrobin; oxadixyl; Oxolinic acid; Oxpoconazole; oxycarboxin; Oxyfenthiin;
• paclobutrazol; Pefurazoate; penconazole; pencycuron; phosdiphen; phthalides; picoxystrobin; piperalin; Polyoxins; Polyoxorim; Probenazole; prochloraz; procymidone; propamocarb; Propanosine-sodium; propiconazole; propineb; proquinazid; prothioconazole; pyraclostrobin; Pyrazohos; pyrifenox; pyrimethanil; pyroquilon; Pyroxyfur; Pyrrolnitrine;
• Quinconazole; quinoxyfen; quintozene;
• Simeconazole; spiroxamine; Sulfur;
• tebuconazole; tecloftalam; Tecnazene; Tetcyclacis; tetraconazole; thiabendazole; Thicyofen; Thifluzamide; Thiophanate-methyl; thiram; Tioxymid; Tolclofosmethyl; tolylfluanid; triadimefon; triadimenol; Triazbutil; triazoxide; Tricyclamide; Tricyclazole; tridemorph; trifloxystrobin; triflumizole; triforine; triticonazole;
• Uniconazole;
• Validamycin A; vinclozolin;
• Zineb; ziram; zoxamide;
• (2S) -N- [2- [4 - [[3- (4-chlorophenyl) -2-propynyl] oxy] -3-methoxyphenyl] ethyl] -3-methyl-2 - [(methylsulfonyl) amino] butanamide ;
• 1- (1-naphthalenyl) -1H-pyrrole-2,5-dione;
• 2,3,5,6-tetrachloroethane-4- (methylsulfonyl) -pyridine;
• 2-amino-4-methyl-N-phenyl-5-thiazolecarboxamide;
• 2-chloro-N- (2,3-dihydro-1,1,3-trimethyl-1H-inden-4-yl) -3-pyridinecarboxamides;
• 3,4,5-trichloro-2,6-pyridinedicarbonitrile;
• Actinovate;
• cis-1- (4-chlorophenyl) -2- (1H-1,2,4-triazol-1-yl) cycloheptanol;
• Methyl 1- (2,3-dihydro-2,2-dimethyl-1H-inden-1-yl) -1H-imidazole-5-carboxylate;
• Monokaliumcarbonat;
• N- (6-methoxy-3-pyridinyl) -cyclopropanecarboxamide;
• sodium tetrathiocarbonate; and copper salts and preparations, like Bordeaux mixture; copper; copper naphthenate; copper oxychloride; Copper sulfate; Cufraneb; copper; mancopper; Oxine-copper.

bactericides:

bronopol, Dichlorophen, nitrapyrin, nickel dimethyldithiocarbamate, kasugamycin, Octhilinone, furancarboxylic acid, Oxytetracycline, probenazole, streptomycin, tecloftalam, copper sulfate and other copper preparations.

Insecticides / acaricides / nematicides:

• Abamectin, ABG-9008, Acephate, Acequinocyl, Acetamiprid, Acetoprole, acrinathrin, AKD-1022, AKD-3059, AKD-3088, alanycarb, Aldicarb, aldoxycarb, allethrin, allethrin 1R-isomers, alpha-cypermethrin (Alphamethrin), amidoflumet, aminocarb, amitraz, avermectin, AZ-60541, Azadirachtin, Azamethiphos, Azinphos-methyl, Azinphos-ethyl, Azocyclotin,
• Bacillus popilliae, Bacillus sphaericus, Bacillus subtilis, Bacillus thuringiensis, Bacillus thuringiensis strain EG-2348, Bacillus thuringiensis strain GC-91, Bacillus thuringiensis strain NCTC-11821, Baculoviruses, Beauveria bassiana, Beauveria tenella, Bendiocarb, Benfuracarb, Bensultap, Benzoximate, Beta-Cyfluthrin, Beta-Cypermethrin, Bifenazate, Bifenthrin, Binapacryl, Bioallethrin, Bioallethrin S-cyclopentyl isomer, Bioethanomethrin, Biopermethrin, Bioresmethrin, Bistrifluron, BPMC, Brofenprox, Bromophos-ethyl, Bromopropylate, Bromfenvinfos (-methyl), BTG-504, BTG-505, Bufencarb, Buprofezin, Butathiofos, Butocarboxime, Butoxycarboxime, butylpyridaben,
• Cadusafos, camphechlor, carbaryl, carbofuran, carbophenothione, Carbosulfan, Cartap, CGA-50439, Quinomethionate, Chlordane, Chlorodimeform, Chloethocarb, chloroethoxyfos, chlorfenapyr, chlorfenvinphos, chlorofluorazuron, Chlormephos, Chlorobenzilate, Chloropicrin, Chloroproxyfen, Chlorpyrifos-methyl, Chlorpyrifos (ethyl), chlovaporthrin, chromafenozide, cis-cypermethrin, Cis-resmethrin, cis-permethrin, Clocythrin, Cloethocarb, Clofentezine, Clothianidin, Clothiazoben, Codlemone, Coumaphos, Cyanofenphos, Cyanophos, Cycloprene, Cycloprothrin, Cydia pomonella, cyfluthrin, cyhalothrin, cyhexatin, cypermethrin, Cyphenothrin (1R-trans isomer), Cyromazine,
• DDT, deltamethrin, demeton-S-methyl, demeton-S-methyl sulphone, diafenthiuron, dialifos, diazinon, dichlo fenthion, dichlorvos, dicofol, dicrotophos, dicyclanil, diflubenzuron, dimethoate, dimethylvinphos, dinobutone, dinocap, dinotefuran, diofenolane, disulfotone, docusate-sodium, dofenapine, DOWCO-439,
• Eflusilanate, emamectin, emamectin benzoate, empenthrin (1R isomer), Endosulfan, Entomopthora spp., EPN, Esfenvalerate, Ethiofencarb, Ethiprole, Ethion, Ethoprophos, Etofenprox, Etoxazole, Etrimfos,
• Famphur, fenamiphos, fenazaquin, fenbutatin oxide, fenfluthrin, Fenitrothion, fenobucarb, fenothiocarb, fenoxacrim, fenoxycarb, Fenpropathrin, fenpyrad, fenpyrithrin, fenpyroximate, fensulfothion, Fenthion, fentrifanil, fenvalerate, fipronil, flonicamid, fluacrypyrim, Fluazuron, Flubenzimine, Flubrocythrinate, Flucyclox uron, Flucythrinate, Flufenerim, Flufenoxuron, Flufenprox, Flumethrin, Flupyrazofos, Flutenzin (Flufenzine), Fluvalinate, Fonofos, Formetanate, Formothion, Fosmethilane, Fosthiazate, Fubfenprox (Fluproxyfen), Furathiocarb,
• Gamma-HCH, Gossyplure, Grandlure, Granuloseviruses,
• Halfenprox, Halofenozide, HCH, HCN-801, Heptenophos, Hexaflumuron, Hexythiazox, hydramethylnone, hydroprene,
• IKA-2002, imidacloprid, imiprothrin, indoxacarb, iodofenofen, Iprobenfos, Isazofos, Isofenphos, Isoprocarb, Isoxathion, Ivermectin,
• Japonilure,
• Kadethrin, nuclear poly-derviruses, kinoprene,
• Lambda-Cyhalothrin, Lindane, Lufenuron,
• Malathion, mecarbam, mesulfenfos, metaldehyde, metam-sodium, Methacrifos, Methamidophos, Metharhizium anisopliae, Metharhizium flavoviride, methidathione, methiocarb, methomyl, methoprene, methoxychlor, Methoxyfenozide, Metolcarb, Metoxadiazone, Mevinphos, Milbemectin, Milbemycin, MKI-245, MON-45700, monocrotophos, moxidectin, MTI-800,
• Naled, NC-104, NC-170, NC-184, NC-194, NC-196, Niclosamide, Nicotine, nitenpyram, nithiazines, NNI-0001, NNI-0101, NNI-0250, NNI-9768, Novaluron, Noviflumuron,
• OK-5101, OK-5201, OK-9601, OK-9602, OK-9701, OK-9802, Omethoate, Oxamyl, oxydemeton-methyl,
• Paecilomyces fumosoroseus, parathion-methyl, parathion (-ethyl), Permethrin (cis-, trans-), petroleum, PH-6045, phenothrin (1R-trans isomer), phenthoates, phorates, phosalones, phosmet, phosphamidone, Phosphocarb, phoxim, piperonyl butoxide, pirimicarb, pirimiphos-methyl, Pirimiphos-ethyl, Prallethrin, Profenofos, Promecarb, Propaphos, Propargites, Propetamphos, Propoxur, Prothiofos, Prothoates, Protrifenbutes, Pymetrozine, Pyraclofos, Pyresmethrin, Pyrethrum, Pyridaben, Pyridalyl, Pyridapenthione, Pyridathione, Pyrimidifen, Pyriproxyfen,
• quinalphos,
• Resmethrin, RH-5849, Ribavirin, RU-12457, RU-15525,
• 5-421, S-1833, Salithion, Sebufos, SI-0009, Silafluofen, Spinosad, Spirodiclofen, spiromesifen, sulfluramid, sulfotep, sulprofos, SZI-121,
• Tau Fluvalinate, Tebufenozide, Tebufenpyrad, Tebupirimfos, Teflubenzuron, Tefluthrin, Temephos, Temivinphos, Terbam, Terbufos, Tetrachlorvinphos, Tetradifon, tetramethrin, tetramethrin (1R-isomer), tetrasul, theta-cypermethrin, Thiacloprid, thiamethoxam, thiapronil, thiatriphos, thiocyclam hydrogen oxalate, thiodicarb, thiofanox, thiometone, thiosultap-sodium, thuringiensin, Tolfenpyrad, tralocythrin, tralomethrin, transfluthrin, triarathene, Triazamates, triazophos, triazuron, trichlorophenidines, trichlorofon, Triflumuron, trimethacarb,
• Vamidothion, Vaniliprole, Verbutin, Verticillium lecanii,
• WL-108477, WL-40027,
• YI-5201, YI-5301, YI-5302,
• XMC, xylylcarb,
• ZA-3274, zeta-cypermethrin, zolaprofos, ZXI-8901, the connection 3-methyl-phenyl-propylcarbamate (Tsumacide Z), the connection 3- (5-Chloro-3-pyridinyl) -8- (2,2,2-trifluoroethyl) -8-azabicyclo [3.2.1] octane-3-carbonitrile (CAS Reg. 185982-80-3) and the corresponding 3-endo isomer (CAS Reg. No. 185984-60-5) (see WO-96/37494, WO-98/25923), as well as preparations, which insecticidal plant extracts, nematodes, fungi or Contain viruses.

Also a mixture with other known active substances, such as herbicides or with fertilizers and growth regulators, safeners or semiochemicals is possible.

In addition, the compounds of the formula (I) according to the invention also have very good antifungal effects. They have a very broad antimycotic spectrum of activity, in particular against dermatophytes and yeasts, mold and diphasic fungi (eg against Candida species such as Candida albicans, Candida glabrata) and Epidermophyton floccosum, Aspergillus species such as Aspergillus niger and Aspergillus fumigatus, Trichophyton species such as Trichophyton mentagrophytes, Microsporon species like Microsporon canis and audouinii. The list of these fungi is by no means a limitation of the detectable mycotic spectrum, but has only an explanatory character.

The Active ingredients can as such, in the form of their formulations or the ones prepared from them Application forms, such as ready-to-use solutions, suspensions, wettable powders, Pastes, soluble Powder, dusts and granules are applied. The application happens in usual Way, e.g. by pouring, squirting, spraying, Scattering, dusting, foaming, Brushing, etc. It is also possible to apply the active ingredients according to the ultra-low-volume method or the active ingredient preparation or the active ingredient itself in the soil to inject. It can also be the seed of the plants to be treated.

At the Use of the active compounds according to the invention as fungicides can the application rates depending on the type of application within a larger area be varied. In the treatment of plant parts are the Application rates of active ingredient generally between 0.1 and 10,000 g / ha, preferably between 10 and 1,000 g / ha. In the seed treatment the application rates of active ingredient are generally between 0.001 and 50 grams per kilogram of seed, preferably between 0.01 and 10 g per kilogram of seed. When treating the soil are the Application rates of active ingredient generally between 0.1 and 10,000 g / ha, preferably between 1 and 5,000 g / ha.

As already mentioned above, can According to the invention, all plants and their parts are treated. In a preferred embodiment are wild or by conventional biological breeding methods, such as crossing or protoplast fusion obtained plant species and Treated plant varieties and their parts. In a further preferred embodiment are transgenic plants and plant varieties produced by genetic engineering Methods if necessary in combination with conventional methods were obtained (Genetically Modified, Organisms) and their parts treated. The term "parts" or "parts of plants "or" plant parts "has been explained above.

Especially plants according to the invention are preferred the respective commercial or plant varieties in use. Among plant varieties one understands plants with new characteristics ("Traits"), which by both conventional breeding, by mutagenesis or by recombinant DNA techniques are. This can Be varieties, breeds, biotypes and genotypes.

ever according to plant species or plant varieties, their location and growth conditions (Floors, Climate, vegetation period, nutrition) can by the treatment according to the invention also superadditives ("Synergistic") effects occur. For example, reduced application rates and / or expansions of the Spectrum of action and / or an increase in the effect of the invention can be used Substances and agents, better plant growth, increased tolerance across from high or low temperatures, increased tolerance to dryness or against water or soil salt content, increased flowering efficiency, easier harvest, Acceleration of maturity, higher Crop yields, higher quality and / or higher Nutritional value of Harvested products, higher Shelf life and / or workability of the harvested products possible, beyond the actually expected Go beyond effects.

The preferred plants or plant cultivars to be treated according to the invention include all plants which have obtained genetic material by the genetic engineering modification which gives these plants particularly advantageous valuable properties ("traits") Examples of such properties are better plant growth. increased tolerance to high or low temperatures, increased tolerance to dryness or to bottoms, increased flowering efficiency, easier harvesting, acceleration of ripeness, higher crop yields, higher quality and / or higher nutritional value of the harvested products, higher shelf life and / or machinability Further and particularly emphasized examples of such properties are an increased defense of the plants against animal and microbial pests, such as insects, mites, phytopathogenic fungi, bacteria and / or viruses as well as an increased tolerance of the plants against certain herbicidal active substances. Examples of transgenic plants include the important crops such as cereals (wheat, rice), corn, soybean, potato, cotton, tobacco, oilseed rape and fruit plants (with the fruits apples, pears, citrus fruits and grapes), with corn, soybean, potato , Cotton, tobacco and oilseed rape. Traits which are particularly emphasized are the increased defense of the plants against insects, arachnids, namatodes and snails by toxins formed in the plants, in particular those which are produced by the genetic material from Bacillus thuringiensis (for example by the genes CryIA (a) , CryIA (b), CryIA (c), CryIIA, CryIIIA, CryIIIB2, Cry9c Cry2Ab, Cry3Bb and CryIF and their combinations) in the plants (hereinafter "Bt plants"). Traits also become especially emphasized the increased defense of plants against fungi, bacteria and viruses Systemic acquired resistance (SAR), systemin, phytoalexins, elicitors and resistance genes and correspondingly expressed proteins and toxins. Traits which are furthermore particularly emphasized are the increased tolerance of the plants to certain herbicidally active compounds, for example imidazolinones, sulphonylureas, glyphosate or phosphinotricin (eg "PAT" gene) .The genes conferring the desired properties ("traits") may also occur in combinations with each other in the transgenic plants. Examples of "Bt plants" are maize varieties, cotton varieties, soya bean varieties and potato varieties may be mentioned, under the trade names YIELD GARD ^® (for example maize, cotton, soya beans), KnockOut ^® (for example maize), StarLink ^® (for example maize), Bollgard ^® ( cotton), Nucoton ^® (cotton) and NewLeaf ^® (potato). Examples of herbicide-tolerant plants are maize varieties, cotton varieties and soybean varieties may be mentioned that against under the trade names Roundup Ready ^® (tolerance to glyphosate, for example maize, cotton, soya bean), Liberty Link ^® (tolerance to phosphinotricin, for example oilseed rape), IMI ^® (tolerance Imidazolinone) and STS ^® (tolerance to sulfonylureas such as corn) are sold. As a herbicide. resistant (conventionally grown on herbicide tolerance) plants are also the varieties sold under the name Clearfield ^® (eg corn) mentioned. Of course, these statements also apply to future or future marketed plant varieties with these or future developed genetic traits.

The listed Plants can particularly advantageous according to the invention with the compounds of the general Treated formula (I) or the Wirkstoffimschungen invention become. The specified in the active ingredients or mixtures above Preferential ranges also apply to the treatment of these plants. Particularly emphasized is the Plant treatment with the compounds specifically listed herein or mixtures.

The Production and use of the active compounds according to the invention is based on following examples.

Preparation Examples

example 1

(Method a)

To a solution of 0.2 g (0.56 mmol) of 3-cyano-5,7-dichloro-6- (3-trifluoromethylpyridin-2-yl) -pyrazolo [1,5-a] pyrimidine in 10 ml of acetonitrile 0.065 g (1.12 mmol) of potassium fluoride, stirred for 2 hours at 80 ° C and then cooled to 0 ° C from. To this solution is added 0.13 g (1.17 mmol) of (S) -2,2,2-trifluoro-isopropylamine and stirred for 18 hours at 80 ° C. Thereafter, the reaction mixture is cooled to room temperature and stirred into 30 ml of dilute hydrochloric acid. It is extracted with dichloromethane, the organic phase is washed twice with water, dried over sodium sulfate and concentrated under reduced pressure. The remaining residue is filtered through a short silica gel column with a mixture of petroleum ether / methyl tert-butyl ether = 15: 1. This gives 0.15 g (58.5% of theory) of 3-cyano-5-chloro-6- (3-trifluoromethyl-pyridin-2-yl) -pyrazolo [1,5-a] -pyrimidine N - [(1 S) -2,2,2-trifluoro-1-methylethyl] -amine.
HPLC: log P = 3.14

hergestellt. Tabelle 1

Tabelle 1 (Fortsetzung)

Tabelle 1 (Fortsetzung)

Tabelle 1 (Fortsetzung)

Tabelle 1 (Fortsetzung)

By the methods given above, the pyrazolopyrimidines of the formula

produced. Table 1

Table 1 (continued)

Table 1 (continued)

Table 1 (continued)

Table 1 (continued)

Production of precursors of the formula (II):

Example 54

Method (d)

To a mixture of 5.8 g (18.1 mmol) of 3-cyano-6- (3-trifluoromethylpyridin-2-yl) pyrazolo [1,5-a] pyrimidine-5,7-diol and 22.15 g (144.5 mmol) of phosphorus oxychloride are added at room temperature with stirring 3.0 g (14.5 mmol) of phosphorus pentachloride in 5 portions. The reaction mixture is heated at reflux for 4 hours, then cooled to room temperature and concentrated under reduced pressure. The remaining residue is mixed with 100 ml of water and then extracted three times with 100 ml of dichloromethane. The combined organic phases are washed twice with 50 ml of water, dried over sodium sulfate and concentrated under reduced pressure. The remaining residue is chromatographed on silica gel with hexane / ethyl acetate = 3: 1. 0.88 g (14.8% of theory) of 3-cyano-5,7-dichloro-6- (3-trifluoromethyl-pyridin-2-yl) -pyrazolo [1,5-a] pyrimidine.
HPLC: log P = 2.68

Example 55

One Mixture of 2.0 g (10.74 mmol) 2-thienyl malonic acid and 1.16 g (10.74 mmol) 3-amino-4-cyano-pyrazole is stirred at room temperature with stirring 2 minutes with 41.13 g (268 mmol) of phosphorus oxychloride added. After that, 18 hours at 90 ° C heated and then cooled to room temperature. The reaction mixture is in 250 ml of ice water, and the resulting suspension is stirred for 1 hour. It sucks and washes with 50 ml of water. For further purification, the product is in 50 ml of cyclohexane / ethyl acetate = 1: 1 and boiled briefly, then cooled, over a short silica column filtered off with suction and 8 times with 50 ml of cyclohexane / ethyl acetate = 1: 1 washed. The filtrate is dried over sodium sulfate and then filtered again. The filter residue is treated with a little cyclohexane / ethyl acetate = 1: 1 washed. The entire filtrate is concentrated under reduced pressure Concentrated pressure. You get 1.48 g (30.34% of theory) of 5,7-dichloro-3-cyano-6- (thien-3-yl) -pyrazolo [1,5-a] pyrtmidine in the form of a solid.

Example 56

In a solution of 7.5 g (25.41 mmol) of 5,7-dichloro-3-cyano-6- (thien-3-yl) -pyrazolo [1,5-a] pyrimidine in 80 ml of dichloromethane at temperatures between -5 ° C and 0 ° C for two hours long introduced a chlorine gas stream. Thereafter, the reaction mixture warmed to room temperature and then concentrated under reduced pressure. Take the remaining one Residue with dichloromethane and sucks. This gives 2.0 g of the desired Product. The previously collected filtrate is after concentration with Cyclohexane / ethyl acetate = 1: 1 chromatographed on silica gel. After concentration of the eluate again 3.5 g of the desired Product isolated. You get in this way a total of 5.5 g (54.13% of theory) of 5,7-dichloro-3-cyano- (2,5-chloro-thien-3-yl) -pyrazolo [1,5-a] pyrimidine

Production of precursor of the formula (VIII):

Example 57

Method (s)

A mixture of 4.1 g (14.8 mmol) of dimethyl 2- (3-trifluoromethyl-pyridin-2-yl) -malonate, 1.6 g (14.8 mmol) of 3-amino-4-cyano-pyrazole and 3 , 02 g (16.3 mmol) of tri-n-butylamine is heated with stirring to 180 ° C for 2 hours. In this case, the methanol formed during the reaction is continuously distilled off. Subsequently, the reaction mixture is cooled to room temperature. The precipitating tri-n-butylamine is decanted off and the remaining mixture is distilled under reduced pressure. This gives 5.8 g of a product which according to HPLC consists of 60% of 3-cyano-6- (3-trifluoromethyl-pyridin-2-yl) -pyrazolo [1,5-a] pyrimidine-5,7-diol , The yield is then calculated to be 73.25% of theory. The product is used without further purification for further syntheses.
HPLC: log P = 0.29

Production of precursor of the formula (IX-a):

Example 58

Method (f)

9 g (207 mmol) of 60% sodium hydride suspension are suspended in 300 ml of dioxane. To this is added dropwise at 55-60 ° C 27.29 g (206.6 mmol) of dimethyl malonate and stirred for another 30 minutes at the same temperature. After addition of 8.18 g (82.63 mmol) of copper (I) chloride is heated to 80 ° C and then added dropwise 15 g (82.63 mmol) of 2-chloro-3-trifluoromethylpyridine. The reaction mixture is then stirred for a further 14 hours at 100.degree. After the subsequent cooling to 15-20 ° C is slowly added dropwise concentrated hydrochloric acid until the mixture is acidic. Then, 600 ml of water and 300 ml of dichloromethane are added and filtered insoluble constituents. From the filtrate, the organic phase is separated, dried over sodium sulfate and concentrated under reduced pressure. The residue is chromatographed on silica gel with hexane / ethyl acetate (4: 1). 10.1 g (40% of theory) of dimethyl 2 - [(3-trifluoromethyl) -pyrimidin-2-yl] malonate are obtained.
HPLC: log P = 2.05

Production of precursor of the formula (IX-b):

Example 59

Method (g)

2.6 g (65.4 mmol) of 60% sodium hydride suspension are suspended in 100 ml of tetrahydrofuran. To this is added at 0 ° C 6.9 g (52.4 mmol) of dimethyl malonate and stirred for 0.5 hours at the same temperature. Then added dropwise to a solution of 6.5 g (43.63 mmol) of 4,5-dichloropyrimidine in 50 ml of tetrahydrofuran and stirred for a further 3 hours at room temperature. Thereafter, 150 ml of 1N hydrochloric acid are slowly added dropwise and then extracted with 100 ml of dichloromethane. The organic phase is separated, dried over sodium sulfate and concentrated under reduced pressure. The residue is chromatographed on silica gel with methyl t-butyl ether / petroleum ether (1: 9). This gives 7 g (65.6% of theory) of 2- (5-chloro-pyrimidin-4-yl) -malonate.
HPLC: log P = 1.33

Preparation of 4,5-dichloropyrimidine

Example 60

To a solution of 112.5 g (673.7 mmol) of 5-chloro-6-oxo-1,6-dihydropyrimidin-1-ium chloride in 630 ml of phosphorus oxychloride are added 1.6 ml of dimethylamine and heated under reflux for 3 hours. Thereafter, the excess phosphorus oxychloride is distilled off under reduced pressure. After cooling, the residue is poured into 1.5 1 of ice water, extracted with 500 ml of dichloromethane, the organic phase is dried over sodium sulfate and concentrated under reduced pressure. This gives 72.3 g (66.3% of theory) of 4,5-dichloropyrimidine.
HPLC: log P = 1.35

Preparation of 5-chloro-6-oxo-1,6-dihydropyrimidine-1-ium chloride

Example 61

To a solution of 77 g (0.8 mol) of 4 (3H) -pyrimidinone in 770 ml of glacial acetic acid are added 6.5 g (40 mmol) of ferric chloride and passes within 2 hours at 40-45 ° C 113.6 g (1.6 moles) of chlorine. The reaction mixture is cooled to 15 ° C, the resulting Filtered off with suction and washed with ether. You get 112.5 g (84% of theory) of 5-chloro-6-oxo-1,6-dihydropyrimidin-1-ium chloride.

Preparation of 4 (3H) -pyrimidinone

Example 62

A mixture of 103 g (0.804 mol) of 6-mercapto-4 (1H) -pyrimidinone ( JP 50053381 , Chem. Abstr. CAN 84: 17404) and 141.5 g (1.2 moles) Raney nickel in 1.21 ethanol is refluxed for 8 hours. The solution is filtered hot, the residue washed with ethanol and the filtrate concentrated under reduced pressure. This gives 67.2 g (87% of theory) of 4 (3H) -pyrimidinone.
^*) The determination of the logP values was carried out according to EEC Directive 79/831 Annex V. A8 by HPLC (gradient method, acetonitrile / 0.1% aqueous phosphoric acid)

Example A

Venturia - test (apple) / protective

• solvent : 24.5 parts by weight of acetone 24.5 parts by weight of dimethylacetamide
• Emulsifier: 1 part by weight of alkyl-aryl-polyglycol ether

to Preparation of a suitable preparation of active ingredient 1 part by weight of active compound is mixed with the stated amounts solvent and emulsifier and diluted concentrate with water to the desired concentration.

to exam Protective effectiveness of young plants with the preparation of active ingredient sprayed in the specified rate. After the spray coating has dried on are the plants with an aqueous Conidia suspension of the apple scab pathogen Venturia inaequalis inoculated and then remain for 1 day at about 20 ° C and 100% relative humidity in an incubation cabin.

The Plants are then grown in the greenhouse at about 21 ° C and a relative humidity of about 90%.

10 Days after the inoculation the evaluation takes place. This means 0% an efficiency equal to that of the control while a Efficiency of 100% means that no infestation is observed.

In This test shows the inventive substance listed in Example 1 at an application rate of 100 g / ha an efficiency of over 90%.

Example B

In vitro test for the determination of ED ₅₀ on microorganisms

• Solvent: methanol
• Emulsifier: alkylaryl polyglycol ether

you mixes 2 mg of active ingredient with 100 μl Methanol and diluted the concentrate thus prepared then with a mixture of 1000 ml Methanol and 6 g of the above emulsifier on each desired Concentration.

In each case 10 .mu.l of the preparation are pipetted into the wells of microtiter plates. After the solvent has evaporated, 200 .mu.l of a potato-dextrose medium are added to each cavity, which was previously added to the respectively desired concentration of spores or mycelium of the microorganism to be tested. The resulting concentrations of active ingredient in the cavities amount
0.1 ppm
1 ppm
10 ppm
or 100 ppm.

The resulting concentration of emulsifier is 300 ppm each.

to Incubation, the microplates are then 3 to 5 days on a Shakers at a temperature of 22 ° C moves until sufficient growth in the untreated control of the respective microorganism is detectable.

The evaluation is carried out photometrically at a wavelength of 620 nm. From the measured data for the various concentrations, the drug dose is calculated, which leads to a 50% inhibition of fungal growth (ED ₅₀ ) compared to the untreated control.

In this test, the ED ₅₀ value of the compound of the invention listed in Example 1 in Botrytis cinerea at an active ingredient dose that is less than 10 ppm.

Claims (14)

Pyrazolopyrimidines of the formula

in which R ^{1 is} optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted cycloalkyl or optionally substituted heterocyclyl, R ^{2 is} hydrogen or alkyl, or R ¹ and R ² together with the nitrogen atom to which they R ^{3 is} optionally substituted heterocyclyl, Hal is halogen and X is halogen, cyano, nitro, alkyl, alkenyl, hydroxyalkyl, alkoxyalkyl, haloalkyl, cycloalkyl, formyl, thiocarbamoyl, alkoxycarbonyl, Alkylcarbonyl, hydroximinoalkyl, alkoximinoalkyl, alkylthio, alkylsulfinyl, alkylsulfonyl or alkylaminocarbonyl. Process for the preparation of pyrazolopyrimidines of the formula (I) according to Claim 1, characterized in that (a) halo-pyrazolopyrimidines of the formula

in which R ³ and Hal have the meanings given in claim 1, X ^{1 is} halogen, cyano, nitro, alkyl, haloalkyl, cycloalkyl, thiocarbamoyl, alkoxycarbonyl, alkylcarbonyl, alkylthio, alkylsulfinyl, alkylsulfonyl or alkylaminocarbonyl and Y ^{1 is} halogen, with amines of the formula

in which R ¹ and R ^{2 have} the meanings given in claim 1, if appropriate in the presence of a diluent, if appropriate in the presence of an acid acceptor and if appropriate in the presence of a catalyst, or b) pyrazolopyrimidines of the formula

in which R ¹ , R ² , R ³ and Hal have the meanings given in claim 1, either α) reacted with diisobutylaluminum hydride in the presence of aqueous ammonium chloride solution and in the presence of an organic diluent, or β) with Grignard compounds of formula R ⁴ -Mg-X ² (IV) in which R ^{4 is} alkyl and X ^{2 is} chlorine or bromine, in the presence of a diluent and optionally in the presence of a catalyst, or c) pyrazolopyrimidines of the formula

in which R ¹ , R ² , R ³ and Hal have the meanings given above and R ^{5 is} hydrogen or alkyl, either α) with amino compounds of the formula H ₂ N-OR ⁶ (V) in which R ^{6 is} hydrogen or alkyl, in the presence of a diluent and optionally in Gegenwan a catalyst, wherein the amino compounds of the formula (V) can also be used in the form of their acid addition salts, or β) with triphenylphosphonium salts of the formula

in which Ph is phenyl and R ^{7 is} hydrogen or alkyl, in the presence of a base and in the presence of a diluent, or γ) with diisobutyl aluminum hydride in the presence of aqueous ammonium chloride solution and in the presence of an organic diluent, or with Sodium borohydride in the presence of a diluent, and optionally the resulting pyrazolopyrimidines of the formula

in which R ¹ , R ² , R ³ , R ⁷ and Hal have the meanings given above, with alkylating agents of the formula R ⁸ -X ³ (VII) in which R ^{8 is} alkyl and X ^{3 is} chlorine, bromine, iodine or the radical R ⁸ O-SO ₂ -O-, if appropriate in the presence of a base and in the presence of a diluent. Means to combat of unwanted Microorganisms characterized by a content of at least a pyrazolopyrimidine of the formula (I) according to claim 1 in addition to extenders and / or surface-active Substances. Use of pyrazolopyrimidines of the formula (I) according to claim 1 to combat of unwanted Microorganisms. Method of control of unwanted Microorganisms, characterized in that pyrazolopyrimidines of the formula (I) according to claim 1 on the unwanted Microorganisms and / or their habitat. Process for the preparation of compositions for controlling undesirable Microorganisms, characterized in that pyrazolopyrimidines of the formula (I) according to claim 1 mixed with extenders and / or surfactants. Halogen-pyrazolopyrimidines of the formula

in which R ^{3 is} optionally substituted heterocyclyl, Hal is halogen, X ^{1 is} halogen, cyano, nitro, alkyl, haloalkyl, cycloalkyl, thiocarbamoyl, alkoxycarbonyl, alkylcarbonyl, alkylthio, alkylsulfinyl, alkylsulfonyl or alkylaminocarbonyl and Y ^{1 is} halogen , Process for the preparation of halo-pyrazolopyrimidines of the formula (II) according to Claim 7, characterized in that d) hydroxy-pyrazolopyrimidines of the formula

in which R ³ and X ^{1 have} the meanings given in claim 7, with halogenating agents, if appropriate in the presence of a diluent. Hydroxy-pyrazolopyrimidines of the formula

in which R ^{3 is} optionally substituted heterocyclyl and X ^{1 is} halogen, cyano, nitro, alkyl, haloalkyl, cycloalkyl, thiocarbamoyl, alkoxycarbonyl, alkylcarbonyl, alkylthio, alkylsulfinyl, alkylsulfonyl or alkylaminocarbonyl. Process for the preparation of hydroxy-pyrazolopyrimidines of the formula (VIII) according to Claim 9, characterized in that (e) heterocyclylmalonic esters of the formula

in which R ^{3 has} the meaning given in claim 9 and R ^{9 is} alkyl having 1 to 4 carbon atoms, with aminopyrazoles of the formula

in which X ^{1 has} the meaning given in claim 9, if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder. Pyridylmalonester of the formula

in which R ^{9 is} the alkyl having 1 to 4 carbon atoms and R ^{10 is} halogen or haloalkyl. A process for the preparation of Pyridylmalonestern of formula (IX-a) according to claim 11, characterized in that (f) halopyridines of the formula

in which R ^{10 has} the meaning given in claim 11 and Y ^{2 is} halogen, with malonic esters of the formula

in which R ^{9 has} the meaning given in claim 11, if appropriate in the presence of a diluent, if appropriate in the presence of a copper salt and if appropriate in the presence of an acid acceptor. Pyrimidylmalonester of the formula

in which R ^{9 is} alkyl having 1 to 4 carbon atoms, R ^{11 is} halogen or haloalkyl, and R ¹² and R ¹³ are each independently hydrogen, fluorine, chlorine, bromine, methyl, ethyl or methoxy. A process for the preparation of Pyrimidylmalonestern of formula (IX-b) according to claim 13, characterized in that (e) halopyrimidines of the formula

in which R ¹¹ , R ¹² and R ^{13 have} the meanings given in claim 13 and Y ^{3 is} halogen, with malonic esters of the formula

in which R ^{9 has} the meaning given in claim 13, if appropriate in the presence of a diluent, if appropriate in the presence of a copper salt and, if appropriate, in the presence of an acid acceptor.