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1. (US20100144674) PYRIDAZINE DERIVATIVES
Note: Texte fondé sur des processus automatiques de reconnaissance optique de caractères. Seule la version PDF a une valeur juridique
      The present invention relates to novel pyridazine derivatives as active ingredients which have microbiocidal activity, in particular fungicidal activity. The invention also relates to preparation of these active ingredients, to novel heterocyclic derivatives used as intermediates in the preparation of these active ingredients, to preparation of these novel intermediates, to agrochemical compositions which comprise at least one of the novel active ingredients, to preparation of these compositions and to use of the active ingredients or compositions in agriculture or horticulture for controlling or preventing infestation of plants, harvested food crops, seeds or non-living materials by phytopathogenic microorganisms, preferably fungi.
      The present invention provides a compound of formula I:

( MOL) ( CDX) wherein

R1 is hydrogen, C1-C6alkyl, C1-C6haloalkyl or C3-C6cycloalkyl;

R2 is cycloalkyl, cycloalkylalkyl, halocycloalkyl, cycloalkoxy, halocycloalkoxy, cycloalkylalkoxy, halocycloalkylalkoxy, alkoxyalkyl, cycloalkoxyalkoxyalkyl, haloalkoxyalkyl, trialkylsilyl, alkylthioalkyl, haloalkylthioalkyl, cycloalkylthio, halocycloalkylthio, cycloalkylalkylthio, halocycloalkylalkylthio, alkylsulfinylalkyl, alkylsulfonylalkyl, alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl, haloalkylsulfonyl, C2-C6alkenyl, C2-C6alkynyl, optionally substituted arylsulfonyl, optionally substituted aryloxy, optionally substituted heteroaryloxy, optionally substituted arylthio, optionally substituted heteroarylthio; or

R2 together with an adjacent carbon atom forms an optionally substituted fused ring;

R3 is an optionally substituted aryl;

R4 is hydrogen, halogen, C1-C6alkyl, C1-C6haloalkyl, C1-C6alkoxy, C1-C6haloalkoxy, hydroxy or cyano; and

n is a whole number from 1 to 4;

or an agrochemically usable salt form thereof.

      When n is 2, 3 or 4, then each R 2 independently of each other and independently at each occurrence can be the same or different.
      In the above definition aryl includes aromatic hydrocarbon rings like phenyl, naphthyl, anthracenyl, phenanthrenyl and biphenyl, with phenyl being preferred.
      Heteroaryl stands for aromatic ring systems comprising mono-, bi- or tricyclic systems wherein at least one oxygen, nitrogen or sulfur atom is present as a ring member. Examples are furyl, thienyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, oxadiazolyl, thiadiazolyl, triazolyl, tetrazolyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, tetrazinyl, indolyl, benzothiophenyl, benzofuranyl, benzimidazolyl, indazolyl, benzotriazolyl, benzothiazolyl, benzoxazolyl, quinolinyl, isoquinolinyl, phthalazinyl, quinoxalinyl, quinazolinyl, cinnolinyl and naphthyridinyl.
      The above or below mentioned fused ring, carbocyclic ring, heterocyclic ring, aryl group and heteroaryl group may be optionally substituted. This means that they may carry one or more identical or different substituents. Normally not more than three substituents are present at the same time. Examples of substituents are: halogen, alkyl, haloalkyl, cycloalkyl, cycloalkylalkyl, alkenyl, haloalkenyl, cycloalkenyl, alkynyl, haloalkynyl, alkyloxy, haloalkyloxy, cycloalkoxy, alkenyloxy, haloalkenyloxy, alkynyloxy, haloalkenyloxy, alkylthio, haloalkylthio, cycloalkylthio, alkenylthio, alkynylthio, alkylcarbonyl, haloalkylcarbonyl, cycloalkylcarbonyl, alkenylcarbonyl, alkynylcarbonyl, alkoxyalkyl, cyano, nitro, hydroxy, mercapto, amino, alkylamino, dialkylamino. Typical examples for optionally substituted aryl include 2-fluorophenyl, 2-chlorophenyl, 2-trifluoromethylphenyl, 2-methylphenyl, 2,3-difluorophenyl, 2,4-difluorophenyl, 2,5-difluorophenyl, 2,6-difluorophenyl, 2,3-dichlorophenyl, 2,4-dichlorophenyl, 2,5-dichlorophenyl, 2,6-dichlorophenyl, 2-chloro-3-fluorophenyl, 2-chloro-4-fluorophenyl, 2-chloro-5-fluorophenyl, 2-chloro-6-fluorophenyl, 3-chloro-2-fluorophenyl, 4-chloro-2-fluorophenyl, 5-chloro-2-fluorophenyl, 2-fluoro-3-trifluoromethylphenyl, 2-fluoro-4-trifluoromethylphenyl, 2-fluoro-5-trifluoromethylphenyl, 2-fluoro-6-trifluoromethylphenyl, 2-chloro-3-trifluoromethylphenyl, 2-chloro-4-trifluoromethylphenyl, 2-chloro-5-trifluoromethylphenyl, 2-chloro-6-trifluoromethylphenyl, 4-fluoro-2-trifluoromethylphenyl, 4-chloro-2-trifluoromethylphenyl, 2-fluoro-3-methylphenyl, 2-fluoro-4-methylphenyl, 2-fluoro-5-methylphenyl, 2-fluoro-6-methylphenyl, 2-chloro-3-methylphenyl, 2-chloro-4-methylphenyl, 2-chloro-5-methylphenyl, 2-chloro-6-methylphenyl, 4-fluoro-2-methylphenyl, 4-chloro-2-methylphenyl, 2,4,6-trifluorophenyl, 2,3,6-trifluorophenyl, 2,3,4-trifluorophenyl, 2,4,6-trichlorophenyl, 2,3,6-trichlorophenyl, 2,3,4-trichlorophenyl, 2,6-difluoro-4-methoxyphenyl, 2,6-difluoro-4-trifluoromethoxyphenyl, 2,6-difluoro-4-trifluoromethylphenyl, 2,6-difluoro-4-cyanophenyl, 2,6-difluoro-4-methylphenyl, 2,6-dichloro-4-methoxyphenyl, 2,6-dichloro-4-trifluoromethoxyphenyl, 2,6-dichloro-4-trifluoromethylphenyl, 2,6-dichloro-4-cyanophenyl, 2,6-dichloro-4-methylphenyl, pentafluorophenyl. Typical examples for optionally substituted heteroaryl include 2-chloro-thiophen-5-yl, 2-bromothiophen-5-yl, 2-methylthiophen-5-yl, 5-chlorothiophen-2-yl, 4-bromo-5-methylthiophen-2-yl, 4-bromothiophen-2-yl, 5-bromothiophen-2-yl, 5-methylthiophen-2-yl, 5-bromofuran-2-yl, 4,5-dimethylfuran-2-yl, 5-methylfuran-2-yl, 5-chlorofuran-2-yl, 3-methylisothiazol-4-yl, 5-methylisoxazol-3-yl, 2-chloropyridin-5-yl, 2-methylpyridin-5-yl, 2-bromopyridin-5-yl, 5-chloropyridin-2-yl, 5-methylpyridin-2-yl, 5-bromopyridin-2-yl, 6-chloropyridin-2-yl, 6-methylpyridin-2-yl, 6-chloropyridin-3-yl, 6-bromopyridin-3-yl, 5-bromopyridin-3-yl, 6-methylpyridin-3-yl, 6-methoxypyridin-3-yl, 5,6-dichloropyridin-3-yl, 2-chloropyridin-4-yl, 2-methylpyridin-4-yl, 2,6-dichloropyridin-4-yl, 2-methylpyrimidin-4-yl.
      In the above definition halogen is fluorine, chlorine, bromine or iodine.
      The alkyl, alkenyl or alkynyl radicals may be straight-chained or branched.
      Alkyl on its own or as part of another substituent is, depending upon the number of carbon atoms mentioned, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl and the isomers thereof, for example, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl or tert-pentyl.
      A haloalkyl group may contain one or more identical or different halogen atoms and, for example, may stand for CH 2Cl, CHCl 2, CCl 3, CH 2F, CHF 2, CF 3, CF 3CH 2, CH 3CF 2, CF 3CF 2 or CCl 3CCl 2.
      Cycloalkyl on its own or as part of another substituent is, depending upon the number of carbon atoms mentioned, for example, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.
      Alkenyl on its own or as part of another substituent is, depending upon the number of carbon atoms mentioned, for example, ethenyl, allyl, 1-propenyl, buten-2-yl, buten-3-yl, penten-1-yl, penten-3-yl, hexen-1-yl or 4-methyl-3-pentenyl.
      Alkynyl on its own or as part of another substituent is, depending upon the number of carbon atoms mentioned, for example, ethynyl, propyn-1-yl, propyn-2-yl, butyn-1-yl, butyn-2-yl, 1-methyl-2-butynyl, hexyn-1-yl or 1-ethyl-2-butynyl.
      The presence of one or more possible asymmetric carbon atoms in a compound of formula I means that the compounds may occur in optically isomeric, that means enantiomeric or diastereomeric forms. As a result of the presence of a possible aliphatic C═C double bond, geometric isomerism, that means cis-trans or (E)-(Z) isomerism may also occur. Also atropisomers may occur as a result of restricted rotation about a single bond. Formula I is intended to include all those possible isomeric forms and mixtures thereof. The present invention intends to include all those possible isomeric forms and mixtures thereof for a compound of formula I.
      In each case, the compounds of formula I according to the invention are in free form or in an agronomically usable salt form.
      In a first embodiment, compounds of formula I according to the invention have R 1 which is hydrogen, C 1-C 6alkyl or C 1-C 6haloalkyl.
      In a second embodiment, compounds of formula I according to the invention have R 2 is cycloalkyl, cycloalkylalkyl, halocycloalkyl, cycloalkoxy, halocycloalkoxy, cycloalkylalkoxy, halocycloalkylalkoxy, alkoxyalkyl, cycloalkoxyalkoxyalkyl, haloalkoxyalkyl, trialkylsilyl, alkylthioalkyl, haloalkylthioalkyl, cycloalkylthio, halocycloalkylthio, cycloalkylalkylthio, halocycloalkylalkylthio, alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl, haloalkylsulfonyl, C 2-C 6alkenyl, C 2-C 6alkynyl, optionally substituted arylsulfonyl, optionally substituted aryloxy, optionally substituted heteroaryloxy, optionally substituted arylthio, optionally substituted heteroarylthio; or

R2 together with an adjacent carbon atom forms an optionally substituted 2- to 7-membered fused ring.

      In a third embodiment, compounds of formula I according to the invention have R 3 which is an optionally substituted phenyl.
      In a fourth embodiment, compounds of formula I according to the invention have R 4 which is halogen, C 1-C 6alkyl, C 1-C 6haloalkyl, C 1-C 6alkoxy, C 1-C 6haloalkoxy, hydroxy or cyano.
      In a fifth embodiment, compounds of formula I according to the invention have wherein n is whole number from 1 to 3.
      Preferred subgroups of compounds of formula I according to the invention are those wherein R 1 is C 1-C 6alkyl or C 1-C 6haloalkyl;

R2 is cycloalkyl, cycloalkylalkyl, halocycloalkyl, cycloalkoxy, cycloalkylalkoxy, alkoxyalkyl, cycloalkoxyalkoxyalkyl, haloalkoxyalkyl, trialkylsilyl, alkylthioalkyl, haloalkylthioalkyl, cycloalkylthio, halocycloalkylthio, cycloalkylalkylthio, halocycloalkylalkylthio, alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl, haloalkylsulfonyl, C2-C6alkenyl, C2-C6alkynyl, optionally substituted arylsulfonyl, optionally substituted aryloxy, optionally substituted heteroaryloxy, optionally substituted arylthio, optionally substituted heteroarylthio; or

R2 together with an adjacent carbon atom forms an optionally substituted 2- to 7-membered aromatic carbocyclic fused ring, an optionally substituted 2- to 7-membered non aromatic carbocyclic fused ring, an optionally substituted 2- to 7-membered aromatic heterocyclic fused ring or an optionally substituted 2- to 7-membered non aromatic heterocyclic fused ring;

R3 is 2-fluorophenyl, 2-chlorophenyl, 2-trifluoromethylphenyl, 2-methylphenyl, 2,3-difluorophenyl, 2,4-difluorophenyl, 2,5-difluorophenyl, 2,6-difluorophenyl, 2,3-dichlorophenyl, 2,4-dichlorophenyl, 2,5-dichlorophenyl, 2,6-dichlorophenyl, 2-chloro-3-fluorophenyl, 2-chloro-4-fluorophenyl, 2-chloro-5-fluorophenyl, 2-chloro-6-fluorophenyl, 3-chloro-2-fluorophenyl, 4-chloro-2-fluorophenyl, 5-chloro-2-fluorophenyl, 2-fluoro-3-trifluoromethylphenyl, 2-fluoro-4-trifluoromethylphenyl, 2-fluoro-5-trifluoromethylphenyl, 2-fluoro-6-trifluoromethylphenyl, 2-chloro-3-trifluoromethylphenyl, 2-chloro-4-trifluoromethylphenyl, 2-chloro-5-trifluoromethylphenyl, 2-chloro-6-trifluoromethylphenyl, 4-fluoro-2-trifluoromethylphenyl, 4-chloro-2-trifluoromethylphenyl, 2-fluoro-3-methylphenyl, 2-fluoro-3-methylphenyl, 2-fluoro-4-methylphenyl, 2-fluoro-5-methylphenyl, 2-fluoro-6-methylphenyl, 2-chloro-3-methylphenyl, 2-chloro-4-methylphenyl, 2-chloro-5-methylphenyl, 2-chloro-6-methylphenyl, 4-fluoro-2-methylphenyl, 4-chloro-2-methylphenyl, 2,4,6-trifluorophenyl, 2,3,6-trifluorophenyl, 2,3,4-trifluorophenyl, 2,4,6-trichlorophenyl, 2,3,6-trichlorophenyl, 2,3,4-trichlorophenyl, 2,6-difluoro-4-methoxyphenyl, 2,6-difluoro-4-trifluoromethoxyphenyl, 2,6-difluoro-4-trifluoromethylphenyl, 2,6-difluoro-4-cyanoyphenyl, 2,6-difluoro-4-cyanoyphenyl, 2,6-difluoro-4-cyanoyphenyl, 2,6-difluoro-4-methylphenyl, 2,6-dichloro-4-methoxyphenyl, 2,6-dichloro-4-methoxyphenyl, 2,6-dichloro-4-methoxyphenyl, 2,6-dichloro-4-trifluoromethoxyphenyl, 2,6-dichloro-4-trifluoromethylphenyl, 2,6-dichloro-4-cyanophenyl, 2,6-dichloro-4-cyanophenyl, 2,6-dichloro-4-cyanophenyl, 2,6-dichloro-4-methylphenyl or pentafluorophenyl;

R4 is halogen, C1-C6alkyl, C1-C6haloalkyl, C1-C6alkoxy, C1-C6haloalkoxy or hydroxy; and

n is a whole number from 1 to 3.

      More preferred subgroups of compounds of formula I according to the invention are those wherein

R1 is C1-C6alkyl;

R2 is cycloalkyl, cycloalkylalkyl, halocycloalkyl, cycloalkoxy, cycloalkylalkoxy, alkoxyalkyl, haloalkoxyalkyl, trialkylsilyl, alkylthioalkyl, haloalkylthioalkyl, cycloalkylthio, cycloalkylalkylthio, halocycloalkylalkylthio, alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl, haloalkylsulfonyl, C2-C6alkenyl, C2-C6alkynyl, optionally substituted arylsulfonyl, optionally substituted aryloxy, optionally substituted heteroaryloxy, optionally substituted arylthio, optionally substituted heteroarylthio; or

R2 together with an adjacent carbon atom forms an optionally substituted 3- to 7-membered aromatic carbocyclic fused ring, an optionally substituted 3- to 7-membered non aromatic carbocyclic fused ring, an optionally substituted 3- to 7-membered aromatic heterocyclic fused ring or an optionally substituted 3- to 7-membered non aromatic heterocyclic fused ring;

R3 is 2-fluorophenyl, 2-chlorophenyl, 2-trifluoromethylphenyl, 2-methylphenyl, 2,3-difluorophenyl, 2,4-difluorophenyl, 2,5-difluorophenyl, 2,6-difluorophenyl, 2,3-dichlorophenyl, 2,4-dichlorophenyl, 2,5-dichlorophenyl, 2,6-dichlorophenyl, 2-chloro-3-fluorophenyl, 2-chloro-4-fluorophenyl, 2-chloro-5-fluorophenyl, 2-chloro-6-fluorophenyl, 3-chloro-2-fluorophenyl; 4-chloro-2-fluorophenyl, 2,4,6-trifluorophenyl, 2,3,6-trifluorophenyl, 2,3,4-trifluorophenyl, 2,4,6-trichlorophenyl, 2,3,6-trichlorophenyl, 2,3,4-trichlorophenyl, 2,6-difluoro-4-methoxyphenyl, 2,6-difluoro-4-trifluoromethoxyphenyl, 2,6-difluoro-4-trifluoromethylphenyl, 2,6-difluoro-4-cyanoyphenyl, 2,6-difluoro-4-cyanoyphenyl, 2,6-difluoro-4-cyanoyphenyl, 2,6-difluoro-4-methylphenyl, 2,6-dichloro-4-methoxyphenyl, 2,6-dichloro-4-methoxyphenyl, 2,6-dichloro-4-methoxyphenyl, 2,6-dichloro-4-trifluoromethoxyphenyl, 2,6-dichloro-4-trifluoromethylphenyl, 2,6-dichloro-4-cyanophenyl, 2,6-dichloro-4-cyanophenyl, 2,6-dichloro-4-cyanophenyl, 2,6-dichloro-4-methylphenyl or pentafluorophenyl;

R4 is halogen, C1-C6alkyl, C1-C6haloalkyl, C1-C6alkoxy or hydroxy;

n is a whole number from 1 to 3.

      Most preferred subgroups of compounds of formula I according to the invention are those wherein

R1 is C1-C3alkyl;

R2 is cycloalkyl, cycloalkylalkyl, halocycloalkyl, cycloalkoxy, cycloalkylalkoxy, alkoxyalkyl, haloalkoxyalkyl, trialkylsilyl, alkylthioalkyl, haloalkylthioalkyl, cycloalkylthio, cycloalkylalkylthio, alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl, haloalkylsulfonyl, optionally substituted arylsulfonyl, optionally substituted aryloxy, optionally substituted heteroaryloxy, optionally substituted arylthio, optionally substituted heteroarylthio; or

R2 together with an adjacent carbon atom forms an optionally substituted 3- to 6-membered aromatic carbocyclic fused ring, an optionally substituted 3- to 6-membered non aromatic carbocyclic fused ring or an optionally substituted 3- to 6-membered aromatic heterocyclic fused ring;

R3 is 2-fluorophenyl, 2-chlorophenyl, 2-trifluoromethylphenyl, 2-methylphenyl, 2,3-difluorophenyl, 2,4-difluorophenyl, 2,5-difluorophenyl, 2,6-difluorophenyl, 2-chloro-3-fluorophenyl, 2-chloro-4-fluorophenyl, 2-chloro-5-fluorophenyl, 2-chloro-6-fluorophenyl, 2,4,6-trifluorophenyl, 2,3,6-trifluorophenyl, 2,3,4-trifluorophenyl;

R4 is halogen, C1-C6alkyl, C1-C6alkoxy or hydroxy; and

n is a whole number from 1 to 2.

      Especially preferred subgroups of compounds of formula I according to the invention are those wherein

R1 is methyl;

R2 is cycloalkoxy, cycloalkylalkoxy, alkylsulfonyl, optionally substituted aryloxy; or

R2 together with an adjacent carbon atom forms an optionally substituted 6-membered aromatic carbocyclic fused ring;

R3 is 2-methylphenyl, 2,6-difluorophenyl, 2-chloro-6-fluorophenyl or 2,4,6-trifluorophenyl;

R4 is fluoro, chloro, methyl, methoxy or hydroxy; and

n is a whole number from 1 to 2.

      Preferred individual compounds are:

3-chloro-5-(4-cyclopropylphenyl)-6-methyl-4-(2,4,6-trifluorophenyl)-pyridazine,

3-chloro-5-(4-methanesulfonylphenyl)-6-methyl-4-(2,4,6-trifluorophenyl)-pyridazine,

3-chloro-6-methyl-5-naphthalen-2-yl-4-(2,4,6-trifluorophenyl)-pyridazine,

3,6-dimethyl-4-naphthalen-2-yl-5-(2,4,6-trifluorophenyl)-pyridazine,

4-(2-chloro-6-fluorophenyl)-3-methoxy-6-methyl-5-naphthalen-2-yl-pyridazine,

4-(2-chloro-6-fluorophenyl)-3,6-dimethyl-5-naphthalen-2-yl-pyridazine,

3-fluoro-6-methyl-5-naphthalen-2-yl-4-(2,4,6-trifluoro-phenyl)-pyridazine,

3-methoxy-6-methyl-5-naphthalen-2-yl-4-(2,4,6-trifluoro-phenyl)-pyridazine,

3-chloro-5-[4-(4-chlorophenoxy)-phenyl]-6-methyl-4-(2,4,6-trifluorophenyl)-pyridazine,

3-chloro-6-methyl-5-(4-phenoxyphenyl)-4-(2,4,6-trifluorophenyl)-pyridazine,

3-chloro-6-methyl-5-(4-phenylsulfanylphenyl)-4-(2,4,6-trifluorophenyl)-pyridazine,

3-chloro-5-[4-(4-chlorophenylsulfanyl)-phenyl]-6-methyl-4-(2,4,6-trifluorophenyl)-pyridazine,

3-chloro-6-methyl-5-(4-trifluoromethanesulfonylphenyl)-4-(2,4,6-trifluorophenyl)-pyridazine,

3-chloro-5-(4-cyclopentyloxyphenyl)-6-methyl-4-(2,4,6-trifluorophenyl)-pyridazine,

3-chloro-5-(4-methoxymethylphenyl)-6-methyl-4-(2,4,6-trifluorophenyl)-pyridazine,

3-chloro-6-methyl-5-(4-methylsulfanylmethylphenyl)-4-(2,4,6-trifluorophenyl)-pyridazine, and

3-chloro-5-(4-cyclopropylmethylphenyl)-6-methyl-4-(2,4,6-trifluorophenyl)-pyridazine.

      Certain pyridazine derivatives with a halogen-, alkyl-, alkoxy-, alkylthio-, nitro- and cyano-substituted phenyl group in position 5 have been proposed for controlling plant-destructive fungi, for example in WO 2005/121104 and WO 2006/001175. However, the action of those preparations is not satisfactory in all aspects of agricultural needs. Surprisingly, with the compounds of formula I, new kinds of fungicides having a high level of biological activity have now been found.
      The compounds of formula I.2, wherein R 1, R 2, R 3 and n are as defined for compound of formula I and R 5 is C 1-C 6alkyl or C 1-C 6haloalkyl, can be obtained by reaction of a compound of formula I.1, wherein R 1, R 2, R 3 and n are as defined for compound of formula I and Hal is halogen, preferably fluorine, chlorine or bromine, with an alcohol R 5OH, wherein R 5 is C 1-C 6alkyl or C 1-C 6haloalkyl, and a base or with a sodium alkoxide NaOR 5, wherein R 5 is C 1-C 6alkyl or C 1-C 6haloalkyl.

( MOL) ( CDX)
      The compounds of formula I.3, wherein R 1, R 2, R 3 and n are as defined for compound of formula I and R 6 is C 1-C 6alkyl, can be obtained by transformation of a compound of formula I.1, wherein R 1, R 2, R 3 and n are as defined for compound of formula I and Hal is halogen, preferably chlorine or bromine, with a Grignard reagent R 6MgHal, wherein R 6 is C 1-C 6alkyl and Hal is halogen, preferably chlorine or bromine, in the presence of a transition metal catalyst.

( MOL) ( CDX)
      The compounds of formula I.4, wherein R 1, R 2, R 3 and n are as defined for compound of formula I, can be obtained by transformation of a compound of formula I.1, wherein R 1, R 2, R 3 and n are as defined for compound of formula I and Hal is halogen, preferably chlorine or bromine, with an inorganic fluoride, e.g. potassium fluoride.

( MOL) ( CDX)
      The compounds of formula I.1, wherein R 1, R 2, R 3 and n are as defined for compound of formula I and Hal is halogen, preferably chlorine or bromine, can be obtained by reaction of a compound of formula I.5, wherein R 1, R 2, R 3 and n are as defined for compound of formula I, with a phosphorus oxyhalide, e.g. phosphorus oxychloride or phosphorus oxybromide, or thionyl halide, e.g. thionyl chloride or thionyl bromide.

( MOL) ( CDX)
      The compounds of formula I.5, wherein R 1, R 2, R 3 and n are as defined for compound of formula I, can be obtained by reaction of a compound of formula II, wherein R 1, R 2, R 3 and n are as defined for compound of formula I, with a hydrazine derivative, e.g. hydrazine hydrate.

( MOL) ( CDX)
      The compounds of formula II, wherein R 1, R 2, R 3 and n are as defined for compound of formula I, can be obtained by oxidation of a compound of formula III, wherein R 1, R 2, R 3 and n are as defined for compound of formula I, with oxygen, air or 3-chloroperbenzoic acid.

( MOL) ( CDX)
      The compounds of formula III, wherein R 1, R 2, R 3 and n are as defined for compound of formula I, can be obtained by reaction of a compound of formula IV, wherein R 1, R 2, R 3 and n are as defined for compound of formula I, with a base, e.g. pyridine, triethylamine, diisopropylethylamine, 1,5-diazabicyclo[4.3.0]non-5-ene or 1,8-diazabicyclo[5.4.0]undec-7-ene.

( MOL) ( CDX)
      The compounds of formula IV, wherein R 1, R 2, R 3 and n are as defined for compound of formula I, can be obtained by reaction of a compound of formula V, wherein R 1, R 2 and n are as defined for compound of formula I and Hal is halogen, preferably chlorine or bromine, with a compound of formula VI, wherein R 3 is as defined for compound of formula I, and a base, e.g. pyridine, triethylamine, diisopropylethylamine, 1,5-diazabicyclo[4.3.0]non-5-ene or 1,8-diazabicyclo[5.4.0]undec-7-ene.

( MOL) ( CDX)
      Surprisingly, it has now been found that the novel compounds of formula I have, for practical purposes, a very advantageous spectrum of activities for protecting plants against diseases that are caused by fungi as well as by bacteria and viruses.
      The compounds of formula I can be used in the agricultural sector and related fields of use as active ingredients for controlling plant pests or on non-living materials for control of spoilage microorganisms or organisms potentially harmful to man. The novel compounds are distinguished by excellent activity at low rates of application, by being well tolerated by plants and by being environmentally safe. They have very useful curative, preventive and systemic properties and are used for protecting numerous cultivated plants. The compounds of formula I can be used to inhibit or destroy the pests that occur on plants or parts of plants (fruit, blossoms, leaves, stems, tubers, roots) of different crops of useful plants, while at the same time protecting also those parts of the plants that grow later e.g. from phytopathogenic microorganisms.
      It is also possible to use compounds of formula I as dressing agents for the treatment of plant propagation material, e.g., seed, such as fruits, tubers or grains, or plant cuttings (for example rice), for the protection against fungal infections as well as against phytopathogenic fungi occurring in the soil. The propagation material can be treated with a composition comprising a compound of formula I before planting: seed, for example, can be dressed before being sown. The active ingredients according to the invention can also be applied to grains (coating), either by impregnating the seeds in a liquid formulation or by coating them with a solid formulation. The composition can also be applied to the planting site when the propagation material is being planted, for example, to the seed furrow during sowing. The invention relates also to such methods of treating plant propagation material and to the plant propagation material so treated.
      Furthermore the compounds according to present invention can be used for controlling fungi in related areas, for example in the protection of technical materials, including wood and wood related technical products, in food storage, in hygiene management.
      In addition, the invention could be used to protect non-living materials from fungal attack, e.g. lumber, wall boards and paint.
      The compounds of formula I are, for example, effective against the phytopathogenic fungi of the following classes: Fungi imperfecti (e.g. Botrytis spp., Alternaria spp.) and Basidiomycetes (e.g. Rhizoctonia spp., Hemileia spp., Puccinia spp., Phakopsora spp., Ustilago spp., Tilletia spp.). Additionally, they are also effective against Ascomycetes (e.g. Venturia spp., Blumeria spp., Podosphaera leucotricha, Monilinia spp., Fusarium spp., Uncinula spp., Mycosphaerella spp., Pyrenophora spp., Rhynchosporium secalis, Magnaporthe spp., Colletotrichum spp., Gaeumannomyces graminis, Tapesia spp., Ramularia spp., Microdochium nivale, Sclerotinia spp.) and Oomycetes (e.g. Phytophthora spp., Pythium spp., Plasmopara spp., Pseudoperonospora cubensis). Outstanding activity has been observed against powdery mildews (e.g. Uncinula necator), rusts (e.g. Puccinia spp.) and leaf spots (e.g. Septoria tritici). Furthermore, the novel compounds of formula I are effective against phytopathogenic bacteria and viruses (e.g. against Xanthomonas spp, Pseudomonas spp, Erwinia amylovora as well as against the tobacco mosaic virus).
      Within the scope of present invention, target crops to be protected typically comprise the following species of plants: cereal (wheat, barley, rye, oat, rice, maize, sorghum and related species); beet (sugar beet and fodder beet); pomes, drupes and soft fruit (apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries and blackberries); leguminous plants (beans, lentils, peas, soybeans); oil plants (rape, mustard, poppy, olives, sunflowers, coconut, castor oil plants, cocoa beans, groundnuts); cucumber plants (pumpkins, cucumbers, melons); fibre plants (cotton, flax, hemp, jute); citrus fruit (oranges, lemons, grapefruit, mandarins); vegetables (spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, paprika); lauraceae (avocado, cinnamomum, camphor) or plants such as tobacco, nuts, coffee, eggplants, sugar cane, tea, pepper, vines, hops, bananas and natural rubber plants, as well as turf and ornamentals.
      The target crops in accordance with the invention include conventional as well as genetically enhanced or engineered varieties such as, for example, insect resistant (e.g. Bt. and VIP varieties) as well as disease resistant, herbicide tolerant (e.g. glyphosate- and glufosinate-resistant maize varieties commercially available under the trade names RoundupReady® and LibertyLink®) and nematode tolerant varieties. By way of example, suitable genetically enhanced or engineered crop varieties include the Stoneville 5599BR cotton and Stoneville 4892BR cotton varieties.
      The compounds of formula I are used in unmodified form or, preferably, together with the adjuvants conventionally employed in the art of formulation. To this end they are conveniently formulated in known manner to emulsifiable concentrates, coatable pastes, directly sprayable or dilutable solutions or suspensions, dilute emulsions, wettable powders, soluble powders, dusts, granulates, and also encapsulations e.g. in polymeric substances. As with the type of the compositions, the methods of application, such as spraying, atomising, dusting, scattering, coating or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances. The compositions may also contain further adjuvants such as stabilizers, antifoams, viscosity regulators, binders or tackifiers as well as fertilizers, micronutrient donors or other formulations for obtaining special effects.
      Suitable carriers and adjuvants can be solid or liquid and are substances useful in formulation technology, e.g. natural or regenerated mineral substances, solvents, dispersants, wetting agents, tackifiers, thickeners, binders or fertilizers. Such carriers are for example described in WO 97/33890.
      The compounds of formula I are normally used in the form of compositions and can be applied to the crop area or plant to be treated, simultaneously or in succession with further compounds. These further compounds can be e.g. fertilizers or micronutrient donors or other preparations, which influence the growth of plants. They can also be selective herbicides or non-selective herbicides as well as insecticides, fungicides, bactericides, nematicides, molluscicides or mixtures of several of these preparations, if desired together with further carriers, surfactants or application promoting adjuvants customarily employed in the art of formulation.
      The compounds of formula I are normally used in the form of fungicidal compositions for controlling or protecting against phytopathogenic microorganisms, comprising as active ingredient at least one compound of formula I, in free form or in agrochemically usable salt form, and at least one of the above-mentioned adjuvants.
      The compounds of formula I can be mixed with other fungicides, resulting in some cases in unexpected synergistic activities. Mixing components which are particularly preferred are:
      Azoles, such as azaconazole, BAY 14120, bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole, epoxiconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imazalil, imibenconazole, ipconazole, metconazole, myclobutanil, pefurazoate, penconazole, prothioconazole, pyrifenox, prochloraz, propiconazole, simeconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triflumizole, triticonazole;
      Pyrimidinyl carbinoles, such as ancymidol, fenarimol, nuarimol;
      2-amino-pyrimidines, such as bupirimate, dimethirimol, ethirimol;
      Morpholines, such as dodemorph, fenpropidine, fenpropimorph, spiroxamine, tridemorph;
      Anilinopyrimidines, such as cyprodinil, mepanipyrim, pyrimethanil;
      Pyrroles, such as fenpiclonil, fludioxonil;
      Phenylamides, such as benalaxyl, furalaxyl, metalaxyl, R-metalaxyl, ofurace, oxadixyl;
      Benzimidazoles, such as benomyl, carbendazim, debacarb, fuberidazole, thiabendazole;
      Dicarboximides, such as chiozolinate, dichlozoline, iprodione, myclozoline, procymidone, vinclozoline;
      Carboxamides, such as boscalid, carboxin, fenfuram, flutolanil, mepronil, oxycarboxin, penthiopyrad, thifluzamide; guanidines, such as guazatine, dodine, iminoctadine;
      Strobilurines, such as azoxystrobin, dimoxystrobin, enestroburin, fluoxastrobin, kresoxim-methyl, metominostrobin, trifloxystrobin, orysastrobin, picoxystrobin, pyraclostrobin;
      Dithiocarbamates, such as ferbam, mancozeb, maneb, metiram, propineb, thiram, zineb, ziram;
      N-halomethylthiotetrahydrophthalimides, such as captafol, captan, dichlofluanid, fluoromides, folpet, tolyfluanid;
      Cu-compounds, such as Bordeaux mixture, copper hydroxide, copper oxychloride, copper sulfate, cuprous oxide, mancopper, oxine-copper;
      Nitrophenol-derivatives, such as dinocap, nitrothal-isopropyl;
      Organo-phosphorus-derivatives, such as edifenphos, iprobenphos, isoprothiolane, phosdiphen, pyrazophos, toiclofos-methyl;
      Pyridazine-derivatives which are known and may be prepared by methods as described in WO 05/121104, WO 06/001175 and WO 07/066601, such as 3-chloro-5-(4-chloro-phenyl)-6-methyl-4-(2,4,6-trifluoro-phenyl)-pyridazine (formula P.1), 3-chloro-6-methyl-5-p-tolyl-4-(2,4,6-trifluoro-phenyl)-pyridazine (formula P.2) and 3-chloro-4-(3-chloro-5-methoxy-pyridin-2-yl)-5-(4-chloro-phenyl)-6-methyl-pyridazine (formula P.3);

( MOL) ( CDX)
      Triazolopyrimidine derivatives which are known and may be prepared by methods as described in WO98/46607, such as 5-chloro-7-(4-methyl-piperidin-1-yl)-6-(2,4,6-trifluoro-phenyl)-[1,2,4]triazolo[1,5-a]pyrimidine (formula T.1);

( MOL) ( CDX)
      Carboxamide derivatives which are known and may be prepared by methods as described in WO04/035589 and in WO06/37632, such as 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid (9-isopropyp-1,2,3,4-tetrahydro-1,4-methano-naphthalen-5-yl)-amide (formula U.1); or

( MOL) ( CDX)
      N-(3′,4′-dichloro-5-fluoro-1,1′-biphenyl-2-yl)-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide (compound F-13)
      Benzamide derivatives which are known and may be prepared by methods as described in WO 2004/016088, such as N-{-2-[3-chloro-5-(trifluoromethyl)-2-pyridinyl]ethyl}-2-trifluoromethylbenzamide, which is also known under the name fluopyram (formula V.1);

( MOL) ( CDX)
      Various others, such as acibenzolar-S-methyl, anilazine, benthiavalicarb, blasticidin-S, chinomethionate, chloroneb, chlorothalonil, cyflufenamid, cymoxanil, dichlone, diclocymet, diclomezine, dicloran, diethofencarb, dimethomorph, flumorph, dithianon, ethaboxam, etridiazole, famoxadone, fenamidone, fenoxanil, fentin, ferimzone, fluazinam, fluopicolide, flusulfamide, fenhexamid, fosetyl-aluminum, hymexazol, iprovalicarb, cyazofamid, kasugamycin, mandipropamid, methasulfocarb, metrafenone, nicobifen, pencycuron, phthalide, polyoxins, probenazole, propamocarb, proquinazid, pyroquilon, quinoxyfen, quintozene, sulfur, tiadinil, triazoxide, tricyclazole, triforine, validamycin, zoxamide and glyphosate.
      Another aspect of invention is related to the use of a compound of formula I, of a composition comprising at least one compound of formula I or of a fungicidal mixture comprising at least one compound of formula I in admixture with other fungicides, as described above, for controlling or preventing infestation of plants, harvested food crops or non-living materials by phytopathogenic microorganisms, preferably fungal organisms.
      A further aspect of invention is related to a method of controlling or preventing an infestation of crop plants or of non-living materials by phytopathogenic or spoilage microorganisms or organisms potentially harmful to man, especially fungal organisms, which comprises the application of a compound of formula I as active ingredient to the plants, to parts of the plants or to the locus thereof, or to any part of the non-living materials. Controlling or preventing means reducing the infestation of crop plants or of non-living materials by phytopathogenic or spoilage microorganisms or organisms potentially harmful to man, especially fungal organisms, to such a level that an improvement is demonstrated.
      A preferred method of controlling or preventing an infestation of crop plants by phytopathogenic microorganisms, especially fungal organisms, which comprises the application of a compound of formula I, or an agrochemical composition which contains at least one of said compounds, is foliar application. The frequency of application and the rate of application will depend on the risk of infestation by the corresponding pathogen. However, the compounds of formula I can also penetrate the plant through the roots via the soil (systemic action) by drenching the locus of the plant with a liquid formulation, or by applying the compounds in solid form to the soil, e.g. in granular form (soil application). In crops of water rice such granulates can be applied to the flooded rice field. The compounds of formula I may also be applied to seeds (coating) by impregnating the seeds or tubers either with a liquid formulation of the fungicide or coating them with a solid formulation.
      A formulation [that is, a composition containing the compound of formula I] and, if desired, a solid or liquid adjuvant or monomers for encapsulating the compound of formula I, is prepared in a known manner, typically by intimately mixing and/or grinding the compound with extenders, for example solvents, solid carriers and, optionally, surface active compounds (surfactants).
      The agrochemical formulations will usually contain from 0.1 to 99% by weight, preferably from 0.1 to 95% by weight, of the compound of formula I, 99.9 to 1% by weight, preferably 99.8 to 5% by weight, of a solid or liquid adjuvant, and from 0 to 25% by weight, preferably from 0.1 to 25% by weight, of a surfactant.
      Advantageous rates of application are normally from 5 g to 2 kg of active ingredient (a.i.) per hectare (ha), preferably from 10 g to 1 kg a.i./ha, most preferably from 20 g to 600 g a.i./ha. When used as seed drenching agent, convenient dosages are from 10 mg to 1 g of active substance per kg of seeds.
      Whereas it is preferred to formulate commercial products as concentrates, the end user will normally use dilute formulations.
      The following non-limiting examples illustrate the above-described invention in more detail.

EXAMPLE 1

This Example Illustrates the Preparation of 3-chloro-6-methyl-5-naphthalen-2-yl-4-(2,4,6-trifluorophenyl)-pyridazine (Compound No. I.ae.198)

a) Preparation of 2-bromo-1-naphthalen-2-yl-propan-1-one

      Bromine (2.2 ml) is added to the mixture of 1-naphthalen-2-yl-propan-1-one (7.6 g), 0.1 ml of hydrobromic acid (48% solution) and 100 ml of acetic acid at 0° C. under a nitrogen atmosphere. Subsequently, the mixture is stirred for 2.0 h at room temperature. The reaction mixture is evaporated under reduced pressure. After chromatography on silica gel, using a mixture of heptane/ethyl acetate 9:1 as eluent, 2-bromo-1-naphthalen-2-yl-propan-1-one is obtained as a yellow oil.

b) Preparation of 5-hydroxy-5-methyl-4-naphthalen-2-yl-3-(2,4,6-trifluorophenyl)-5H-furan-2-one (Compound No. II.ae.040)

      A mixture of 2-bromo-1-naphthalen-2-yl-propan-1-one (3.1 g), 2,4,6-trifluorophenylacetic acid (2.5 g), 1.3 ml of triethylamine and 30 ml of acetonitrile is stirred for 16 h at room temperature. Subsequently 30 ml of acetonitrile and 4.3 ml of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) are added under cooling and stirring is continued for further 3 h. Then air is blown through the reaction mixture for 3 h. An aqueous ammonium chloride solution is added and the mixture is extracted with ethyl acetate. The combined organic layer is washed with a saturated aqueous sodium bicarbonate solution and with brine, dried over sodium sulfate and evaporated under reduced pressure. The remainder is purified by chromatography on silica gel, using a mixture of heptane/ethyl acetate 9:1 as eluent to obtain 5-hydroxy-5-methyl-4-naphthalen-2-yl-3-(2,4,6-trifluorophenyl)-5H-furan-2-one (Compound No. II.ae.040) as colourless crystals, m.p. 164-165° C.

c) Preparation of 6-methyl-5-naphthalen-2-yl-4-(2,4,6-trifluorophenyl)-2H-pyridazin-3-one (Compound No. I.ae.196)

      A mixture of 5-hydroxy-5-methyl-4-naphthalen-2-yl-3-(2,4,6-trifluorophenyl)-5H-furan-2-one (Compound No. II.ae.040, 2.8 g), 0.4 ml of hydrazine hydrate and 30 ml of 1-butanol is heated for 16 h to 120° C. Subsequently, the mixture is cooled to 0° C. The hereby obtained solid is filtered and washed with hexane to obtain 6-methyl-5-naphthalen-2-yl-4-(2,4,6-trifluorophenyl)-2H-pyridazin-3-one (Compound No. I.ae.196) as colourless crystals, m.p. 266-268° C.
      d) A mixture of 6-methyl-5-naphthalen-2-yl-4-(2,4,6-trifluorophenyl)-2H-pyridazin-3-one (Compound No. I.ae.196, 1.8 g) and 7.0 ml of phosphorus oxychloride are mixed and heated at 110° C. for 1 h. After cooling the reaction mixture is evaporated under reduced pressure. The remainder is taken up with ethyl acetate and water and the phases are separated. The organic layer is washed with water and brine, dried over sodium sulfate and evaporated under reduced pressure. The residue is purified by chromatography on silica gel, using a mixture of heptane/ethyl acetate 9:1 as eluent, to deliver 3-chloro-6-methyl-5-naphthalen-2-yl-4-(2,4,6-trifluorophenyl)-pyridazine (Compound No. I.ae.198) as beige crystals (from diethyl ether/hexane), m.p. 86-89° C.

EXAMPLE 2

This Example Illustrates the Preparation of 3-methoxy-6-methyl-5-naphthalen-2-yl-4-(2,4,6-trifluorophenyl)-pyridazine (Compound No. I.ae.199) and 4-(2,6-difluoro-4-methoxyphenyl)-3-methoxy-6-methyl-5-naphthalen-2-yl-pyridazine (Compound No. I.ae.254)

      A mixture of 3-chloro-6-methyl-5-naphthalen-2-y-4-(2,4,6-trifluorophenyl)-pyridazine (Compound No. I.ae.198, 0.9 g), sodium methoxide (30% solution in methanol, 0.7 g) and 10 ml of methanol is heated for 16 h to 60° C. Subsequently the reaction mixture is cooled, diluted with water and extracted with ethyl acetate. The combined organic layer is washed with water and brine, dried over sodium sulfate and evaporated under reduced pressure. The remainder is purified by chromatography on silica gel, using a mixture of hexane/tert.butyl methyl ether 4:1 as eluent to obtain 3-methoxy-6-methyl-5-naphthalen-2-yl-4-(2,4,6-trifluorophenyl)-pyridazine (Compound I.ae.199) as colourless crystals, m.p. 138-140° C. and 4-(2,6-difluoro-4-methoxyphenyl)-3-methoxy-6-methyl-5-naphthalen-2-yl-pyridazine (Compound I.ae.254) as a foam.

EXAMPLE 3

This Example Illustrates the Preparation of 3-fluoro-6-methyl-5-naphthalen-2-yl-4-(2,4,6-trifluorophenyl)-pyridazine (Compound No. I.ae.197)

      A mixture of 3-chloro-6-methyl-5-naphthalen-2-yl-4-(2,4,6-trifluorophenyl)-pyridazine (Compound No. I.ae.198, 0.5 g), potassium fluoride (0.2 g) and 8 ml of dimethyl sulfoxide are mixed and heated to 140° C. for 72 h. Subsequently the reaction mixture is cooled, diluted with water and extracted with ethyl acetate. The combined organic layer is washed with water and brine, dried over sodium sulfate and evaporated under reduced pressure. The remainder is purified by chromatography on silica gel, using a mixture of hexane/ethyl acetate 9:1 as eluent to obtain 3-fluoro-6-methyl-5-naphthalen-2-yl-4-(2,4,6-trifluorophenyl)-pyridazine (Compound No. I.ae.197) as colourless crystals (from diethyl ether/hexane), m.p. 108-110° C.

EXAMPLE 4

This Example Illustrates the Preparation of 3,6-dimethyl-4-naphthalen-2-yl-5-(2,4,6-trifluorophenyl)-pyridazine (Compound No. I.ae.200)

      1.5 ml of a 3 M solution of methylmagnesium bromide in diethyl ether is added slowly to a solution of 3-chloro-6-methyl-5-naphthalen-2-yl-4-(2,4,6-trifluorophenyl)-pyridazine (Compound No. I.ae.198, 0.3 g) and iron(III) acetylacetonate (0.03 g) in 10 ml of tetrahydrofuran and 1.5 ml of 1-methyl-2-pyrrolidinone (NMP) at room temperature. This mixture is stirred for 1.5 h at room temperature. The reaction is quenched with dilute HCl and the aqueous phase is extracted with tert-butyl methyl ether. The combined organic layer is dried over sodium sulfate and evaporated under reduced pressure. The residue is purified by chromatography on silica gel, using a mixture of hexane/ethyl acetate 3:1 as eluent to give 3,6 dimethyl-4-naphthalen-2-yl-5-(2,4,6-trifluorophenyl)-pyridazine (Compound No. I.ae.200) as an oil.
      Tables 1 and 2 below illustrate examples of individual compounds of formula I and formula II according to the invention.
[TABLE-US-00001]
TABLE 1
 
individual compounds of formula I according to the invention
Compound      
No. R1 R3 R4
 
001 CH3 2-fluorophenyl OH
002 CH3 2-fluorophenyl F
003 CH3 2-fluorophenyl Cl
004 CH3 2-fluorophenyl OCH3
005 CH3 2-fluorophenyl CH3
006 CH3 2-chlorophenyl OH
007 CH3 2-chlorophenyl F
008 CH3 2-chlorophenyl Cl
009 CH3 2-chlorophenyl OCH3
010 CH3 2-chlorophenyl CH3
011 CH3 2-trifluoromethylphenyl OH
012 CH3 2-trifluoromethylphenyl F
013 CH3 2-trifluoromethylphenyl Cl
014 CH3 2-trifluoromethylphenyl OCH3
015 CH3 2-trifluoromethylphenyl CH3
016 CH3 2-methylphenyl OH
017 CH3 2-methylphenyl F
018 CH3 2-methylphenyl Cl
019 CH3 2-methylphenyl OCH3
020 CH3 2-methylphenyl CH3
021 CH3 2,3-difluorophenyl OH
022 CH3 2,3-difluorophenyl F
023 CH3 2,3-difluorophenyl Cl
024 CH3 2,3-difluorophenyl OCH3
025 CH3 2,3-difluorophenyl CH3
026 CH3 2,4-difluorophenyl OH
027 CH3 2,4-difluorophenyl F
028 CH3 2,4-difluorophenyl Cl
029 CH3 2,4-difluorophenyl OCH3
030 CH3 2,4-difluorophenyl CH3
031 CH3 2,5-difluorophenyl OH
032 CH3 2,5-difluorophenyl F
033 CH3 2,5-difluorophenyl Cl
034 CH3 2,5-difluorophenyl OCH3
035 CH3 2,5-difluorophenyl CH3
036 CH3 2,6-difluorophenyl OH
037 CH3 2,6-difluorophenyl F
038 CH3 2,6-difluorophenyl Cl
039 CH3 2,6-difluorophenyl OCH3
040 CH3 2,6-difluorophenyl CH3
041 CH3 2,3-dichlorophenyl OH
042 CH3 2,3-dichlorophenyl F
043 CH3 2,3-dichlorophenyl Cl
044 CH3 2,3-dichlorophenyl OCH3
045 CH3 2,3-dichlorophenyl CH3
046 CH3 2,4-dichlorophenyl OH
047 CH3 2,4-dichlorophenyl F
048 CH3 2,4-dichlorophenyl Cl
049 CH3 2,4-dichlorophenyl OCH3
050 CH3 2,4-dichlorophenyl CH3
051 CH3 2,5-dichlorophenyl OH
052 CH3 2,5-dichlorophenyl F
053 CH3 2,5-dichlorophenyl Cl
054 CH3 2,5-dichlorophenyl OCH3
055 CH3 2,5-dichlorophenyl CH3
056 CH3 2,6-dichlorophenyl OH
057 CH3 2,6-dichlorophenyl F
058 CH3 2,6-dichlorophenyl Cl
059 CH3 2,6-dichlorophenyl OCH3
060 CH3 2,6-dichlorophenyl CH3
061 CH3 2-chloro-3-fluorophenyl OH
062 CH3 2-chloro-3-fluorophenyl F
063 CH3 2-chloro-3-fluorophenyl Cl
064 CH3 2-chloro-3-fluorophenyl OCH3
065 CH3 2-chloro-3-fluorophenyl CH3
066 CH3 2-chloro-4-fluorophenyl OH
067 CH3 2-chloro-4-fluorophenyl F
068 CH3 2-chloro-4-fluorophenyl Cl
069 CH3 2-chloro-4-fluorophenyl OCH3
070 CH3 2-chloro-4-fluorophenyl CH3
071 CH3 2-chloro-5-fluorophenyl OH
072 CH3 2-chloro-5-fluorophenyl F
073 CH3 2-chloro-5-fluorophenyl Cl
074 CH3 2-chloro-5-fluorophenyl OCH3
075 CH3 2-chloro-5-fluorophenyl CH3
076 CH3 2-chloro-6-fluorophenyl OH
077 CH3 2-chloro-6-fluorophenyl F
078 CH3 2-chloro-6-fluorophenyl Cl
079 CH3 2-chloro-6-fluorophenyl OCH3
080 CH3 2-chloro-6-fluorophenyl CH3
081 CH3 3-chloro-2-fluorophenyl OH
082 CH3 3-chloro-2-fluorophenyl F
083 CH3 3-chloro-2-fluorophenyl Cl
084 CH3 3-chloro-2-fluorophenyl OCH3
085 CH3 3-chloro-2-fluorophenyl CH3
086 CH3 4-chloro-2-fluorophenyl OH
087 CH3 4-chloro-2-fluorophenyl F
088 CH3 4-chloro-2-fluorophenyl Cl
089 CH3 4-chloro-2-fluorophenyl OCH3
090 CH3 4-chloro-2-fluorophenyl CH3
091 CH3 5-chloro-2-fluorophenyl OH
092 CH3 5-chloro-2-fluorophenyl F
093 CH3 5-chloro-2-fluorophenyl Cl
094 CH3 5-chloro-2-fluorophenyl OCH3
095 CH3 5-chloro-2-fluorophenyl CH3
096 CH3 2-fluoro-3-trifluoromethylphenyl OH
097 CH3 2-fluoro-3-trifluoromethylphenyl F
098 CH3 2-fluoro-3-trifluoromethylphenyl Cl
099 CH3 2-fluoro-3-trifluoromethylphenyl OCH3
100 CH3 2-fluoro-3-trifluoromethylphenyl CH3
101 CH3 2-fluoro-4-trifluoromethylphenyl OH
102 CH3 2-fluoro-4-trifluoromethylphenyl F
103 CH3 2-fluoro-4-trifluoromethylphenyl Cl
104 CH3 2-fluoro-4-trifluoromethylphenyl OCH3
105 CH3 2-fluoro-4-trifluoromethylphenyl CH3
106 CH3 2-fluoro-5-trifluoromethylphenyl OH
107 CH3 2-fluoro-5-trifluoromethylphenyl F
108 CH3 2-fluoro-5-trifluoromethylphenyl Cl
109 CH3 2-fluoro-5-trifluoromethylphenyl OCH3
110 CH3 2-fluoro-5-trifluoromethylphenyl CH3
111 CH3 2-fluoro-6-trifluoromethylphenyl OH
112 CH3 2-fluoro-6-trifluoromethylphenyl F
113 CH3 2-fluoro-6-trifluoromethylphenyl Cl
114 CH3 2-fluoro-6-trifluoromethylphenyl OCH3
115 CH3 2-fluoro-6-trifluoromethylphenyl CH3
116 CH3 2-chloro-3-trifluoromethylphenyl OH
117 CH3 2-chloro-3-trifluoromethylphenyl F
118 CH3 2-chloro-3-trifluoromethylphenyl Cl
119 CH3 2-chloro-3-trifluoromethylphenyl OCH3
120 CH3 2-chloro-3-trifluoromethylphenyl CH3
121 CH3 2-chloro-4-trifluoromethylphenyl OH
122 CH3 2-chloro-4-trifluoromethylphenyl F
123 CH3 2-chloro-4-trifluoromethylphenyl Cl
124 CH3 2-chloro-4-trifluoromethylphenyl OCH3
125 CH3 2-chloro-4-trifluoromethylphenyl CH3
126 CH3 2-chloro-5-trifluoromethylphenyl OH
127 CH3 2-chloro-5-trifluoromethylphenyl F
128 CH3 2-chloro-5-trifluoromethylphenyl Cl
129 CH3 2-chloro-5-trifluoromethylphenyl OCH3
130 CH3 2-chloro-5-trifluoromethylphenyl CH3
131 CH3 2-chloro-6-trifluoromethylphenyl OH
132 CH3 2-chloro-6-trifluoromethylphenyl F
133 CH3 2-chloro-6-trifluoromethylphenyl Cl
134 CH3 2-chloro-6-trifluoromethylphenyl OCH3
135 CH3 2-chloro-6-trifluoromethylphenyl CH3
136 CH3 4-fluoro-2-trifluoromethylphenyl OH
137 CH3 4-fluoro-2-trifluoromethylphenyl F
138 CH3 4-fluoro-2-trifluoromethylphenyl Cl
139 CH3 4-fluoro-2-trifluoromethylphenyl OCH3
140 CH3 4-fluoro-2-trifluoromethylphenyl CH3
141 CH3 4-chloro-2-trifluoromethylphenyl OH
142 CH3 4-chloro-2-trifluoromethylphenyl F
143 CH3 4-chloro-2-trifluoromethylphenyl Cl
144 CH3 4-chloro-2-trifluoromethylphenyl OCH3
145 CH3 4-chloro-2-trifluoromethylphenyl CH3
146 CH3 2-fluoro-3-methylphenyl OH
147 CH3 2-fluoro-3-methylphenyl F
148 CH3 2-fluoro-3-methylphenyl Cl
149 CH3 2-fluoro-3-methylphenyl OCH3
150 CH3 2-fluoro-3-methylphenyl CH3
151 CH3 2-fluoro-4-methylphenyl OH
152 CH3 2-fluoro-4-methylphenyl F
153 CH3 2-fluoro-4-methylphenyl Cl
154 CH3 2-fluoro-4-methylphenyl OCH3
155 CH3 2-fluoro-4-methylphenyl CH3
156 CH3 2-fluoro-5-methylphenyl OH
157 CH3 2-fluoro-5-methylphenyl F
158 CH3 2-fluoro-5-methylphenyl Cl
159 CH3 2-fluoro-5-methylphenyl OCH3
160 CH3 2-fluoro-5-methylphenyl CH3
161 CH3 2-fluoro-6-methylphenyl OH
162 CH3 2-fluoro-6-methylphenyl F
163 CH3 2-fluoro-6-methylphenyl Cl
164 CH3 2-fluoro-6-methylphenyl OCH3
165 CH3 2-fluoro-6-methylphenyl CH3
166 CH3 2-chloro-3-methylphenyl OH
167 CH3 2-chloro-3-methylphenyl F
168 CH3 2-chloro-3-methylphenyl Cl
169 CH3 2-chloro-3-methylphenyl OCH3
170 CH3 2-chloro-3-methylphenyl CH3
171 CH3 2-chloro-4-methylphenyl OH
172 CH3 2-chloro-4-methylphenyl F
173 CH3 2-chloro-4-methylphenyl Cl
174 CH3 2-chloro-4-methylphenyl OCH3
175 CH3 2-chloro-4-methylphenyl CH3
176 CH3 2-chloro-5-methylphenyl OH
177 CH3 2-chloro-5-methylphenyl F
178 CH3 2-chloro-5-methylphenyl Cl
179 CH3 2-chloro-5-methylphenyl OCH3
180 CH3 2-chloro-5-methylphenyl CH3
181 CH3 2-chloro-6-methylphenyl OH
182 CH3 2-chloro-6-methylphenyl F
183 CH3 2-chloro-6-methylphenyl Cl
184 CH3 2-chloro-6-methylphenyl OCH3
185 CH3 2-chloro-6-methylphenyl CH3
186 CH3 4-fluoro-2-methylphenyl OH
187 CH3 4-fluoro-2-methylphenyl F
188 CH3 4-fluoro-2-methylphenyl Cl
189 CH3 4-fluoro-2-methylphenyl OCH3
190 CH3 4-fluoro-2-methylphenyl CH3
191 CH3 4-chloro-2-methylphenyl OH
192 CH3 4-chloro-2-methylphenyl F
193 CH3 4-chloro-2-methylphenyl Cl
194 CH3 4-chloro-2-methylphenyl OCH3
195 CH3 4-chloro-2-methylphenyl CH3
196 CH3 2,4,6-trifluorophenyl OH
197 CH3 2,4,6-trifluorophenyl F
198 CH3 2,4,6-trifluorophenyl Cl
199 CH3 2,4,6-trifluorophenyl OCH3
200 CH3 2,4,6-trifluorophenyl CH3
201 CH3 2,3,6-trifluorophenyl OH
202 CH3 2,3,6-trifluorophenyl F
203 CH3 2,3,6-trifluorophenyl Cl
204 CH3 2,3,6-trifluorophenyl OCH3
205 CH3 2,3,6-trifluorophenyl CH3
206 CH3 2,3,4-trifluorophenyl OH
207 CH3 2,3,4-trifluorophenyl F
208 CH3 2,3,4-trifluorophenyl Cl
209 CH3 2,3,4-trifluorophenyl OCH3
210 CH3 2,3,4-trifluorophenyl CH3
211 CH3 2,4,6-trichlorophenyl OH
212 CH3 2,4,6-trichlorophenyl F
213 CH3 2,4,6-trichlorophenyl Cl
214 CH3 2,4,6-trichlorophenyl OCH3
215 CH3 2,4,6-trichlorophenyl CH3
216 CH3 2,3,6-trichlorophenyl OH
217 CH3 2,3,6-trichlorophenyl F
218 CH3 2,3,6-trichlorophenyl Cl
219 CH3 2,3,6-trichlorophenyl OCH3
220 CH3 2,3,6-trichlorophenyl CH3
221 CH3 2,3,4-trichlorophenyl OH
222 CH3 2,3,4-trichlorophenyl F
223 CH3 2,3,4-trichlorophenyl Cl
224 CH3 2,3,4-trichlorophenyl OCH3
225 CH3 2,3,4-trichlorophenyl CH3
226 CH3 2,6-difluoro-4-methoxyphenyl OH
227 CH3 2,6-difluoro-4-methoxyphenyl F
228 CH3 2,6-difluoro-4-methoxyphenyl Cl
229 CH3 2,6-difluoro-4-methoxyphenyl OCH3
230 CH3 2,6-difluoro-4-methoxyphenyl CH3
231 CH3 2,6-difluoro-4-trifluoromethoxyphenyl OH
232 CH3 2,6-difluoro-4-trifluoromethoxyphenyl F
233 CH3 2,6-difluoro-4-trifluoromethoxyphenyl Cl
234 CH3 2,6-difluoro-4-trifluoromethoxyphenyl OCH3
235 CH3 2,6-difluoro-4-trifluoromethoxyphenyl CH3
236 CH3 2,6-difluoro-4-trifluoromethylphenyl OH
237 CH3 2,6-difluoro-4-trifluoromethylphenyl F
238 CH3 2,6-difluoro-4-trifluoromethylphenyl Cl
239 CH3 2,6-difluoro-4-trifluoromethylphenyl OCH3
240 CH3 2,6-difluoro-4-trifluoromethylphenyl CH3
241 CH3 2,6-difluoro-4-cyanoyphenyl OH
242 CH3 2,6-difluoro-4-cyanoyphenyl F
243 CH3 2,6-difluoro-4-cyanophenyl Cl
244 CH3 2,6-difluoro-4-cyanophenyl OCH3
245 CH3 2,6-difluoro-4-cyanophenyl CH3
246 CH3 2,6-difluoro-4-methylphenyl OH
247 CH3 2,6-difluoro-4-methylphenyl F
248 CH3 2,6-difluoro-4-methylphenyl Cl
249 CH3 2,6-difluoro-4-methylphenyl OCH3
250 CH3 2,6-difluoro-4-methylphenyl CH3
251 CH3 2,6-dichloro-4-methoxyphenyl OH
252 CH3 2,6-dichloro-4-methoxyphenyl F
253 CH3 2,6-dichloro-4-methoxyphenyl Cl
254 CH3 2,6-dichloro-4-methoxyphenyl OCH3
255 CH3 2,6-dichloro-4-methoxyphenyl CH3
256 CH3 2,6-dichloro-4-trifluoromethoxyphenyl OH
257 CH3 2,6-dichloro-4-trifluoromethoxyphenyl F
258 CH3 2,6-dichloro-4-trifluoromethoxyphenyl Cl
259 CH3 2,6-dichloro-4-trifluoromethoxyphenyl OCH3
260 CH3 2,6-dichloro-4-trifluoromethoxyphenyl CH3
261 CH3 2,6-dichloro-4-trifluoromethylphenyl OH
262 CH3 2,6-dichloro-4-trifluoromethylphenyl F
263 CH3 2,6-dichloro-4-trifluoromethylphenyl Cl
264 CH3 2,6-dichloro-4-trifluoromethylphenyl OCH3
265 CH3 2,6-dichloro-4-trifluoromethylphenyl CH3
266 CH3 2,6-dichloro-4-cyanophenyl OH
267 CH3 2,6-dichloro-4-cyanophenyl F
268 CH3 2,6-dichloro-4-cyanophenyl Cl
269 CH3 2,6-dichloro-4-cyanophenyl OCH3
270 CH3 2,6-dichloro-4-cyanophenyl CH3
271 CH3 2,6-dichloro-4-methylphenyl OH
272 CH3 2,6-dichloro-4-methylphenyl F
273 CH3 2,6-dichloro-4-methylphenyl Cl
274 CH3 2,6-dichloro-4-methylphenyl OCH3
275 CH3 2,6-dichloro-4-methylphenyl CH3
276 CH3 pentafluorophenyl OH
277 CH3 pentafluorophenyl F
278 CH3 pentafluorophenyl Cl
279 CH3 pentafluorophenyl OCH3
280 CH3 pentafluorophenyl CH3
 

where

a) 280 compounds of formula (I.a):


( MOL) ( CDX) wherein R 1, R 3 and R 4 are as defined in Table 1.

b) 280 compounds of formula (I.b):


( MOL) ( CDX) wherein R 1, R 3 and R 4 are as defined in Table 1.

c) 280 compounds of formula (I.c):


( MOL) ( CDX) wherein R 1, R 3 and R 4 are as defined in Table 1.

d) 280 compounds of formula (I.d):


( MOL) ( CDX) wherein R 1, R 3 and R 4 are as defined in Table 1.

e) 280 compounds of formula (I.e):


( MOL) ( CDX) wherein R 1, R 3 and R 4 are as defined in Table 1.

f) 280 compounds of formula (I.f):


( MOL) ( CDX) wherein R 1, R 3 and R 4 are as defined in Table 1.

g) 280 compounds of formula (I.g):


( MOL) ( CDX) wherein R 1, R 3 and R 4 are as defined in Table 1.

h) 280 compounds of formula (I.h):


( MOL) ( CDX) wherein R 1, R 3 and R 4 are as defined in Table 1.

i) 280 compounds of formula (I.i):


( MOL) ( CDX) wherein R 1, R 3 and R 4 are as defined in Table 1.

j) 280 compounds of formula (I.j):


( MOL) ( CDX) wherein R 1, R 3 and R 4 are as defined in Table 1.

k) 280 compounds of formula (I.k):


( MOL) ( CDX) wherein R 1, R 3 and R 4 are as defined in Table 1.

l) 280 compounds of formula (I.l):


( MOL) ( CDX) wherein R 1, R 3 and R 4 are as defined in Table 1.

m) 280 compounds of formula (I.m):


( MOL) ( CDX) wherein R 1, R 3 and R 4 are as defined in Table 1.

n) 280 compounds of formula (I.n):


( MOL) ( CDX) wherein R 1, R 3 and R 4 are as defined in Table 1.

o) 280 compounds of formula (I.o):


( MOL) ( CDX) wherein R 1, R 3 and R 4 are as defined in Table 1.

p) 280 compounds of formula (I.p):


( MOL) ( CDX) wherein R 1, R 3 and R 4 are as defined in Table 1.

q) 280 compounds of formula (I.q):


( MOL) ( CDX) wherein R 1, R 3 and R 4 are as defined in Table 1.

r) 280 compounds of formula (I.r):


( MOL) ( CDX) wherein R 1, R 3 and R 4 are as defined in Table 1.

s) 280 compounds of formula (I.s):


( MOL) ( CDX) wherein R 1, R 3 and R 4 are as defined in Table 1.

t) 280 compounds of formula (I.t):


( MOL) ( CDX) wherein R 1, R 3 and R 4 are as defined in Table 1.

u) 280 compounds of formula (I.u):


( MOL) ( CDX) wherein R 1, R 3 and R 4 are as defined in Table 1.

v) 280 compounds of formula (I.v):


( MOL) ( CDX) wherein R 1, R 3 and R 4 are as defined in Table 1.

w) 280 compounds of formula (I.w):


( MOL) ( CDX) wherein R 1, R 3 and R 4 are as defined in Table 1.

x) 280 compounds of formula (I.x):


( MOL) ( CDX) wherein R 1, R 3 and R 4 are as defined in Table 1.

y) 280 compounds of formula (I.y):


( MOL) ( CDX) wherein R 1, R 3 and R 4 are as defined in Table 1.

z) 280 compounds of formula (I.z):


( MOL) ( CDX) wherein R 1, R 3 and R 4 are as defined in Table 1.

aa) 280 compounds of formula (I.aa):


( MOL) ( CDX) wherein R 1, R 3 and R 4 are as defined in Table 1.

ab) 280 compounds of formula (I.ab):


( MOL) ( CDX) wherein R 1, R 3 and R 4 are as defined in Table 1.

ac) 280 compounds of formula (I.ac):


( MOL) ( CDX) wherein R 1, R 3 and R 4 are as defined in Table 1.

ad) 280 compounds of formula (I.ad):


( MOL) ( CDX) wherein R 1, R 3 and R 4 are as defined in Table 1.

ae) 280 compounds of formula (I.ae):


( MOL) ( CDX) wherein R 1, R 3 and R 4 are as defined in Table 1.

af) 280 compounds of formula (I.af):


( MOL) ( CDX) wherein R 1, R 3 and R 4 are as defined in Table 1.

ag) 280 compounds of formula (I.ag):


( MOL) ( CDX) wherein R 1, R 3 and R 4 are as defined in Table 1.

ah) 280 compounds of formula (I.ah):


( MOL) ( CDX) wherein R 1, R 3 and R 4 are as defined in Table 1.

ai) 280 compounds of formula (I.ai):


( MOL) ( CDX) wherein R 1, R 3 and R 4 are as defined in Table 1.

aj) 280 compounds of formula (I.aj):


( MOL) ( CDX) wherein R 1, R 3 and R 4 are as defined in Table 1.

ak) 280 compounds of formula (I.ak):


( MOL) ( CDX) wherein R 1, R 3 and R 4 are as defined in Table 1.

al) 280 compounds of formula (I.al):


( MOL) ( CDX) wherein R 1, R 3 and R 4 are as defined in Table 1.

am) 280 compounds of formula (I.am):


( MOL) ( CDX) wherein R 1, R 3 and R 4 are as defined in Table 1.

an) 280 compounds of formula (I.an):


( MOL) ( CDX) wherein R 1, R 3 and R 4 are as defined in Table 1.

ao) 280 compounds of formula (I.ao):


( MOL) ( CDX) wherein R 1, R 3 and R 4 are as defined in Table 1.

ap) 280 compounds of formula (I.ap):


( MOL) ( CDX) wherein R 1, R 3 and R 4 are as defined in Table 1.

aq) 280 compounds of formula (I.aq):


( MOL) ( CDX) wherein R 1, R 3 and R 4 are as defined in Table 1.

ar) 280 compounds of formula (I.ar):


( MOL) ( CDX) wherein R 1, R 3 and R 4 are as defined in Table 1.

as) 280 compounds of formula (I.as):


( MOL) ( CDX) wherein R 1, R 3 and R 4 are as defined in Table 1.

at) 280 compounds of formula (I.at):


( MOL) ( CDX) wherein R 1, R 3 and R 4 are as defined in Table 1.

au) 280 compounds of formula (I.au):


( MOL) ( CDX) wherein R 1, R 3 and R 4 are as defined in Table 1.

av) 280 compounds of formula (I.av):


( MOL) ( CDX) wherein R 1, R 3 and R 4 are as defined in Table 1.

aw) 280 compounds of formula (I.aw):


( MOL) ( CDX) wherein R 1, R 3 and R 4 are as defined in Table 1.

ax) 280 compounds of formula (I.ax):


( MOL) ( CDX) wherein R 1, R 3 and R 4 are as defined in Table 1.

ay) 280 compounds of formula (I.ay):


( MOL) ( CDX) wherein R 1, R 3 and R 4 are as defined in Table 1.

az) 280 compounds of formula (I.az):


( MOL) ( CDX) wherein R 1, R 3 and R 4 are as defined in Table 1.
[TABLE-US-00002]
TABLE 2
 
individual compounds of formula II according to the invention
Compound    
No. R1 R3
 
001 CH3 2-fluorophenyl
002 CH3 2-chlorophenyl
003 CH3 2-trifluoromethylphenyl
004 CH3 2-methylphenyl
005 CH3 2,3-difluorophenyl
006 CH3 2,4-difluorophenyl
007 CH3 2,5-difluorophenyl
008 CH3 2,6-difluorophenyl
009 CH3 2,3-dichlorophenyl
010 CH3 2,4-dichlorophenyl
011 CH3 2,5-dichlorophenyl
012 CH3 2,6-dichlorophenyl
013 CH3 2-chloro-3-fluorophenyl
014 CH3 2-chloro-4-fluorophenyl
015 CH3 2-chloro-5-fluorophenyl
016 CH3 2-chloro-6-fluorophenyl
017 CH3 3-chloro-2-fluorophenyl
018 CH3 4-chloro-2-fluorophenyl
019 CH3 5-chloro-2-fluorophenyl
020 CH3 2-fluoro-3-trifluoromethylphenyl
021 CH3 2-fluoro-4-trifluoromethylphenyl
022 CH3 2-fluoro-5-trifluoromethylphenyl
023 CH3 2-fluoro-6-trifluoromethylphenyl
024 CH3 2-chloro-3-trifluoromethylphenyl
025 CH3 2-chloro-4-trifluoromethylphenyl
026 CH3 2-chloro-5-trifluoromethylphenyl
027 CH3 2-chloro-6-trifluoromethylphenyl
028 CH3 4-fluoro-2-trifluoromethylphenyl
029 CH3 4-chloro-2-trifluoromethylphenyl
030 CH3 2-fluoro-3-methylphenyl
031 CH3 2-fluoro-4-methylphenyl
032 CH3 2-fluoro-5-methylphenyl
033 CH3 2-fluoro-6-methylphenyl
034 CH3 2-chloro-3-methylphenyl
035 CH3 2-chloro-4-methylphenyl
036 CH3 2-chloro-5-methylphenyl
037 CH3 2-chloro-6-methylphenyl
038 CH3 4-fluoro-2-methylphenyl
039 CH3 4-chloro-2-methylphenyl
040 CH3 2,4,6-trifluorophenyl
041 CH3 2,3,6-trifluorophenyl
042 CH3 2,3,4-trifluorophenyl
043 CH3 2,4,6-trichlorophenyl
044 CH3 2,3,6-trichlorophenyl
045 CH3 2,3,4-trichlorophenyl
046 CH3 2,6-difluoro-4-methoxyphenyl
047 CH3 2,6-difluoro-4-trifluoromethoxyphenyl
048 CH3 2,6-difluoro-4-trifluoromethylphenyl
049 CH3 2,6-difluoro-4-cyanoyphenyl
050 CH3 2,6-difluoro-4-methylphenyl
051 CH3 2,6-dichloro-4-methoxyphenyl
052 CH3 2,6-dichloro-4-trifluoromethoxyphenyl
053 CH3 2,6-dichloro-4-trifluoromethylphenyl
054 CH3 2,6-dichloro-4-cyanophenyl
055 CH3 2,6-dichloro-4-methylphenyl
056 CH3 pentafluorophenyl
 

where

a) 56 compounds of formula (II.a):


( MOL) ( CDX) wherein R 1 and R 3 are as defined in Table 2.

b) 56 compounds of formula (II.b):


( MOL) ( CDX) wherein R 1 and R 3 are as defined in Table 2.

c) 56 compounds of formula (II.c):


( MOL) ( CDX) wherein R 1 and R 3 are as defined in Table 2.

d) 56 compounds of formula (II.d):


( MOL) ( CDX) wherein R 1 and R 3 are as defined in Table 2.

e) 56 compounds of formula (II.e):


( MOL) ( CDX) wherein R 1 and R 3 are as defined in Table 2.

f) 56 compounds of formula (II.f):


( MOL) ( CDX) wherein R 1 and R 3 are as defined in Table 2.

g) 56 compounds of formula (II.g):


( MOL) ( CDX) wherein R 1 and R 3 are as defined in Table 2.

h) 56 compounds of formula (II.h):


( MOL) ( CDX) wherein R 1 and R 3 are as defined in Table 2.

i) 56 compounds of formula (II.i):


( MOL) ( CDX) wherein R 1 and R 3 are as defined in Table 2.

j) 56 compounds of formula (II.j):


( MOL) ( CDX) wherein R 1 and R 3 are as defined in Table 2.

k) 56 compounds of formula (II.k):


( MOL) ( CDX) wherein R 1 and R 3 are as defined in Table 2.

l) 56 compounds of formula (II.l):


( MOL) ( CDX) wherein R 1 and R 3 are as defined in Table 2.

m) 56 compounds of formula (II.m):


( MOL) ( CDX) wherein R 1 and R 3 are as defined in Table 2.

n) 56 compounds of formula (II.n):


( MOL) ( CDX) wherein R 1 and R 3 are as defined in Table 2.

o) 56 compounds of formula (II.o):


( MOL) ( CDX) wherein R 1 and R 3 are as defined in Table 2.

p) 56 compounds of formula (II.p):


( MOL) ( CDX) wherein R 1 and R 3 are as defined in Table 2.

q) 56 compounds of formula (II.q):


( MOL) ( CDX) wherein R 1 and R 3 are as defined in Table 2.

r) 56 compounds of formula (II.r):


( MOL) ( CDX) wherein R 1 and R 3 are as defined in Table 2.

s) 56 compounds of formula (II.s):


( MOL) ( CDX) wherein R 1 and R 3 are as defined in Table 2.

t) 56 compounds of formula (II.t):


( MOL) ( CDX) wherein R 1 and R 3 are as defined in Table 2.

u) 56 compounds of formula (II.u):


( MOL) ( CDX) wherein R 1 and R 3 are as defined in Table 2.

v) 56 compounds of formula (II.v):


( MOL) ( CDX) wherein R 1 and R 3 are as defined in Table 2.

w) 56 compounds of formula (II.w):


( MOL) ( CDX) wherein R 1 and R 3 are as defined in Table 2.

x) 56 compounds of formula (II.x):


( MOL) ( CDX) wherein R 1 and R 3 are as defined in Table 2.

y) 56 compounds of formula (II.y):


( MOL) ( CDX) wherein R 1 and R 3 are as defined in Table 2.

z) 56 compounds of formula (II.z):


( MOL) ( CDX) wherein R 1 and R 3 are as defined in Table 2.

aa) 56 compounds of formula (II.aa):


( MOL) ( CDX) wherein R 1 and R 3 are as defined in Table 2.

ab) 56 compounds of formula (II.ab):


( MOL) ( CDX) wherein R 1 and R 3 are as defined in Table 2.

ac) 56 compounds of formula (II.ac):


( MOL) ( CDX) wherein R 1 and R 3 are as defined in Table 2.

ad) 56 compounds of formula (II.ad):


( MOL) ( CDX) wherein R 1 and R 3 are as defined in Table 2.

ae) 56 compounds of formula (II.ae):


( MOL) ( CDX) wherein R 1 and R 3 are as defined in Table 2.

af) 56 compounds of formula (II.af):


( MOL) ( CDX) wherein R 1 and R 3 are as defined in Table 2.

ag) 56 compounds of formula (II.ag):


( MOL) ( CDX) wherein R 1 and R 3 are as defined in Table 2.

ah) 56 compounds of formula (II.ah):


( MOL) ( CDX) wherein R 1 and R 3 are as defined in Table 2.

ai) 56 compounds of formula (II.ai):


( MOL) ( CDX) wherein R 1 and R 3 are as defined in Table 2.

aj) 56 compounds of formula (II.aj):


( MOL) ( CDX) wherein R 1 and R 3 are as defined in Table 2.

ak) 56 compounds of formula (II.ak):


( MOL) ( CDX) wherein R 1 and R 3 are as defined in Table 2.

al) 56 compounds of formula (II.al):


( MOL) ( CDX) wherein R 1 and R 3 are as defined in Table 2.

am) 56 compounds of formula (II.am):


( MOL) ( CDX) wherein R 1 and R 3 are as defined in Table 2.

an) 56 compounds of formula (II.an):


( MOL) ( CDX) wherein R 1 and R 3 are as defined in Table 2.

ao) 56 compounds of formula (II.ao):


( MOL) ( CDX) wherein R 1 and R 3 are as defined in Table 2.

ap) 56 compounds of formula (II.ap):


( MOL) ( CDX) wherein R 1 and R 3 are as defined in Table 2.

aq) 56 compounds of formula (II.aq):


( MOL) ( CDX) wherein R 1 and R 3 are as defined in Table 2.

ar) 56 compounds of formula (II.ar):


( MOL) ( CDX) wherein R 1 and R 3 are as defined in Table 2.

as) 56 compounds of formula (II.as):


( MOL) ( CDX) wherein R 1 and R 3 are as defined in Table 2.

at) 56 compounds of formula (II.at):


( MOL) ( CDX) wherein R 1 and R 3 are as defined in Table 2.

au) 56 compounds of formula (II.au):


( MOL) ( CDX) wherein R 1 and R 3 are as defined in Table 2.

av) 56 compounds of formula (II.av):


( MOL) ( CDX) wherein R 1 and R 3 are as defined in Table 2.

aw) 56 compounds of formula (II.aw):


( MOL) ( CDX) wherein R 1 and R 3 are as defined in Table 2.

ax) 56 compounds of formula (II.ax):


( MOL) ( CDX) wherein R 1 and R 3 are as defined in Table 2.

ay) 56 compounds of formula (II.ay):


( MOL) ( CDX) wherein R 1 and R 3 are as defined in Table 2.

az) 56 compounds of formula (II.az):


( MOL) ( CDX) wherein R 1 and R 3 are as defined in Table 2.
      Throughout this description, temperatures are given in degrees Celsius, m.p. means melting point and “%” is percent by weight, unless corresponding concentrations are indicated in other units.
      Table 3 shows selected melting point for compounds of Tables 1 and 2.
[TABLE-US-00003]
TABLE 3
 
Melting point for compounds of Tables 1 and 2
  Compound  
  Number m.p. (° C.)
   
  I.f.196 196-198
  I.q.196 273-275
  I.t.196 297-298
  I.t.198 210-211
  I.ac.196 224-226
  I.ac.197 109-112
  I.ac.199 124-127
  I.ae.076 285-287
  I.ae.079 182-184
  I.ae.080 120-123
  I.ae.196 266-268
  I.ae.197 108-110
  I.ae.198 86-89
  I.ae.199 138-140
  II.f.040 150-152
  II.q.040 170-171
  II.t.040 220-222
  II.ae.016 170-172
  II.ae.040 164-165
   
      The compounds according to the present invention can be prepared according to the above-mentioned reaction schemes, in which, unless otherwise stated, the definition of each variable is as defined above for a compound of formula (I).

BIOLOGICAL EXAMPLES

       Alternaria Solani/Tomato/Preventive (Action Against Alternaria on Tomato)
      4 weeks old tomato plants cv. Roter Gnom are treated with the formulated test compound in a spray chamber. Two days after application tomato plants are inoculated by spraying a spore suspension on the test plants. After an incubation period of 4 days at 22° C./18° C. and 95% r. h. in a greenhouse the disease incidence is assessed.
      Compounds of formula I according to the invention, in particular compounds I.t.198, I.ac.197, I.ae.080, I.ae.198 and I.ae.199 at 200 ppm inhibit fungal infestation in this test to at least 80%, while under the same conditions untreated control plants are infected by the phytopathogenic fungi to over 80%.
       Botrytis Cinerea/Tomato/Preventive (Action Against Botrytis on Tomato)
      4 weeks old tomato plants cv. Roter Gnom are treated with the formulated test compound in a spray chamber. Two days after application tomato plants are inoculated by spraying a spore suspension on the test plants. After an incubation period of 3 days at 20° C. and 95% r. h. in a greenhouse the disease incidence is assessed.
      Compounds of formula I according to the invention, in particular compounds I.ac.197, I.ac.199, I.ae.079, I.ae.197, I.ae.198 and I.ae.199 at 200 ppm inhibit fungal infestation in this test to at least 80%, while under the same conditions untreated control plants are infected by the phytopathogenic fungi to over 80%.
       Puccinia Recondita/Wheat/Preventive (Action Against Brown Rust on Wheat)
      1 week old wheat plants cv. Arina are treated with the formulated test compound in a spray chamber. One day after application wheat plants are inoculated by spraying a spore suspension (1×105 uredospores/ml) on the test plants. After an incubation period of 1 day at 20° C. and 95% r. h. plants are kept for 10 days 20° C./18° C. (day/night) and 60% r.h. in a greenhouse. The disease incidence is assessed 11 days after inoculation.
      Compounds of formula I according to the invention, in particular compounds I.ac.197, I.ae.197 and I.ae.198 at 200 ppm inhibits fungal infestation in this test to at least 80%, while under the same conditions untreated control plants are infected by the phytopathogenic fungi to over 80%.
       Magnaporthe Grisea ( Pyricularia Oryzae)/Rice/Preventive (Action Against Rice Blast)
      3 weeks old rice plants cv. Koshihikari are treated with the formulated test compound in a spray chamber. Two days after application rice plants are inoculated by spraying a spore suspension (1×10 5 conidia/ml) on the test plants. After an incubation period of 6 days at 25° C. and 95% r. h. the disease incidence is assessed.
      Compounds of formula I according to the invention, in particular compounds I.t.198, I.ac.199, I.ae.079, I.ae.080, I.ae.197 and I.ae.198 at 200 ppm inhibit fungal infestation in this test to at least 80%, while under the same conditions untreated control plants are infected by the phytopathogenic fungi to over 80%.
       Pyrenophora Teres ( Helminthosporium Teres)/Barley/Preventive (Action Against Net Blotch on Barley)
      1-week-old barley plants cv. Regina are treated with the formulated test compound in a spray chamber. Two days after application barley plants are inoculated by spraying a spore suspension (2.6×10 4 conidia/ml) on the test plants. After an incubation period of 4 days at 20° C. and 95% r. h. the disease incidence is assessed.
      Compounds of formula I according to the invention, in particular compounds I.t.198, I.ac.197, I.ae.197, I.ae.198 and I.ae.199 at 200 ppm inhibit fungal infestation in this test to at least 80%, while under the same conditions untreated control plants are infected by the phytopathogenic fungi to over 80%.
       Septoria Tritici/Wheat/Preventive (Action Against Septoria Leaf Spot on Wheat)
      2 weeks old wheat plants cv. Riband are treated with the formulated test compound in a spray chamber. One day after application wheat plants are inoculated by spraying a spore suspension (10 6 conidia/ml) on the test plants. After an incubation period of 1 day at 22° C./21° C. and 95% r. h. plants are kept at 22° C./21° C. and 70% r.h. in a greenhouse. The disease incidence is assessed 16-18 days after inoculation.
      Compounds of formula I according to the invention, in particular compounds I.ac.197, I.ac.199, I.ae.080, I.ae.197 and I.ae.198 at 200 ppm inhibits fungal infestation in this test to at least 80%, while under the same conditions untreated control plants are infected by the phytopathogenic fungi to over 80%.
       Uncinula Necator/Grape/Preventive (Action Against Powdery Mildew on Grape)
      5 weeks old grape seedlings cv. Gutedel are treated with the formulated test compound in a spray chamber. One day after application grape plants are inoculated by shaking plants infected with grape powdery mildew above the test plants. After an incubation period of 7 days at 24° C./22° C. and 70% r. h. under a light regime of 14/10 h (light/dark) the disease incidence is assessed.
      Compounds of formula I according to the invention, in particular compounds I.ac.197, I.ac.199, I.ae.079, I.ae.198 and I.ae.199 at 200 ppm inhibit fungal infestation in this test to at least 80%, while under the same conditions untreated control plants are infected by the phytopathogenic fungi to over 80%.