DE19938737A1 - Aminosalicylic acid amides - Google Patents

Abstract

The invention relates to known and novel acylaminosalicylic acid amides, to several methods for producing them and to their use for combating organisms that are harmful to plants, and to novel intermediate products and methods for producing the same.

Description

The invention relates to known and new acylaminosalicylic acid amides, several Processes for their preparation and their use for controlling plants harmful organisms, as well as new intermediates and processes for their Manufacturing.

Certain aminosalicylic acid amides, as well as their fungicidal activity, are already available become known (compare, for example, WO 97-08135 or WO 98-41513). The effect However, these previously known compounds are particularly inexpensive quantities and concentrations are not completely satisfied in all areas of application posed.

It has now been found that the acylaminosalicylic acid amides of the general formula (I)

in which
R ^{1 represents} hydrogen or alkyl,
R ^{2 represents} hydrogen or alkyl, or
R ³ for a grouping

stands in what
A represents oxygen, sulfur or - (NR ⁹ ) -, in which
R ^{9 represents} hydrogen or alkyl or, together with R ⁶ and the nitrogen atom to which they are attached, forms an optionally substituted heterocyclic ring,
R ^{4 represents} hydrogen, optionally substituted alkyl or optionally substituted aryl or
R ² and R ⁴ together with the nitrogen atom to which they are attached form a heterocyclic ring,
R ^{5 represents} hydrogen or alkyl or
R ⁴ and R ⁵ together with the carbon atom to which they are attached form a carbocyclic ring,
R ^{6 represents} hydrogen or in each case optionally substituted alkyl, cycloalkyl, aryl or heterocyclyl,
R ^{7 represents} hydrogen or alkyl,
R ^{8 represents} hydrogen or alkyl and
Z represents hydrogen or in each case optionally substituted alkyl, alkylcarbonyl, cycloalkyl, cycloalkylcarbonyl, aryl, arylcarbonyl, heterocyclyl or heterocyclylcarbonyl,
are suitable for controlling organisms that cause plant damage and damage to technical materials.

In the definitions are the hydrocarbon chains, such as alkyl, alkylene, alkenyl or alkynyl, also in combination with heteroatoms, such as in alkoxy, alkylthio or Alkylamino, each straight-chain or branched. Are preferred if not different indicated, hydrocarbon chains with 1 to 6 carbon atoms.

Halogen generally represents fluorine, chlorine, bromine or iodine, preferably Fluorine, chlorine or bromine, especially for fluorine or chlorine.

Aryl stands for aromatic, mono or polycyclic hydrocarbon rings, such as e.g. As phenyl, naphthyl, anthranyl, phenanthryl, preferably for phenyl or Naphthyl, especially for phenyl.

Heterocyclyl stands for saturated or unsaturated, as well as aromatic, ring-shaped Connections with up to eight ring links, in which at least one ring link Heteroatom, i. H. is an atom other than carbon. Contains the ring several heteroatoms, these can be the same or different. Are heteroatoms preferably oxygen, nitrogen or sulfur. If the ring contains several acids atoms of matter, these are not directly adjacent. If necessary, form the ring shaped compounds with other carbocyclic or heterocyclic, ankon dense or bridged rings together form a polycyclic ring system. Mono- or bicyclic ring systems are preferred, in particular mono- or bicyclic, aromatic ring systems.  

Cycloalkyl stands for saturated, carbocyclic, ring-shaped compounds which optionally with other carbocyclic, fused or bridged Rings form a polycyclic ring system.

Cycloalkenyl stands for carbocyclic, ring-shaped compounds that at least contain a double bond and optionally with other carbocyclic, fused or bridged rings form a polycyclic ring system.

Haloalkoxy stands for partially or completely halogenated alkyl. With multiple halogenated haloalkoxy, the halogen atoms may be the same or different his. Preferred halogen atoms are fluorine or chlorine, especially fluorine. Wearing that Haloalkoxy and other substituents, the maximum possible is reduced Number of halogen atoms on the different free valences.

Haloalkyl stands for partially or completely halogenated alkyl. With multiple halogenated haloalkyl, the halogen atoms may be the same or different. Preferred halogen atoms are fluorine, or chlorine, especially fluorine. Wearing that Haloalkyl or other substituents, the maximum possible number is reduced of the halogen atoms to the different free valences.

The compounds of formula (I) are optionally different as mixtures their possible isomeric forms, especially stereoisomers, such as. B. E- and Z, threo and erythro, as well as optical isomers. Both the Use of the E and the Z isomers, as well as the threo and erythro, and the optical isomers and any mixtures of these isomers.

Preferred is the use of compounds of formula (I) in which
R ^{1 represents} hydrogen or methyl,
R ^{2 represents} hydrogen or C ₁ -C ₄ alkyl and
R ³ for a grouping

stands in what
A represents oxygen, sulfur or - (NR ⁹ ) -, in which
R ^{9 represents} hydrogen or alkyl having 1 to 4 carbon atoms or, together with R ⁶ and the nitrogen atom to which they are bonded, forms a heterocyclic ring with 3 to 7 ring members optionally substituted by C ₁ -C ₄ alkyl,
R ^{4 represents} hydrogen or optionally substituted by hydroxyl, formyloxy, optionally substituted arylcarbonyloxy or alkoxy, alkylthio, alkoxycarbonyl or alkylcarbonyloxy each having 1 to 6 carbon atoms in the alkyl part substituted alkyl or optionally substituted aryl, or heterocyclyl part aryl, heterocyclyl, optionally substituted in the aryl part, Arylalkyl or heterocyclylalkyl each having 1 to 6 carbon atoms in the alkyl part or
R ² and R ⁴ together with the nitrogen atom to which they are attached form a heterocyclic ring with 3 to 6 ring members,
R ^{5 represents} hydrogen or C ₁ -C ₄ alkyl or
R ⁴ and R ⁵ together with the carbon atom to which they are attached form a carbocyclic ring with 3 to 6 ring members,
R ⁶ for hydrogen or C ₁ -C ₁₂ alkyl, optionally substituted by C ₁ -C ₄ alkyl substituted C ₃ -C ₇ cycloalkyl, each optionally substituted in the aryl or heterocyclyl part aryl, arylalkyl with 1 to 6 carbon atoms in Alkyl part, heterocyclyl or heterocyclylalkyl having 1 to 6 carbon atoms in the alkyl part,
R ^{7 represents} hydrogen or C ₁ -C ₄ alkyl,
R ^{8 represents} hydrogen or C ₁ -C ₄ alkyl and
Z represents hydrogen or C ₁ -C ₁₂ alkyl or alkylcarbonyl, optionally substituted by C ₁ -C ₄ alkyl substituted C ₃ -C ₇ cycloalkyl or cycloalkyl carbonyl, in each case optionally substituted aryl, arylcarbonyl, arylalkyl in the aryl or heterocyclyl part , Arylalkylcarbonyl having 1 to 6 carbon atoms in the alkyl part, heterocyclyl, heterocyclylcarbonyl, heterocyclylalkyl or heterocyclylalkylcarbonyl having 1 to 6 carbon atoms in the alkyl part.

Preferred substituents for aryl or arylalkyl are listed in the following:
Halogen, cyano, amino, hydroxy, formyl, carboxy, carbamoyl, thiocarbamoyl;
in each case straight-chain or branched alkyl, alkoxy, alkylthio, alkylsulfinyl or alkylsulfonyl each having 1 to 6 carbon atoms;
each straight-chain or branched alkenyl or alkenyloxy, each with 2 to 6
Carbon atoms;
each straight-chain or branched haloalkyl, haloalkoxy, haloalkyl thio, haloalkylsulfinyl or haloalkylsulfonyl each having 1 to 6 carbon atoms and 1 to 13 identical or different halogen atoms;
each straight-chain or branched haloalkenyl or haloalkenyloxy each having 2 to 6 carbon atoms and 1 to 13 identical or different halogen atoms;
each share straight-chain or branched alkylamino, dialkylamino, alkylcarbonyl, alkylcarbonyloxy, alkoxycarbonyl, alkylsulfonyloxy, hydroxyiminoalkyl or alkoxyiminoalkyl each having 1 to 6 carbon atoms in the individual alkyl;
each optionally mono- or polysubstituted, identically or differently, by halogen and / or straight-chain or branched alkyl having 1 to 4 carbon atoms and / or straight-chain or branched haloalkyl having 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms, each substituted twice Alkylene or dioxyalkylene, each with 1 to 6 carbon atoms; such as
Cycloalkyl of 3 to 6 carbon atoms, aryl and aryloxy.

Preferred substituents for heterocyclyl or heterocyclylalkyl are listed in the list below:
Halogen, amino, hydroxy, oxo,
Alkyl, alkoxy, alkylthio, alkylamino, dialkylamino, each with 1 to 6 carbon atoms in the individual alkyl parts.

Particular preference is given to the use of compounds of the formula (I) in which
R ^{1 represents} hydrogen or methyl,
R ^{2 represents} hydrogen, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl and
R ³ for a grouping

stands in what
A represents oxygen, sulfur or - (NR ⁹ ) -, in which
R ^{9 represents} hydrogen or methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl or together with R ⁶ and the nitrogen atom to which they are attached, optionally by methyl or ethyl substituted pyrrolidinyl, morpholinyl, piperidinyl, piperazinyl or hexahydroazepinyl,
R ^{4 represents} hydrogen or optionally substituted by hydroxyl, formyloxy, phenylcarbonyloxy, methoxy, ethoxy, methylthio, ethylthio, methoxycarbonyl, ethoxycarbonyl, methylcarbonyloxy, ethylcarbonyloxy, propylcarbonyloxy, pentylcarbonyloxy or hexylcarbonyloxy optionally substituted in the phenyl part, methyl, ethyl, n- or i- Propyl, n-, i-, s- or t-butyl or phenyl, benzyl, 1-phenethyl, 2-phenethyl or indolylmethyl which is optionally substituted in the phenyl part or heterocyclyl part or
R ² and R ⁴ together with the nitrogen atom to which they are attached represent a pyrrolidine or piperidine ring,
R ^{5 represents} hydrogen, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl or
R ⁴ and R ⁵ together with the carbon atom to which they are attached represent a cyclopropane ring, cyclopentane or cyclohexane ring,
R ^{6 represents} hydrogen, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, pentyl, hexyl, heptyl, octyl, optionally by methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl substituted cyclopentyl or cyclohexyl, each optionally substituted in the phenyl or heterocyclyl part, phenyl, benzyl, 1-phenethyl, 2-phenethyl, phenylpropyl, phenylbutyl, phenylpentyl or phenylhexyl, pyrrolidinyl, morpholine linyl , Pyrrolidinylbutyl, morpholinylbutyl or methyl, ethyl or propyl substituted by pyrrolidonyl,
R ^{7 represents} hydrogen, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl,
R ^{8 represents} hydrogen, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl and
Z for hydrogen, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, pentyl, hexyl, heptyl, octyl, methylcarbonyl, ethylcarbonyl, n- or i-propylcarbonyl, n-, i-, s- or t-butylcarbonyl, pentylcarbonyl, hexyl carbonyl, heptylcarbonyl, octylcarbonyl, optionally substituted by methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl substituted cyclopentyl, cyclohexyl, cyclopentylcarbonyl or cyclohexylcarbonyl, in each case optionally substituted phenyl, benzyl, 1-phenethyl, 2-phenethyl, phenylpropyl, phenylbutyl, phenylpentyl or phenylhexyl, pyrrolidinyl, morpholinyl, pyrrolidinylbutyl, morpholinylbutyl, phenylcarbonyl, phenylcarbonyl, phenylcarbonyl, phenylcarbonyl, phenylpropyl , 2-phenethylcarbonyl, phenylcarbonylpropylcarbonyl, phenylcarbonylbutylcarbonyl, phenylcarbonylpentylcarbonyl or phenylcarbonylhexylcarbonyl, pyrrolidinylcarbonyl, morpholinylcarbonyl, pyrrolidinylcarbonylbutylcarbonyl or morpholinylcarbonylbutyl carbonyl.

Particularly preferred substituents for phenyl are listed in the following:
Fluorine, chlorine, bromine, cyano, amino, hydroxy, formyl, carboxy, carbamoyl, thio carbamoyl, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n - or i-propoxy, methylthio, ethylthio, n- or i-propylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl or ethylsulfonyl, trifluoromethyl, trifluoromethyl, difluoromethoxy, trifluoromethoxy, difluorochloromethoxy, trifluorethoxy, diformifluoromethylthio, difluoromifluoromethyl, difluoromethylfluoromethyl, difluoromifluoromethyl, Acetylamino, formylamino, N-formyl-N-methylamino, methyl amino, ethylamino, n- or i-propylamino, dimethylamino, diethylamino, acetyl, propionyl, acetyloxy, methoxycarbonyl, ethoxycarbonyl, methylsulfonyloxy, ethylsulfonyloxy, hydroxyyiminomethyl, methoxyiminomethyl, methyliminomethyl Methoxyiminoethyl or ethoxyiminoethyl,
each optionally optionally up to four times, identical or different, substituted by fluorine, chlorine, methyl, trifluoromethyl, ethyl, n- or i-propyl, in each case two times linked trimethylene (propane-1,3-diyl), tetramethylene (1,4-butane -diyl), methylenedioxy or ethylenedioxy,
Cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl or phenoxy.

Particularly preferred substituents for heterocyclyl or heterocyclylalkyl are listed in the list below:
Halogen, amino, hydroxy, oxo, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio, n- or i-propyl thio, methylamino, ethylamino, n- or i-propylamino, dimethylamino or diethylamino.

The present application further relates to new substituted acylaminosalicylic acid amides of the general formula (Ia),

in which
R ^{11 represents} hydrogen or alkyl,
R ^{12 represents} hydrogen or alkyl, or
R ¹³ for a grouping

stands in what
A represents oxygen, sulfur or - (NR ¹⁹ ) -, in which
R ^{19 represents} hydrogen or alkyl or, together with R ¹⁶ and the nitrogen atom to which they are attached, forms an optionally substituted heterocyclic ring,
R ^{14 represents} hydrogen, optionally substituted alkyl or optionally substituted aryl or
R ¹² and R ¹⁴ together with the nitrogen atom to which they are attached form a heterocyclic ring,
R ^{15 represents} hydrogen or alkyl or
R ¹⁴ and R ¹⁵ together with the carbon atom to which they are attached form a carbocyclic ring,
R ^{16 represents} hydrogen or in each case optionally substituted alkyl, cycloalkyl, aryl or heterocyclyl,
R ^{17 represents} hydrogen or alkyl and
R ^{18 represents} hydrogen or alkyl,
Z ^{1 represents} hydrogen or optionally substituted alkyl, alkyl carbonyl, cycloalkyl, cycloalkylcarbonyl, aryl, arylcarbonyl, heterocyclic or heterocyclylcarbonyl,
R ^{20 represents} hydrogen, optionally substituted alkyl or optionally substituted aryl or hetaryl or
R ¹² and R ²⁰ together with the nitrogen atom to which they are attached form a heterocyclic ring,
R ^{21 represents} hydrogen or alkyl or
R ²⁰ and R ²¹ together with the carbon atom to which they are attached form a carbocyclic ring.

Furthermore, it was found that the new substituted acylaminosalicylic acid amides of the general formula (Ia) are obtained if

• a) minosalicylic acid amides of the general formula (II),
  in which
  R ¹² and R ^{13 have} the meanings given above, with an acylating agent of the general formula (III),
  in which
  R ^{11 has} the meaning given above and
  X ^{1 represents} halogen, hydroxy, alkoxy or alkylcarbonyloxy,
  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 further reaction auxiliary, or if
• b) nitrosalicylic acid amides of the general formula (IV)
  in which
  R ¹² and R ^{13 have} the meanings given above, with formic acid, if appropriate in the presence of a catalyst and, if appropriate, in the presence of a further reaction auxiliary.

The compounds according to the invention are optionally in the form of mixtures various possible isomeric forms, in particular stereoisomers, such as. B. E and Z, threo and erythro and optical isomers before. Both the E as well as the Z isomers, as well as the threo- and erythro-, as well as the optical Isomers and any mixtures of these isomers claimed.

Preferred are the new compounds of formula (Ia) in which
R ^{11 represents} hydrogen or methyl,
R ^{12 represents} hydrogen or C ₁ -C ₄ alkyl and
R ¹³ for a grouping

stands in what
A represents oxygen, sulfur or - (NR ¹⁹ ) -, in which
R ^{19 represents} hydrogen or alkyl having 1 to 4 carbon atoms or, together with R ¹⁶ and the nitrogen atom to which they are bound, forms a heterocyclic ring with 3 to 7 ring members optionally substituted by C ₁ -C ₄ alkyl,
R ^{14 represents} hydrogen or optionally substituted by hydroxyl, formyloxy, optionally substituted arylcarbonyloxy or alkoxy, alkylthio, alkoxycarbonyl or alkylcarbonyloxy each having 1 to 6 carbon atoms in the alkyl part substituted alkyl or optionally substituted aryl, or heterocyclyl part aryl, heterocyclyl, optionally substituted in the aryl part, Arylalkyl or heterocyclylalkyl each having 1 to 6 carbon atoms in the alkyl part or
R ¹² and R ¹⁴ together with the nitrogen atom to which they are attached form a heterocyclic ring with 3 to 6 ring members,
R ^{15 represents} hydrogen or C ₁ -C ₄ alkyl or
R ¹⁴ and R ¹⁵ together with the carbon atom to which they are attached form a carbocyclic ring with 3 to 6 ring members,
R ¹⁶ for hydrogen or C ₁ -C ₁₂ alkyl, optionally substituted by C ₁ -C ₄ alkyl, C ₃ -C ₇ cycloalkyl, each optionally substituted in the aryl or heterocyclyl part aryl, arylalkyl having 1 to 6 carbon atoms in the Alkyl part, heterocyclyl, heterocyclylalkyl having 1 to 6 carbon atoms in the alkyl part, or C ₁ -C ₄ -alkyl substituted by pyrrolidonyl,
R ^{17 represents} hydrogen or C ₁ -C ₄ alkyl and
R ^{18 represents} hydrogen or C ₁ -C ₄ alkyl,
Z ^{1 represents} hydrogen or C ₁ -C ₁₂ alkyl or alkylcarbonyl, C ₃ -C ₇ cycloalkyl or cycloalkyl carbonyl optionally substituted by C ₁ -C ₄ alkyl, each optionally substituted aryl, arylcarbonyl in the aryl or heterocyclyl part, Arylalkyl, arylalkylcarbonyl having 1 to 6 carbon atoms in the alkyl part, heterocyclyl, heterocyclylcarbonyl, heterocyclylalkyl or heterocyclylalkylcarbonyl having 1 to 6 carbon atoms in the alkyl part,
R ²⁰ for hydrogen or optionally substituted by formyloxy, optionally substituted arylcarbonyloxy or alkoxy, alkylthio, alkoxycarbonyl or alkylcarbonyloxy each having 1 to 6 carbon atoms in the alkyl part substituted C ₁ -C ₄ alkyl or optionally substituted in the aryl part or heterocyclyl part Aryl, heterocyclyl, arylalkyl having 2 to 6 carbon atoms in the alkyl part or heterocyclylalkyl having 1 to 6 carbon atoms in the alkyl part or substituted benzyl or
R ¹² and R ²⁰ together with the nitrogen atom to which they are attached form a heterocyclic ring with 3 to 6 ring members,
R ^{21 represents} hydrogen or C ₁ -C ₄ alkyl or
R ²⁰ and R ²¹ together with the carbon atom to which they are attached form a carbocyclic ring with 3 to 6 ring members.

Preferred substituents for aryl or arylalkyl are listed in the following:
Halogen, cyano, amino, hydroxy, formyl, carboxy, carbamoyl, thiocarbamoyl;
in each case straight-chain or branched alkyl, alkoxy, alkylthio, alkylsulfinyl or alkylsulfonyl each having 1 to 6 carbon atoms;
each straight-chain or branched alkenyl or alkenyloxy each having 2 to 6 carbon atoms;
each straight-chain or branched haloalkyl, haloalkoxy, haloalkyl thio, haloalkylsulfinyl or haloalkylsulfonyl each having 1 to 6 carbon atoms and 1 to 13 identical or different halogen atoms;
each straight-chain or branched haloalkenyl or haloalkenyloxy each having 2 to 6 carbon atoms and 1 to 13 identical or different halogen atoms;
each share straight-chain or branched alkylamino, dialkylamino, alkylcarbonyl, alkylcarbonyloxy, alkoxycarbonyl, alkylsulfonyloxy, hydroxyiminoalkyl or alkoxyiminoalkyl each having 1 to 6 carbon atoms in the individual alkyl;
each optionally mono- or polysubstituted, identically or differently, by halo and / or straight-chain or branched alkyl having 1 to 4 carbon atoms and / or straight-chain or branched haloalkyl having 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms, in each case linked twice Alkylene or dioxyalkylene each having 1 to 6 carbon atoms; such as
Cycloalkyl of 3 to 6 carbon atoms, aryl and aryloxy.

Preferred substituents for heterocyclyl or heterocyclylalkyl are listed in the list below:
Halogen, amino, hydroxy, oxo,
Alkyl, alkoxy, alkylthio, alkylamino, dialkylamino, each with 1 to 6 carbon atoms in the individual alkyl parts.

The invention relates in particular to the new compounds of formula (I) in which
R ^{11 represents} hydrogen or methyl,
R ^{12 represents} hydrogen, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl and
R ¹³ for a grouping

stands in what
A represents oxygen, sulfur or - (NR ¹⁹ ) -, in which
R ^{19 represents} hydrogen or methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl or together with R ¹⁶ and the nitrogen atom to which they are attached, optionally by methyl or ethyl substituted pyrrolidinyl, morpholinyl, piperidinyl, piperazinyl or hexahydroazepinyl,
R ^{14 represents} hydrogen or optionally substituted by hydroxyl, formyloxy, phenylcarbonyloxy, methoxy, ethoxy, methylthio, ethylthio, methoxycarbonyl, ethoxycarbonyl, methylcarbonyloxy, ethylcarbonyloxy, propylcarbonyloxy, pentylcarbonyloxy or hexylcarbonyloxy optionally substituted in the phenyl part, methyl, ethyl, n- or i- Propyl, n-, i-, s- or t-butyl or phenyl, benzyl, 1-phenethyl, 2-phenethyl or indolylmethyl which is optionally substituted in the phenyl part or heterocyclyl part or
R ¹² and R ¹⁴ together with the nitrogen atom to which they are attached represent a pyrrolidine or piperidine ring,
R ^{15 represents} hydrogen, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl or
R ¹⁴ and R ¹⁵ together with the carbon atom to which they are attached represent a cyclopropane, cyclopentane or cyclohexane ring,
R ^{16 represents} hydrogen, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, pentyl, hexyl, heptyl, octyl, optionally by methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl substituted cyclopentyl or cyclohexyl, each optionally substituted in the phenyl or heterocyclyl part, phenyl, benzyl, 1-phenethyl, 2-phenethyl, phenylpropyl, phenylbutyl, phenylpentyl or phenylhexyl, pyrrolidinyl, morpholine linyl , Pyrrolidinylbutyl, morpholinylbutyl or methyl, ethyl or propyl substituted by pyrrolidonyl,
R ^{17 represents} hydrogen, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl and
R ^{18 represents} hydrogen, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl,
Z ¹ for hydrogen, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, pentyl, hexyl, heptyl, octyl, methylcarbonyl, ethylcarbonyl, n- or i-propylcarbonyl, n- , i-, s- or t-butylcarbonyl, pentylcarbonyl, hexyl carbonyl, heptylcarbonyl, octylcarbonyl, optionally substituted by methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl substituted cyclopentyl, cyclohexyl, Cyclopentylcarbonyl or cyclohexylcarbonyl, in each case optionally substituted phenyl, benzyl, 1-phenethyl, 2-phenethyl, phenylpropyl, phenylbutyl, phenyl pentyl or phenylhexyl, pyrrolidinyl, morpholinyl, pyrrolidinylbutyl, phenylbutyl, morpholylylbutyl, morpholylylbutyl, morpholylylbutyl, morpholylylbutyl carbonyl, 2-phenethylcarbonyl, phenylcarbonylpropylcarbonyl, phenylcarbonylbutylcarbonyl, phenylcarbonylpentylcarbonyl or phenylcarbonylhexylcarbonyl, pyrrolidinylcarbonyl, morpholinylcarbonyl, pyrrolidinylcarbonylbutylcarbonyl or morpholinylcarbonylbutyl carbonyl,
R ²⁰ for hydrogen or phenylcarbonyloxy, methoxy, ethoxy, methylthio, ethylthio, methoxycarbonyl, ethoxycarbonyl, methyl carbonyloxy, ethylcarbonyloxy, propylcarbonyloxy, pentylcarbonyloxy or hexylcarbonyloxy substituted methyl, ethyl, n- or i-propyl, n -, i-, s- or t-butyl or in each case optionally substituted phenyl, 1-phenethyl, 2-phenethyl or indolylmethyl or substituted benzyl in the phenyl part or heterocyclyl part or R ¹² and R ²⁰ together with the nitrogen atom to which they are attached , represent a pyrrolidine or piperidine ring,
R ^{21 represents} hydrogen, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl or
R ²⁰ and R ²¹ together with the carbon atom to which they are attached represent a cyclopropane ring, cyclopentane or cyclohexane ring.

Particularly preferred substituents for phenyl are listed in the following:
Fluorine, chlorine, bromine, cyano, amino, hydroxy, formyl, carboxy, carbamoyl, thio carbamoyl, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n - or i-propoxy, methylthio, ethylthio, n- or i-propylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl or ethylsulfonyl, trifluoromethyl, trifluoromethyl, difluoromethoxy, trifluoromethoxy, difluorochloromethoxy, trifluorethoxy, diformifluoromethylthio, difluoromifluoromethyl, difluoromethylfluoromethyl, difluoromifluoromethyl, Acetylamino, formylamino, N-formyl-N-methylamino, methyl amino, ethylamino, n- or i-propylamino, dimethylamino, diethylamino, acetyl, propionyl, acetyloxy, methoxycarbonyl, ethoxycarbonyl, methylsulfonyloxy, ethylsulfonyloxy, hydroxyyiminomethyl, methoxyiminomethyl, methyliminomethyl Methoxyiminoethyl or ethoxyiminoethyl,
each optionally optionally up to four times, identical or different, substituted by fluorine, chlorine, methyl, trifluoromethyl, ethyl, n- or i-propyl, in each case two times linked trimethylene (propane-1,3-diyl), tetramethylene (1,4-butane -diyl), methylenedioxy or ethylenedioxy,
Cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl or phenoxy.

Particularly preferred substituents for heterocyclyl or heterocyclylalkyl are in listed below:

Halogen, amino, hydroxy, oxo, methyl, ethyl, n- or i-propyl, n-, i-, s- or t- Butyl, methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio, n- or i-propyl thio, methylamino, ethylamino, n- or i-propylamino, dimethylamino or di ethylamino.

The radicals listed above or specified in preferred ranges definitions apply both to the end products of the formula (I) and correspondingly for the raw materials or intermediate products required for the production.

Those in the respective combinations or preferred combinations of residues in particular for the specified radical definitions are independent of each other of the respectively specified combinations of the residues, optionally also by residues definitions of others replaced.

Formula (II) provides a general definition of the aminosalicylic acid amides required as starting materials for carrying out process a) according to the invention. In this formula (II), R ¹² and R ¹³ preferably or in particular have those meanings which have already been given as preferred or as particularly preferred for R ¹² and R ¹³ in connection with the description of the compounds of the formula (I) according to the invention .

Some of the starting materials of the formula (II) are known (see, for example, J. Heterocycl. Chem. (1971), 8 (6), 989-91).  

New and also the subject of the present application are aminosalicylic acid amides of the formula (II-a),

in which
R ^{12 has} the meaning given above, and
R ¹³ for a grouping

stands in what
A, R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , Z ¹ and R ^{21 have} the meanings given above,
R ²² for aryl carbonyloxy or alkoxy, alkylthio, alkoxycarbonyl or alkyl carbonyloxy, each substituted by formyloxy, optionally substituted in the aryl part, each having 1 to 6 carbon atoms in the alkyl part substituted C ₁ -C ₄ alkyl or unsubstituted C ₂ -C ₄ alkyl, each optionally in Aryl part or heterocyclyl part substituted aryl, heterocyclyl, arylalkyl having 2 to 6 carbon atoms in the alkyl part or heterocyclylalkyl having 1 to 6 carbon atoms in the alkyl part or substituted benzyl or
R ²² and R ¹² together with the nitrogen atom to which they are attached form a heterocyclic ring,
R ²² and R ²¹ together with the carbon atom to which they are attached form a carbocyclic ring.

Aminosalicylic acid amides of the formula (II-a) are preferred, in which
R ^{12 has} the meaning given above, and
R ¹³ for a grouping

stands in what
A, R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , Z ¹ and R ^{21 have} the meanings given above,
R ²² for formyloxy, optionally substituted in the aryl carbonyloxy or alkoxy, alkylthio, alkoxycarbonyl or alkyl carbonyloxy each having 1 to 6 carbon atoms in the alkyl part substituted C ₁ -C ₄ alkyl or unsubstituted C ₂ -C ₄ alkyl, each against aryl, heterocyclyl, arylalkyl with 2 to 6 carbon atoms in the alkyl part or heterocyclylalkyl with 1 to 6 carbon atoms in the alkyl part or substituted benzyl, or substituted in the aryl part or heterocyclyl part or
R ²² and R ¹² together with the nitrogen atom to which they are attached represent a pyrrolidine or piperidine ring or
R ²² and R ²¹ together with the carbon atom to which they are attached represent a cyclopentane or cyclohexane ring.

Aminosalicylic acid amides of the formula (II-a), in which
R ^{12 has} the meaning given above, and
R ¹³ for a grouping

stands in what
A, R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , Z ¹ and R ^{21 have} the meanings given above,
R ²² for phenylcarbonyloxy, methoxy, ethoxy, methylthio, ethylthio, methoxycarbonyl, ethoxycarbonyl, methylcarbonyloxy, ethylcarbonyloxy, propylcarbonyloxy, pentylcarbonyloxy or hexylcarbonyloxy, each substituted by formyloxy, optionally substituted in the phenyl part, methyl, ethyl, n- or i-propyl, n- , i-, s- or t-butyl or unsubstituted ethyl, n- or i-propyl, n-, i-, s- or t-butyl, each optionally substituted in the phenyl part or heterocyclyl part, phenyl, 1-phenethyl, 2-phenethyl or indolylmethyl or substituted benzyl or
R ²² and R ¹² together with the nitrogen atom to which they are attached represent a pyrrolidine or piperidine ring or
R ²² and R ²¹ together with the carbon atom to which they are attached represent a cyclopentane or cyclohexane ring.

The aminosalicylic acid amides of the formula (II-a) are obtained if (process c) nitrosalicylic acid amides of the general formula (IV-a),

in which
R ¹² and R ^{13 have} the meanings given above,
with hydrogen, optionally in the presence of a diluent, preferably an ester such as methyl acetate or ethyl acetate; an alcohol, such as methanol, ethanol, n- or i-propanol, n-, i-, sec- or tert-butanol, ethane diol, propane-1,2-diol, ethoxyethanol, methoxyethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether; Water, a salt solution, such as ammonium chloride solution, an acid, such as hydrochloric acid or acetic acid, and any mixtures of the diluents mentioned and, if appropriate, in the presence of a catalyst, such as Raney nickel, palladium or platinum, if appropriate on a support material, such as activated carbon .

Formula (IV-a) provides a general definition of the nitrosalicylic acid amides required to carry out process c) as starting materials. In this formula (IV-a), R ¹² and R ¹³ preferably or in particular have those meanings which, in connection with the description of the compounds of the formula (II-a) according to the invention, are preferred or particularly preferred for R ¹² and R ^{13 have been} given.

The nitrosalicylic acid amides of the formula (IV-a) are new and also the subject of present application.

They are obtained if (process d) 2-hydroxy-3-nitrobenzoic acid or 2-hydroxy-3-nitrobenzoyl chloride with an amine of the formula (V),

in which
R ¹² and R ^{13 have} the meanings given above,
optionally in the presence of a diluent, by way of example and in preference an aliphatic, alicyclic or aromatic hydrocarbon, such as, for example, petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene or decalin; a halogenated hydrocarbon, such as, for example, chlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, dichloroethane or trichloroethane; an ether such as, for example, diethyl ether, diisopropyl ether, methyl t-butyl ether, methyl t-amyl ether, dioxane, tetrahydro furan, 1,2-dimethoxyethane, 1,2-diethoxyethane or anisole; a ketone such as acetone, butanone, methyl isobutyl ketone or cyclohexanone; a Ni trile, such as acetonitrile, propionitrile, n- or i-butyronitrile or benzo nitrile; an amide such as N, N-dimethylformamide, N, N-dimethyl acetamide, N-methylformanilide, N-methylpyrrolidone or hexamethylphosphoric acid triamide; an ester such as methyl acetate or ethyl acetate; a sulfoxide such as dimethyl sulfoxide; or a sulfone, such as sulfolane, optionally in the presence of a condensing agent, for example an acid halide former such as phosgene, phosphorus tribromide, phosphorus trichloride, phosphorus pentachloride, phosphorus oxychloride or thionyl chloride; an anhydride former such as ethyl chloroformate, methyl chloroformate, isopropyl chloroformate, isobutyl chloroformate or methanesulfonyl chloride; a carbodiimide such as N, N'-dicyclohexylcarbodiimide (DCC) or another conventional condensing agent such as phosphorus pentoxide, polyphosphoric acid, N, N'-carbonyldiiniidazole, 2-ethoxy-N-ethoxycarbonyl-1,2-dihydroquinoline (EEDQ) or triphenylphosphine / carbon tetrachloride and optionally in the presence of an acid acceptor, for example and preferably an alkaline earth metal or alkali metal hydrides, hydroxides, amides, alcoholates, acetates, carbonates or hydrogen carbonates, such as sodium hydride, sodium amide, sodium methylate, Sodium ethylate, potassium tert-butoxide, sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium acetate, potassium acetate, calcium acetate, ammonium acetate, sodium carbonate, potassium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate or ammonium carbonate, or a tertiary amine such as tri methylamine, triethylamine, tributylamine , N, N-dimethylaniline, N, N-dimethylbenzylamine, pyridine, N- Methylpiperidine, N-methylmorpholine, N, N-dimethylamino pyridine, diazabicyclooctane (DABCO), diazabicyclonones (DBN) or diazabicycloundecene (DBU).

The be to carry out the method d) according to the invention as starting materials required 2-hydroxy-3-nitrobenzoic acid or 2-hydroxy-3-nitrobenzoic acid chloride are known (see, e.g., J. Het. Chem., 1971, 8 (6), 889-891, J. Chem. Soc., 1953 2049, 2050 or U.S. Patent 03527865).

Formula (V) provides a general definition of the amines required to carry out process d) according to the invention as starting materials. In this formula (V), R ¹² and R ^{13 have} examples and preferably or in particular those meanings which, in connection with the description of the compounds of the formula (I) according to the invention, are preferred or particularly preferred for R ¹² and R ¹³ were specified.

The amines of the formula (VII) are known reagents in organic chemistry.

Some of the compounds of the formula (I) are known and can be partially modified known processes can be prepared (cf. Biochim. Biophys. Acta 1993, 262-268).

Formula (III) provides a general definition of the acylating agents required to carry out process a) according to the invention as starting materials. In this formula (III), R ¹¹ preferably or in particular has the meaning which has already been given as preferred or as particularly preferred for R ¹¹ in connection with the description of the compounds of the formula (I) according to the invention. X ¹ stands for halogen, hydroxy, alkoxy or alkylcarbonyloxy, preferably for chlorine, hydroxy, methoxy, ethoxy or acetoxy.

The acylating agents of the general formula (III) are known reagents in the organic chemistry.  

Formula (IV) provides a general definition of the nitrosalicylic acid amides required as starting materials for carrying out process b) according to the invention. In this formula (IV), R ¹² and R ¹³ preferably or in particular have those meanings which, in connection with the description of the compounds of the formula (I) according to the invention, are indicated as preferred or as particularly preferred for R ¹² and R ¹³ were.

Some of the starting materials of the formula (IV) are known (see, for example, J. Heterocycl. Chem. (1971), 8 (6), 989-991).

The nitrosalicylic acid amides of the formula (IV-a) are new and are already mentioned above in Connection with the description of the method c) according to the invention have been written.

As a diluent for carrying out process a) according to the invention all inert organic solvents are suitable. These include at playful and preferably aliphatic, alicyclic or aromatic kohlwas substances such as petroleum ether, hexane, heptane, cyclohexane, methylcyclo hexane, benzene, toluene, xylene or decalin; halogenated hydrocarbons, such as for example chlorobenzene, dichlorobenzene, dichloromethane, chloroform, tetra chloromethane, dichloroethane or trichloroethane; Ethers such as diethyl ether, diisopropyl ether, methyl t-butyl ether, methyl t-amyl ether, dioxane, tetra hydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane or anisole; Ketones like for example acetone, butanone, methyl isobutyl ketone or cyclohexanone; 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; Esters such as, for example, methyl acetate or ethyl acetate; Sulfoxides, such as for example dimethyl sulfoxide or sulfones, such as sulfolane.  

If appropriate, process a) according to the invention is suitable in the presence of a Neten acid acceptor performed. All the usual inorganic ones come as such or organic bases. These preferably include alkaline earth metal or Alkali metal hydroxides, acetates, carbonates or bicarbonates, such as wise sodium hydroxide, potassium hydroxide, sodium acetate, potassium acetate, calcium acid tat, sodium carbonate, potassium carbonate, potassium hydrogen carbonate or sodium hydro gene 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), diaza bicyclonones (DBN) or diazabicycloundecene (DBU).

Process b) according to the invention is optionally carried out in the presence of a catalyst lysators performed. As such, all catalysts come into question that are also suitable for Hydrogenations are commonly used. Examples include: Raney- Nickel, palladium or platinum, optionally on a support material, as in for example activated carbon.

The reaction temperatures can be carried out when carrying out the inventive Processes a) and b) can be varied over a wide range. In general one works at temperatures from 0 ° C to 180 ° C, preferably at temperatures from 0 ° C to 130 ° C.

To carry out the method a) for the production of the verb The formula (I) is used per mole of the aminosalicylic acid amide of the formula (II) generally 1 to 2000 moles, preferably 1 to 800 moles of acylating agent of formula (III).

To carry out the process b) according to the invention for producing the verbin The formula (I) is used per mole of the nitrosalicylic acid amide of the formula  (IV-a) generally 100 to 2000 moles, preferably 200 to 1000 moles of ants acid.

The processes according to the invention are generally carried out under normal pressure guided. However, it is also possible, under increased or reduced pressure - im generally between 0.1 bar and 10 bar - to work.

The substances according to the invention have a strong microbicidal action and can fight unwanted microorganisms, such as fungi and Bacteria can be used in crop protection and material protection.

Fungicides can be used to control Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes and Use Deuteromycetes.

Bactericides can be used in plant protection to combat Pseudomonadaceae, Rhizobiaceae, Enterobacteriaceae, Corynebacteriaceae and Streptomycetaceae put.

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

The good plant tolerance of the active ingredients in the control of plants Concentrations necessary for diseases allow treatment above ground Parts of plants, of seedlings, and of the soil.  

The active compounds according to the invention can be particularly successful Combating diseases in wine, fruit and vegetable growing, such as wise against Botrytis, Phytophtora and Plasmopara species, or from rice sick units, such as against Pyricularia species.

Grain diseases are also combated with good success.

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

The active ingredients can depend on their respective physical and / or chemical properties are converted into the usual formulations, such as Lö solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, Fine encapsulation in polymeric substances and in coating compositions for seeds, as well ULV cold and warm fog formulations.

These formulations are prepared in a known manner, e.g. B. by mixing of the active substances with extenders, i.e. liquid solvents, under pressure liquefied gases and / or solid carriers, optionally using of surface-active agents, i.e. emulsifiers and / or dispersants and / or foam-generating agents. In the case of using water as a stretch means can e.g. B. also used organic solvents as auxiliary solvents become. The following are essentially suitable as liquid solvents: aromatics, such as Xylene, toluene or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic Hydrocarbons such as chlorobenzenes, chlorethylenes or methylene chloride, alipha table hydrocarbons, such as cyclohexane or paraffins, e.g. B. 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 solution medium, such as dimethylformamide and dimethyl sulfoxide, and water. With liquefied gaseous extenders or carriers are meant such liquids  which are gaseous at normal temperature and pressure, e.g. B. Aerosol Propellants, such as halogenated hydrocarbons, butane, propane, nitrogen and Koh oil dioxide. As solid carriers come into question: B. natural stone powder, such as Kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diato sea earth and synthetic rock powder, such as highly disperse silica, aluminum oxide and silicates. Possible solid carriers for granules are: B. ge broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, Dolomite and synthetic granules from inorganic and organic flours as well as granules of organic material such as sawdust, coconut shells, corn piston and tobacco stem. As emulsifiers and / or foaming agents come in Question: e.g. B. non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid ester, polyoxyethylene fatty alcohol ether, e.g. B. alkylaryl polyglycol ethers, alkyl sulfonates, Alkyl sulfates, aryl sulfonates and protein hydrolyzates. As dispersants come in Question: e.g. B. lignin sulfite and methyl cellulose.

Adhesives such as carboxymethyl cellulose, natural, can be used in the formulations and synthetic powdery, granular or latex-shaped polymers are used, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and natural phospholi pide, such as cephalins and lecithins, and synthetic phospholipids. Other additives can be mineral and vegetable oils.

Dyes such as inorganic pigments, e.g. B. iron oxide, titanium oxide, ferro cyan 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 can be used.

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

The active compounds according to the invention can be used as such or in their formulations also in a mixture with known fungicides, bactericides, acaricides, nematicides or insecticides can be used, e.g. B. to broaden the spectrum of activity or to prevent the development of resistance. In many cases you get syner gistic effects, d. H. the effectiveness of the mixture is greater than the effectiveness of the individual components.

The following connections can be considered as mixed partners:

Fungicides

Aldimorph, ampropylfos, ampropylfos potassium, andoprim, anilazine, azaconazole, azoxystrobin,
Benalaxyl, Benodanil, Benomyl, Benzamacril, Benzamacryl-Isobutyl, Bialaphos, Binapacryl, Biphenyl, Bitertanol, Blasticidin-S, Bromuconazol, Bupirimat, Buthiobat, Calciumpolysulfid, Capsimycin, Captafol, Captan, Carbendazat, Quinominionononvon, Carboxiniononvonvon , Chlorfenazole, chloroneb, chloropicrin, chlorothalonil, chlorozolinate, clozylacon, cufraneb, cymoxanil, cyproconazole, cyprodinil, cyprofuram,
Debacarb, dichlorophene, diclobutrazole, diclofluanide, diclomezin, dicloran, diethofencarb, difenoconazole, dimethirimol, dimethomorph, diniconazole, diniconazol-M, dinocap, diphenylamine, dipyrithione, ditalimfos, dithorphoxinodonine, dithorphononodine
Ediphenphos, Epoxiconazole, Etaconazole, Ethirimol, Etridiazole,
Famoxadone, fenapanil, fenarimol, fenbuconazole, fenfuram, fenitropan, fenpiclonil, fenpropidin, fenpropimorph, fentin acetate, fentin hydroxide, ferbam, ferimzon, fluazinam, flumetover, fluoromid, fluquinconazole, flurprimolol, flusulfazolutol, flusulfazolutol, flusulfazolutol, flusulfazolutol, flusulfazolutol, flusulfazolutol, flusulfazolutol, flusulfazolutol, flusulfazolutol, flusulfazolutol, flusulfazolutol, flusulfazolutol, flusulfazolutol, flusulfazolutol, flusulfazolutol, flusulfazolutol, flusilazolutol, flusulfazolutol, flusulfazolutol, flusilazolutol, flusilazolutol, flusilazolutolol Fosetyl sodium, fthalide, fuberidazole, furalaxyl, furametpyr, furcarbonil, furconazole, furconazole-cis,
Furmecyclox,
Guazatin,
Hexachlorobenzene, hexaconazole, hymexazole,
Imazalil, Imibenconazol, Iminoctadin, Iminoctadinealbesilat, Iminoctadinetriacetat, Iodocarb, Ipconazol, Iprobefos (IBP), Iprodione, Irumamycin, Isoprothiolan, Isovaledione,
Kasugamycin, Kresoxim-methyl, copper preparations, such as: copper hydroxide, copper naphthenate, copper oxychloride, copper sulfate, copper oxide, oxine-copper and Bordeaux mixture,
Mancopper, Mancozeb, Maneb, Meferimzone, Mepanipyrim, Mepronil, Metalaxyl, Metconazol, Methasulfocarb, Methfuroxam, Metiram, Metomeclam, Metsulfovax, Mildiomycin, Myclobutanil, Myclozolin,
Nickel dimethyldithiocarbamate, nitrothal isopropyl, Nuarimol,
Ofurace, Oxadixyl, Oxamocarb, Oxolinicacid, Oxycarboxim, Oxyfenthiin,
Paclobutrazole, pefurazoate, penconazole, pencycuron, phosdiphen, pimaricin, piperalin, polyoxin, polyoxorim, probenazole, prochloraz, procymidon, propamocarb, propanosine sodium, propiconazole, propineb, pyrazophos, pyrifen, pyifenox, pyrroyilonil
Quinconazole, quintozen (PCNB),
Sulfur and sulfur preparations,
Tebuconazole, tecloftalam, tecnazene, Tetcyclacis, tetraconazole, thiabendazole, Thicyofen, Thifluzamide, thiophanate-methyl, thiram, Tioxymid, tolclofos-methyl, tolylfluanid, triadimefon, triadimenol, Triazbutil, triazoxide, Trichlamid, tricyclazole, tridemorph, triflumizole, triforine, triticonazole,
Uniconazole,
Validamycin A, vinelozolin, viniconazole,
Zarilamid, Zineb, Ziram as well
Dagger G,
OK-8705,
OK-8801,
α- (1,1-dimethylethyl) -β- (2-phenoxyethyl) -1H-1,2,4-triazole-1-ethanol,
α- (2,4-dichlorophenyl) -β-fluoro-b-propyl-1H-1,2,4-triazole-1-ethanol,
a- (2,4-dichlorophenyl) -β-methoxy-a-methyl-1H-1,2,4-triazole-1-ethanol,
α- (5-methyl-1,3-dioxan-5-yl) -β - [[4- (trifluoromethyl) phenyl] methylene] -1H-1,2,4-triazol-1-ethanol,
(5RS, 6RS) -6-Hydroxy-2,2,7,7-tetramethyl-5- (1H-1,2,4-triazol-1-yl) -3-octanone, (E) -a- (methoxyimino ) -N-methyl-2-phenoxy-phenylacetamide,
{2-Methyl-1 - [[[1- (4-methylphenyl) ethyl] amino] carbonyl] propyl} carbamic acid 1-isopropyl ester
1- (2,4-dichlorophenyl) -2- (1H-1,2,4-triazol-1-yl) -ethanone-O- (phenylmethyl) oxime,
1- (2-methyl-1-naphthalenyl) -1H-pyrrole-2,5-dione,
1- (3,5-dichlorophenyl) -3- (2-propenyl) -2,5-pyrrolidinedione,
1 - [(diiodomethyl) sulfonyl] -4-methyl-benzene,
1 - [[2- (2,4-dichlorophenyl) -1,3-dioxolan-2-yl] methyl] -1H-imidazole,
1 - [[2- (4-chlorophenyl) -3-phenyloxiranyl] methyl] -1H-1,2,4-triazole,
1- [1- [2 - [(2,4-dichlorophenyl) methoxy] phenyl] ethenyl] -1H-imidazole,
1-methyl-5-nonyl-2- (phenylmethyl) -3-pyrrolidinol,
2 ', 6'-dibromo-2-methyl-4'-trifluoromethoxy-4'-trifluoromethyl-1,3-thiazole-5-carboxanilide,
2,2-dichloro-N- [1- (4-chlorophenyl) ethyl] -1-ethyl-3-methyl-cyclopropanecarboxamide,
2,6-dichloro-5- (methylthio) -4-pyrimidinyl-thiocyanate,
2,6-dichloro-N- (4-trifluoromethylbenzyl) benzamide,
2,6-dichloro-N - [[4- (trifluoromethyl) phenyl] methyl] benzamide,
2- (2,3,3-triiodo-2-propenyl) -2H-tetrazole,
2 - [(1-methylethyl) sulfonyl] -5- (trichloromethyl) -1,3,4-thiadiazole,
2 - [[6-Deoxy-4-O- (4-O-methyl-β-D-glycopyranosyl) -aD-glucopyranosyl] amino] -4- methoxy-1H-pyrrolo [2,3-d] pyrimidine- 5-carbonitrile,
2-aminobutane,
2-bromo-2- (bromomethyl) pentandinitrile,
2-chloro-N- (2,3-dihydro-1,1,3-trimethyl-1H-inden-4-yl) -3-pyridinecarboxamide,
2-chloro-N- (2,6-dimethylphenyl) -N- (isothiocyanatomethyl) acetamide,
2-phenylphenol (OPP),
3,4-dichloro-1- [4- (difluoromethoxy) phenyl] -1H-pyrrole-2,5-dione,
3,5-dichloro-N- [cyan [(1-methyl-2-propynyl) oxy] methyl] benzamide,
3- (1,1-dimethylpropyl-1-oxo-1H-indene-2-carbonitrile,
3- [2- (4-chlorophenyl) -5-ethoxy-3-isoxazolidinyl] pyridine,
4-chloro-2-cyan-N, N-dimethyl-5- (4-methylphenyl) -1H-imidazole-1-sulfonamide,
4-methyl-tetrazolo [1,5-a] quinazolin-5 (4H) -one,
8- (1,1-dimethylethyl) -N-ethyl-N-propyl-1,4-dioxaspiro [4.5] decane-2-methanamine,
8-hydroxyquinoline sulfate,
9H-xanthene-9-carboxylic acid 2 - [(phenylamino) carbonyl] hydrazide,
bis- (1-methylethyl) -3-methyl-4 - [(3-methylbenzoyl) -oxy] -2,5-thiophene dicarboxylate,
cis-1- (4-chlorophenyl) -2- (1H-1,2,4-triazol-1-yl) cycloheptanol,
cis-4- [3- [4- (1,1-dimethylpropyl) phenyl-2-methylpropyl] -2,6-dimethylmorpholine hydrochloride,
Ethyl - [(4-chlorophenyl) azo] cyanoacetate,
Potassium hydrogen carbonate,
Methane tetrathiol sodium salt,
Methyl 1- (2,3-dihydro-2,2-dimethyl-1H-inden-1-yl) -1H-imidazole-5-carboxylate,
Methyl N- (2,6-dimethylphenyl) -N- (5-isoxazolylcarbonyl) -DL-alaninate,
Methyl N- (chloroacetyl) -N- (2,6-dimethylphenyl) -DL-alaninate,
N- (2,3-dichloro-4-hydroxyphenyl) -1-methyl-cyclohexane carboxamide,
N- (2,6-dimethylphenyl) -2-methoxy-N- (tetrahydro-2-oxo-3-furanyl) acetamide,
N- (2,6-dimethylphenyl) -2-methoxy-N- (tetrahydro-2-oxo-3-thienyl) acetamide,
N- (2-chloro-4-nitrophenyl) -4-methyl-3-nitro-benzenesulfonamide,
N- (4-cyclohexylphenyl) -1,4,5,6-tetrahydro-2-pyrimidinamine,
N- (4-hexylphenyl) -1,4,5,6-tetrahydro-2-pyrimidinamine,
N- (5-chloro-2-methylphenyl) -2-methoxy-N- (2-oxo-3-oxazolidinyl) acetamide,
N- (6-methoxy) -3-pyridinyl) cyclopropanecarboxamide,
N- [2,2,2-trichloro-1 - [(chloroacetyl) amino] ethyl] benzamide,
N- [3-chloro-4,5-bis (2-propynyloxy) phenyl] -N'-methoxymanimidamide,
N-formyl-N-hydroxy-DL-alanine sodium salt,
O, O-diethyl- [2- (dipropylamino) -2-oxoethyl] ethylphosphoramidothioate,
O-methyl-S-phenyl-phenylpropylphosphoramidothioate,
S-methyl-1,2,3-benzothiadiazole-7-carbothioate,
spiro [2H] -1-benzopyran-2,1 '(3'H) -isobenzofuran] -3'-one,

Bactericides

Bronopol, dichlorophene, nitrapyrin, nickel dimethyldithiocarbamate, kasugamycin, Octhilinone, furan carboxylic acid, oxytetracycline, probenazole, streptomycin, tecloftalam, Copper sulfate and other copper preparations.

Insecticides / acaricides / nematicides

Abamectin, Acephate, Acetamiprid, Acrinathrin, Alanycarb, Aldicarb, Aldoxycarb, Alpha-cypermethrin, Alphamethrin, Amitraz, Avermectin, AZ 60541, Azadirachtin, Azamethiphos, Azinphos A, Azinphos M, Azocyclotin,
Bacillus popilliae, Bacillus sphaericus, Bacillus subtilis, Bacillus thuringiensis, Baculoviruses, Beauveria bassiana, Beauveria tenella, Bendiocarb, Benfuracarb, Bensultap, Benzoximate, Betacyfluthrin, Bifenazate, Bifenthrin, Biethanomofufoxin, Bethanomethofinoxin, Bethenomethrin Butyl pyridaben
Cadusafos, carbaryl, carbofuran, carbophenothion, carbosulfan, cartap, Chloethocarb, chlorethoxyfos, chlorfenapyr, chlorfenvinphos, chlorfluazuron, chlormephos, chlorpyrifos, chlorpyrifos M, Chlovaporthrin, cis-resmethrin, Cispermethrin, Clocythrin, cloethocarb, clofentezine, cyanophos, Cycloprene, cycloprothrin, cyfluthrin , Cyhalothrin, Cyhexatin, Cypermethrin, Cyromazine, Deltamethrin, Demeton M, Demeton S, Demeton-S-methyl, Diafenthiuron, Diazinon, Dichlorvos, Diflubenzuron, Dimethoat, Dimethylvinphos, Diofenolan, Disulfoton, Docusap, sodium
Eflusilanate, Emamectin, Empenthrin, Endosulfan, Entomopfthora spp., Esfenvalerate, Ethiofencarb, Ethion, Ethoprophos, Etofenprox, Etoxazole, Etrimfos, Fenamiphos, Fenazaquin, Fenbutatin oxide, Fenitrothion, Fenothiocarb, Fenoxpyrimpyrpyrimpyrpyroxpyrin, pyroximate, phenoxpyrpyrimate, phenoxpyrpyrimate, phenoxpyrrimate, phenoxpyrrimate, phenoxpyrate, pyroxymate, phenoxpyrrimate, phenoxpyrinate, pyroxymate, phenoxpyrimate, phenoxpyrate, pyroxymate, phenoxpyrate, pyroxymate, phenoxpyrate, phenoxpyrate, pyroxymate, phenoxpyrrimate, phenoxpyrate, pyrone , Fipronil, Fluazinam, Fluazuron, Flubrocythrinate, Flucycloxuron, Flucythrinate, Flufenoxuron, Flutenzine, Fluvalinate, Fonophos, Fosmethilan, Fosthiazate, Fubfenprox, Furathiocarb,
Granulosis viruses
Halofenozide, HCH, Heptenophos, Hexaflumuron, Hexythiazox, Hydroprene,
Imidacloprid, isazofos, isofenphos, isoxathion, ivermectin,
Nuclear polyhedron viruses
Lambda cyhalothrin, lufenuron
Malathion, Mecarbam, Metaldehyde, Methamidophos, Metharhician anisopliae, Metharhician flavoviride, Methidathione, Methiocarb, Methomyl, Methoxyfenozide, Metolcarb, Metoxadiazone, Mevinphos, Milbemectin, Monocrotophos,
Naled, Nitenpyram, Nithiazine, Novaluron
Omethoate, Oxamyl, Oxydemethon M
Paecilomyces fumosoroseus, Parathion A, Parathion M, Permethrin, Phenthoat, Phorat, Phosalone, Phosmet, Phosphamidon, Phoxim, Pirimicarb, Pirimiphos A, Pirimiphos M, Profenofos, Promecarb, Propoxur, Prothiofos, Prothoat, Pyromhrhridosine, Pymmethrofinos, Pymmethrofinos , Pyridathione, pyrimidifene,
Pyriproxyfen,
Quinalphos,
Ribavirin
Salithion, Sebufos, Silafluofen, Spinosad, Sulfotep, Sulprofos,
Tau-fluvalinate, oxalate hydrogen tebufenozide, tebufenpyrad, Tebupirimiphos, teflubenzuron, tefluthrin, temephos, Temivinphos, terbufos, tetrachlorvinphos, theta cypermethrin, thiamethoxam, Thiapronil, Thiatriphos, thiocyclam, thiodicarb, thiofanox, thuringiensin, Tralocythrin, tralomethrin, triarathene, Triazamate, triazophos , Triazuron, trichlophenidine, trichlorfon, triflumuron, trimethacarb,
Vamidothion, Vaniliprole, Verticillium lecanii
YI 5302
Zeta-cypermethrin, zolaprofos
(1R-cis) - [5- (phenylmethyl) -3-furanyl] methyl-3 - [(dihydro-2-oxo-3 (2H) - furanylidene) methyl] -2,2-dimethylcyclopropane carboxylate
(3-phenoxyphenyl) methyl 2,2,3,3-tetramethylcyclopropane decarboxylate
1 - [(2-Chloro-5-thiazolyl) methyl] tetrahydro-3,5-dimethyl-N-nitro-1,3,5-triazine-2 (1 H) - imine
2- (2-chloro-6-fluorophenyl) -4- [4- (1,1-dimethylethyl) phenyl] -4,5-dihydro-oxazole
2- (acetyloxy) -3-dodecyl-1,4-naphthalenedione
2-Chloro-N - [[[4- (1-phenylethoxy) phenyl] amino] carbonyl] benzamide
2-Chloro-N - [[[4- (2,2-dichloro-1,1-difluoroethoxy) phenyl] amino] carbonyl] benzamide
3-methylphenyl propyl carbamate
4- [4- (4-ethoxyphenyl) -4-methylpentyl] -1-fluoro-2-phenoxy-benzene
4-chloro-2- (1,1-dimethylethyl) -5 - [[2- (2,6-dimethyl-4-phenoxyphenoxy) ethyl] thio] - 3 (2H) pyridazinone
4-chloro-2- (2-chloro-2-methylpropyl) -5 - [(6-iodo-3-pyridinyl) methoxy] -3 (2H) - pyridazinone
4-Chloro-5 - [(6-chloro-3-pyridinyl) methoxy] -2- (3,4-dichlorophenyl) -3 (2H) -pyridazinone Bacillus thuringiensis strain EG-2348
Benzoic acid [2-benzoyl-1- (1,1-dimethylethyl) hydrazide
Butanoic acid 2,2-dimethyl-3- (2,4-dichlorophenyl) -2-oxo-1-oxaspiro [4.5] dec-3-en-4-yl ester
[3 - [(6-chloro-3-pyridinyl) methyl] -2-thiazolidinylidene] cyanamide
Dihydro-2- (nitromethylene) -2H-1,3-thiazine-3 (4H) carboxaldehyde
Ethyl [2 - [[1,6-dihydro-6-oxo-1- (phenylmethyl) -4-pyridazinyl] oxy] ethyl] carbamate
N- (3,4,4-trifluoro-1-oxo-3-butenyl) glycine
N- (4-chlorophenyl) -3- [4- (difluoromethoxy) phenyl] -4,5-dihydro-4-phenyl-1H-pyrazole-1-carboxamide
N - [(2-chloro-5-thiazolyl) methyl] -N'-methyl-N "-nitro-guanidine
N-methyl-N '- (1-methyl-2-propenyl) -1,2-hydrazinedicarbothioamide
N-methyl-N'-2-propenyl-1,2-hydrazinedicarbothioamide
O, O-Diethyl- [2- (dipropylamino) -2-oxoethyl] ethyl phosphoramidothioate.

A mixture with other known active ingredients, such as herbicides or with Fertilizers and growth regulators are possible.

In addition, the compounds of the formula (I) according to the invention also very good antifungal effects. They have a very broad antimyko spectrum of activity, in particular against dermatophytes and shoots, Mold and diphasic fungi (e.g. against Candida species such as Candida albicans, Candida glabrata) such as Epidermophyton floccosum, Aspergillus species such as Aspergillus niger and Aspergillus fumigatus, Trichophyton species like Tricho phyton mentagrophytes, microsporon species such as microsporon canis and audouinii. The list of these mushrooms in no way places a restriction on what can be detected mycotic spectrum, but is only explanatory.

The active substances can be used as such, in the form of their formulations or in the form thereof rode application forms, such as ready-made solutions, suspensions, spray powders, pastes, soluble powders, dusts and granules can be used. The Application happens in the usual way, e.g. B. by pouring, spraying, spraying, Scattering, dusting, foaming, brushing, etc. It is also possible to use the Apply active ingredients according to the ultra-low-volume process or the active ingredient preparation or inject the active substance yourself into the soil. It can also do that Seeds of the plants are treated.

When using the active compounds according to the invention as fungicides, the effort can be reduced quantities can be varied within a wide range depending on the type of application. When treating parts of plants, the active compound application rates are in the generally between 0.1 and 10,000 g / ha, preferably between 10 and 1,000 g / ha. In the case of seed treatment, the active compound application rates are in general between 0.001 and 50 g per kilogram of seed, preferably between 0.01 and 10 g per kilogram of seed. When treating the floor, there are problems  wall amounts of active ingredient in general between 0.1 and 10,000 g / ha preferably between 1 and 5,000 g / ha.

Manufacturing examples example 1 2 - {[3- (Formylamino) -2-hydroxybenzoylamino} -3- (4-hydroxyphenyl) propane acid ethyl ester Procedure b)

2.0 g (5.1 mmol) of ethyl 2 - [(2-hydroxy-3-nitrobenzoyl) amino] -3- (4-hydroxyphenyl) propane were suspended in 60 ml of formic acid and 2.0 g of Raney nickel were added. The mixture was stirred at 90 ° C for 1 hour and then filtered. The filtrate was evaporated, the residue taken up in dichloromethane and with dist. Washed water. The organic phase was dried over sodium sulfate and then evaporated to dryness. The purification was carried out on silica gel using the mobile phase mixture ethyl acetate / cyclohexane in a ratio of 6: 1. 1.34 g (70% of theory) of 2 - {[3- (formylamino) -2-hydroxybenzoyl] amino} -3- (4- hydroxyphenyl) propanoic acid ethyl ester.
PLC: logP = 1.83

Analogously to Example 1 and in accordance with the general description of the processes according to the invention, the compounds of the general formula (Ia) listed in Table 1 below are obtained:

Table 1

The logP values were determined in accordance with EEC Directive 79/831 Annex V. A8 by HPLC (gradient method, acetonitrile / 0.1% aqueous phosphoric acid)  

Production of precursors of formula (IV) Example (IV-1) 2 - [(2-Hydroxy-3-nitrobenzoyl) amino] -3- (4-hydroxyphenyl) propanoic acid ethyl ester Procedure d)

1.78 g (8.0 mmol) D, L-tyrosine ethyl ester hydrochloride are dissolved in 20 mL tetrahydro furan dissolved and mixed with 1.1 mL (8 mmol) triethylamine. To the reaction mix with stirring at 0 ° C 1.61 g (8.0 mmol) 3-nitrosalicylic acid chloride, dissolved in 25 mL tetrahydrofuran, added dropwise. The reaction mixture is left inside Warm to room temperature for half a hour. The fancy triethyl Ammonium chloride is filtered off and the remaining solution on the rotary ver concentrated steamer. The residue is taken up in 200 ml of ethyl acetate and with 200 mL dist. Water extracted. The organi is then dried phase over sodium sulfate. The solvent was on a rotary evaporator away. The cleaning is carried out on silica gel with the mobile phase mixture ethyl acetate / cyclohexane in a ratio of 10: 1.

2.14 g (69% of theory) of ethyl 2 - [(2-hydroxy-3-nitrobenzoyl) amino] -3- (4-hydroxyphenyl) propanoate are obtained.
HPLC: logP = 2.28

Analogously to Example (IV-1) and in accordance with the general description of the processes according to the invention, the compounds of the general formula (IV) listed in Table 2 below are obtained:

Table 2

The logP values were determined in accordance with EEC Directive 79/831 Annex V. A8 by HPLC (gradient method, acetonitrile / 0.1% aqueous phosphoric acid).  

Examples of use Example A Phytophthora test (tomato) / protective

Solvent: 24.5 parts by weight of acetone
24.5 parts by weight of dimethylacetamide
Emulsifier: 1.0 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 weight is mixed some active ingredient with the specified amounts of solvent and emulsifier and ver thin the concentrate with water to the desired concentration.

To test for protective effectiveness, young plants are used with the active ingredient preparation sprayed in the specified application rate. After the The plants are sprayed with an aqueous spore suspension of Phy tophthora infestans inoculated. The plants are then in an incubation cabin set up at approx. 20 ° C and 100% relative humidity.

Evaluation is carried out 3 days after the inoculation. 0% means a Efficiency that corresponds to that of the control, while an efficiency 100% means that no infection is observed.

This test shows those listed in Examples (2), (4), (8) and (12) Substances according to the invention have an efficiency at an application rate of 100 g / ha of 92% or more.  

Example B Plasmopara test (Reb 04062 00070 552 001000280000000200012000285910395100040 0002019938737 00004 03943e) / protective

Solvent: 24.5 parts by weight of acetone
24.5 parts by weight of dimethylacetamide
Emulsifier: 1.0 part by weight of alkylaryl polyglycol ether

To prepare a suitable preparation of active compound, 1 Ge is mixed most of the active ingredient with the specified amounts of solvent and emulsifier and dilute the concentrate with water to the desired concentration.

To test for protective effectiveness, young plants are treated with the active ingredient sprayed substance preparation in the specified application rate. After the The plants are sprayed with an aqueous spore suspension of Plasmopara viticola inoculated and then remain in an incubation cabin for 1 day at approx. 20 ° C and 100% relative humidity. Then the plants 5 Set up days in the greenhouse at approx. 21 ° C and approx. 90% humidity. The Plants are then moistened and placed in an incubation cabin for 1 day.

Evaluation is carried out 6 days after the inoculation. 0% means a Efficiency that corresponds to that of the control, while an efficiency 100% means that no infection is observed.

This test shows those listed in Examples (2), (4), (6), (8) and (12) Substances according to the invention have an efficiency at an application rate of 100 g / ha of 97% or more.  

Example C Botrytis test (bean) / protective

Solvent: 24.5 parts by weight of acetone
24.5 parts by weight of dimethylacetamide
Emulsifier: 1.0 part by weight of alkylaryl polyglycol ether

To prepare a suitable preparation of active compound, 1 Ge is mixed most of the active ingredient with the specified amounts of solvent and emulsifier and dilute the concentrate with water to the desired concentration.

To test for protective effectiveness, young plants are treated with the active ingredient sprayed substance preparation in the specified application rate. After the Spray pads are covered with 2 small botrytis cinerea on each leaf Pieces of agar placed on top. The inoculated plants are darkened in a Chamber set up at about 20 ° C and 100% relative humidity.

2 days after the inoculation, the size of the infection spots on the leaves evaluated. 0% means an efficiency level that that of the control corresponds, while an efficiency of 100% means that no infection is observed becomes.

This test shows those listed in Examples (2), (4), (6), (8) and (12) Substances according to the invention have an efficiency at an application rate of 500 g / ha of 90% or more.  

Example D Pyricularia test (rice) / protective

Solvent: 48.8 parts by weight of acetone
Emulsifier: 1.2 parts by weight of alkylaryl polyglycol ether

To prepare a suitable preparation of active compound, 1 Ge is mixed most of the active ingredient with the specified amount of solvent and emulsifier and dilute the concentrate with water to the desired concentration.

To test for protective effectiveness, young rice plants are sprayed with the Active ingredient preparation in the specified application rate. After drying the The plants are sprayed with an aqueous spore suspension of Pyricu laria oryzae inoculated and then remain at 100% rel. Humidity and 26 ° C. Then the plants in a greenhouse at 80% relative Humidity and a temperature of 26 ° C.

Evaluation is carried out 7 days after the inoculation. 0% means a Efficiency that corresponds to that of the control, while an efficiency 100% means that no infection is observed.

This test shows those listed in Examples (1), (8), (9), (10) and (12) Substances according to the invention have an efficiency at an application rate of 750 g / ha of 89% or more.

Claims (15)

1. Use of compounds of the formula (I),
in which
R ^{1 represents} hydrogen or alkyl,
R ^{2 represents} hydrogen or alkyl, or
R ³ for a grouping
stands in what
A represents oxygen, sulfur or - (NR ⁹ ) -, in which
R ^{9 represents} hydrogen or alkyl or, together with R ⁶ and the nitrogen atom to which they are attached, forms an optionally substituted heterocyclic ring,
R ^{4 represents} hydrogen, optionally substituted alkyl or optionally substituted aryl or
R ² and R ⁴ together with the nitrogen atom to which they are bound form a heterocyclic ring,
R ^{5 represents} hydrogen or alkyl or
R ⁴ and R ⁵ together with the carbon atom to which they are bound form a carbocyclic ring,
R ^{6 represents} hydrogen or in each case optionally substituted alkyl, cycloalkyl, aryl or heterocyclyl,
R ^{7 represents} hydrogen or alkyl,
R ^{8 represents} hydrogen or alkyl and
Z represents hydrogen or in each case optionally substituted alkyl, alkylcarbonyl, cycloalkyl, cycloalkylcarbonyl, aryl, arylcarbonyl, heterocyclyl or heterocyclylcarbonyl,
to control organisms that cause plant damage and damage to technical materials. 2. Use of compounds of formula (I), according to claim 1, characterized in that
R ^{1 represents} hydrogen or methyl,
R ^{2 represents} hydrogen or C ₁ -C ₄ alkyl and
R ³ for a grouping
stands in what
A represents oxygen, sulfur or - (NR ⁹ ) -, in which
R ^{9 represents} hydrogen or alkyl having 1 to 4 carbon atoms or, together with R ⁶ and the nitrogen atom to which they are attached, forms a heterocyclic ring with 3 to 7 ring members which is optionally substituted by C ₁ -C ₄ alkyl,
R ^{4 represents} hydrogen or optionally substituted by hydroxyl, formyloxy, optionally substituted arylcarbonyloxy or alkoxy, alkylthio, alkoxycarbonyl or alkylcarbonyloxy each having 1 to 6 carbon atoms in the alkyl part substituted alkyl or optionally substituted in the aryl part or heterocyclic part, aryl, heterocyclyl, arylalkyl or heterocyclylalkyl each having 1 to 6 carbon atoms in the alkyl part or
R ² and R ⁴ together with the nitrogen atom to which they are bound form a heterocyclic ring with 3 to 6 ring members,
R ^{5 represents} hydrogen or C ₁ -C ₄ alkyl or
R ⁴ and R ⁵ together with the carbon atom to which they are bound form a carbocyclic ring with 3 to 6 ring members,
R ⁶ for hydrogen or C ₁ -C ₁₂ alkyl, optionally substituted by C ₁ -C ₄ alkyl substituted C ₃ -C ₇ cycloalkyl, aryl or aryl alkyl having 1 to 6 carbon atoms optionally substituted in the aryl or heterocyclyl part in the alkyl part, heterocyclyl or heterocyclylalkyl having 1 to 6 carbon atoms in the alkyl part,
R ^{7 represents} hydrogen or C ₁ -C ₄ alkyl,
R ^{8 represents} hydrogen or C ₁ -C ₄ alkyl and
Z represents hydrogen or C ₁ -C ₁₂ alkyl or alkylcarbonyl, optionally C ₃ -C ₇ cycloalkyl or cycloalkylcarbonyl, optionally substituted by C ₁ -C ₄ alkyl, aryl, arylcarbonyl, arylalkyl optionally substituted in the aryl or heterocyclyl part, Arylalkylcarbonyl having 1 to 6 carbon atoms in the alkyl part, heterocyclyl, heterocyclylcarbonyl, heterocyclylalkyl or heterocyclylalkylcarbonyl having 1 to 6 carbon atoms in the alkyl part,
to control organisms that cause plant damage and damage to technical materials. 3. Use of compounds of formula (I) according to claim 1, characterized in that
R ^{1 represents} hydrogen or methyl,
R ^{2 represents} hydrogen, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl and
R ³ for a grouping
stands in what
A represents oxygen, sulfur or - (NR ⁹ ) -, in which
R ^{9 represents} hydrogen or methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl or together with R ⁶ and the nitrogen atom to which they are attached, if appropriate by methyl or Ethyl substituted pyrrolidinyl, morpholinyl, piperidinyl, piperazinyl or hexahydro azepinyl,
R ^{4 represents} hydrogen or phenylcarbonyloxy optionally substituted by hydroxyl, formyloxy, methoxy, ethoxy, methylthio, ethylthio, methoxycarbonyl, ethoxycarbonyl, methylcarbonyloxy, ethylcarbonyloxy, propylcarbonyloxy, pentylcarbonyloxy or hexylcarbonyloxy substituted methyl, ethyl, n- or i- Propyl, n-, i-, s- or t-butyl or phenyl, benzyl, 1-phenethyl, 2-phenethyl or indolylmethyl optionally substituted in the phenyl part or heterocyclyl part or
R ² and R ⁴ together with the nitrogen atom to which they are bound represent a pyrrolidine or piperidine ring,
R ^{5 represents} hydrogen, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl or
R ⁴ and R ⁵ together with the carbon atom to which they are bound represent a cyclopropane ring, cyclopentane or cyclohexane ring,
R ^{6 represents} hydrogen, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, pentyl, hexyl, heptyl, octyl, optionally by methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl substituted cyclopentyl or cyclohexyl, each optionally substituted in the phenyl or heterocyclyl part, phenyl, benzyl, 1-phenethyl, 2-phenethyl, phenylpropyl, phenylbutyl, phenylpentyl or phenylhexyl, pyrrolidinyl, Morpholinyl, pyrrolidinylbutyl or morpholinylbutyl, methyl, ethyl or propyl substituted by pyrrolidonyl,
R ^{7 represents} hydrogen, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl,
R ^{8 represents} hydrogen, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl and
Z for hydrogen, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, pentyl, hexyl, heptyl, octyl, methylcarbonyl, ethylcarbonyl, n- or i-propylcarbonyl, n-, i-, s- or t-butylcarbonyl, pentylcarbonyl, hexylcarbonyl, heptylcarbonyl, octylcarbonyl, optionally substituted by methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl substituted cyclopentyl, cyclohexyl, cyclopentylcarbonyl or Cyclohexyl carbonyl, each optionally substituted in the phenyl or heterocyclyl part, phenyl, benzyl, 1-phenethyl, 2-phenethyl, phenylpropyl, phenylbutyl, phenylpentyl or phenylhexyl, pyrrolidinyl, morpholinyl, pyrrolidinylbutyl, morpholinylbutyl, phenylcarbonyl, phenylcarbonyl, 1 -Phenethylcarbonyl, phenyl carbonylpropylcarbonyl, phenylcarbonylbutylcarbonyl, phenyl carbonylpentylcarbonyl or phenylcarbonylhexylcarbonyl, pyrrolidinylcarbonyl, morpholinylcarbonyl, pyrrolidinylcarbonylbutyl carbonyl or morpholinylcarbonylbutylcarbonyl to combat vo n Organisms that cause plant damage and damage to technical materials. 4. Compounds of the formula (Ia),
in which
R ^{11 represents} hydrogen or alkyl,
R ^{12 represents} hydrogen or alkyl, or
R ¹³ for a grouping
stands in what
A represents oxygen, sulfur or - (NR ¹⁹ ) -, in which
R ^{19 represents} hydrogen or alkyl or, together with R ¹⁶ and the nitrogen atom to which they are attached, forms an optionally substituted heterocyclic ring,
R ^{14 represents} hydrogen, optionally substituted alkyl or optionally substituted aryl or
R ¹² and R ¹⁴ together with the nitrogen atom to which they are bound form a heterocyclic ring,
R ^{15 represents} hydrogen or alkyl or
R ¹⁴ and R ¹⁵ together with the carbon atom to which they are bound form a carbocyclic ring,
R ^{16 represents} hydrogen or in each case optionally substituted alkyl, cycloalkyl, aryl or heterocyclyl,
R ^{17 represents} hydrogen or alkyl and
R ^{18 represents} hydrogen or alkyl,
Z ^{1 represents} hydrogen or in each case optionally substituted alkyl, alkylcarbonyl, cycloalkyl, cycloalkylcarbonyl, aryl, aryl carbonyl, heterocyclyl or heterocyclylcarbonyl,
R ^{20 represents} hydrogen, optionally substituted alkyl or optionally substituted aryl or hetaryl or
R ¹² and R ²⁰ together with the nitrogen atom to which they are bound form a heterocyclic ring,
R ^{21 represents} hydrogen or alkyl or
R ²⁰ and R ²¹ together with the carbon atom to which they are bound form a carbocyclic ring. 5. Compounds of formula (Ia), according to claim 4, characterized in that
R ^{11 represents} hydrogen or methyl,
R ^{12 represents} hydrogen or C ₁ -C ₄ alkyl and
R ¹³ for a grouping
stands in what
A represents oxygen, sulfur or - (NR ¹⁹ ) -, in which
R ^{19 represents} hydrogen or alkyl having 1 to 4 carbon atoms or, together with R ¹⁶ and the nitrogen atom to which they are attached, forms a heterocyclic ring with 3 to 7 ring members which is optionally substituted by C ₁ -C ₄ alkyl,
R ^{14 represents} hydrogen or optionally substituted by hydroxyl, formyloxy, optionally substituted arylcarbonyloxy or alkoxy, alkylthio, alkoxycarbonyl or alkylcarbonyloxy each having 1 to 6 carbon atoms in the alkyl part substituted alkyl or optionally substituted in the aryl part or heterocyclic part, aryl, heterocyclyl, arylalkyl or heterocyclylalkyl each having 1 to 6 carbon atoms in the alkyl part or
R ¹² and R ¹⁴ together with the nitrogen atom to which they are bound form a heterocyclic ring with 3 to 6 ring members,
R ^{15 represents} hydrogen or C ₁ -C ₄ alkyl or
R ¹⁴ and R ¹⁵ together with the carbon atom to which they are bound form a carbocyclic ring with 3 to 6 ring members,
R ¹⁶ for hydrogen or C ₁ -C ₁₂ alkyl, optionally substituted by C ₁ -C ₄ alkyl substituted C ₃ -C ₇ cycloalkyl, in each case optionally substituted aryl or aryl alkyl with 1 to 6 carbon atoms in the aryl or heterocyclyl part in the alkyl part, heterocyclyl, heterocyclylalkyl having 1 to 6 carbon atoms in the alkyl part or C ₁ -C ₄ -alkyl substituted by pyrrolidonyl,
R ^{17 represents} hydrogen or C ₁ -C ₄ alkyl and
R ^{18 represents} hydrogen or C ₁ -C ₄ alkyl,
Z ^{1 represents} hydrogen or C ₁ -C ₁₂ alkyl or alkylcarbonyl, optionally substituted by C ₁ -C ₄ alkyl substituted C ₃ -C ₇ cycloalkyl or cycloalkylcarbonyl, in each case optionally substituted aryl, arylcarbonyl, arylalkyl in the aryl or heterocyclyl part Arylalkylcarbonyl having 1 to 6 carbon atoms in the alkyl part, heterocyclyl, heterocyclylcarbonyl, heterocyclylalkyl or heterocyclylalkylcarbonyl having 1 to 6 carbon atoms in the alkyl part,
R ^{20 represents} hydrogen or optionally substituted by formyloxy, optionally substituted arylcarbonyloxy or alkoxy, alkylthio, alkoxycarbonyl or alkylcarbonyloxy each having 1 to 6 carbon atoms in the alkyl part, substituted C ₁ -C ₄ -alkyl or optionally substituted in the aryl part or heterocyclic part Aryl, heterocyclyl, arylalkyl having 2 to 6 carbon atoms in the alkyl part or heterocyclylalkyl having 1 to 6 carbon atoms in the alkyl part or substituted benzyl or
R ¹² and R ²⁰ together with the nitrogen atom to which they are bound form a heterocyclic ring with 3 to 6 ring members,
R ^{21 represents} hydrogen or C ₁ -C ₄ alkyl or
R ²⁰ and R ²¹ together with the carbon atom to which they are bound form a carbocyclic ring with 3 to 6 ring members. 6. Compounds of formula (Ia), according to claim 4, characterized in that
R ^{11 represents} hydrogen or methyl,
R ^{12 represents} hydrogen, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl and
R ¹³ for a grouping
stands in what
A represents oxygen, sulfur or - (NR ¹⁹ ) -, in which
R ^{19 represents} hydrogen or methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl or together with R ¹⁶ and the nitrogen atom to which they are attached, if appropriate by methyl or Ethyl substituted pyrrolidinyl, morpholinyl, piperidinyl, piperazinyl or hexahydro azepinyl,
R ^{14 represents} hydrogen or phenylcarbonyloxy, optionally substituted in the phenyl part, by hydroxy, formyloxy, methoxy, ethoxy, methylthio, ethylthio, methoxycarbonyl, ethoxycarbonyl, methylcarbonyloxy, ethylcarbonyloxy, propylcarbonyloxy, pentylcarbonyloxy or hexylcarbonyloxy substituted methyl, ethyl, n- or i- Propyl, n-, i-, s- or t-butyl or phenyl, benzyl, 1-phenethyl, 2-phenethyl or indolylmethyl optionally substituted in the phenyl part or heterocyclyl part or
R ¹² and R ¹⁴ together with the nitrogen atom to which they are bound represent a pyrrolidine or piperidine ring,
R ^{15 represents} hydrogen, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl or
R ¹⁴ and R ¹⁵ together with the carbon atom to which they are bound represent a cyclopropane, cyclopentane or cyclohexane ring,
R ^{16 represents} hydrogen, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, pentyl, hexyl, heptyl, octyl, optionally by methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl substituted cyclopentyl or cyclohexyl, each optionally substituted in the phenyl or heterocyclyl part, phenyl, benzyl, 1-phenethyl, 2-phenethyl, phenylpropyl, phenylbutyl, phenyl pentyl or phenylhexyl, pyrrolidinyl, Morpholinyl, pyrrolidinylbutyl, morpholinylbutyl or methyl, ethyl or propyl substituted by pyrrolidonyl,
R ^{17 represents} hydrogen, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl and
R ^{18 represents} hydrogen, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl,
Z ¹ for hydrogen, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, pentyl, hexyl, heptyl, octyl, methylcarbonyl, ethyl carbonyl, n- or i-propylcarbonyl, n -, i-, s- or t-butyl carbonyl, pentylcarbonyl, hexylcarbonyl, heptylcarbonyl, octylcarbonyl, optionally substituted by methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl substituted cyclopentyl, cyclohexyl , Cyclopentylcarbonyl or cyclohexylcarbonyl, each because phenyl, benzyl, 1-phenethyl, 2-phenethyl, phenylpropyl, phenylbutyl, phenylpentyl or phenylhexyl, pyridylinyl, morpholinyl, pyrrolidinylbutyl, morpholcarbonylbutyl, morpholcarbonylbutyl 1-phenethylcarbonyl, 2-phen ethylcarbonyl, phenylcarbonylpropylcarbonyl, phenylcarbonyl butylcarbonyl, phenylcarbonylpentylcarbonyl or phenyl carbonylhexylcarbonyl, pyrrolidinylcarbonyl, morpholinyl carbonyl, pyrrolidinylcarbonylbutylcarbonyl or morpholinyl carbonylbutylcarbonyl,
R ²⁰ for hydrogen or optionally substituted by formyloxy, optionally substituted phenylcarbonyloxy, methoxy, ethoxy, methylthio, ethylthio, methoxycarbonyl, ethoxycarbonyl, methylcarbonyloxy, ethylcarbonyloxy, propyl carbonyloxy, pentylcarbonyloxy or hexylcarbonyloxy substituted methyl, ethyl, n- or i-propyl , n-, i-, s- or t-butyl or in each case optionally substituted phenyl, 1-phenethyl, 2-phenethyl or indolyl methyl or substituted benzyl in the phenyl part or heterocyclyl part or
R ¹² and R ²⁰ together with the nitrogen atom to which they are bound represent a pyrrolidine or piperidine ring,
R ^{21 represents} hydrogen, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl or
R ²⁰ and R ²¹ together with the carbon atom to which they are bound represent a cyclopropane ring, cyclopentane or cyclohexane ring. 7. Compounds of the formula (II-a),
in which
R ^{12 has} the meaning given above, and
R ¹³ for a grouping
stands in what
A, R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , Z ¹ and R ^{21 have} the meanings given above,
R ²² is by formyloxy, optionally in the aryl moiety substituted arylcarbonyloxy, or alkoxy, alkylthio, alkoxycarbonyl or alkylcarbonyloxy with in each case 1 to 6 carbon atoms in the alkyl-substituted C ₁ -C ₄ alkyl or unsubstituted C ₂ - C ₄ alkyl, each optionally substituted in the aryl moiety, or heterocyclic substituted aryl, heterocyclyl, arylalkyl having 2 to 6 carbon atoms in the alkyl part or heterocyclylalkyl having 1 to 6 carbon atoms in the alkyl part or substituted benzyl or
R ²² and R ¹² together with the nitrogen atom to which they are bound form a heterocyclic ring,
R ²² and R ²¹ together with the carbon atom to which they are bound form a carbocyclic ring. 8. Compounds of formula (II-a), according to claim 7, characterized in that
R ^{12 has} the meaning given above, and
R ¹³ for a grouping
stands in what
A, R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , Z ¹ and R ^{21 have} the meanings given above,
R ²² is by formyloxy, optionally in the aryl moiety substituted arylcarbonyloxy, or alkoxy, alkylthio, alkoxycarbonyl or alkylcarbonyloxy with in each case 1 to 6 carbon atoms in the alkyl-substituted C ₁ -C ₄ alkyl or unsubstituted C ₂ - C ₄ alkyl, each optionally substituted in the aryl moiety, or heterocyclic substituted aryl, heterocyclyl, arylalkyl having 2 to 6 carbon atoms in the alkyl part or heterocyclylalkyl having 1 to 6 carbon atoms in the alkyl part or substituted benzyl or
R ²² and R ¹² together with the nitrogen atom to which they are bound represent a pyrrolidine or piperidine ring or
R ²² and R ²¹ together with the carbon atom to which they are bound represent a cyclopentane or cyclohexane ring. 9. Compounds of formula (II-a), according to claim 7, characterized in that
R ^{12 has} the meaning given above, and
R ¹³ for a grouping
stands in what
A, R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , Z ¹ and R ^{21 have} the meanings given above,
R ²² represents phenylcarbonyloxy, methoxy, ethoxy, methylthio, ethylthio, methoxycarbonyl, ethoxycarbonyl, methyl carbonyloxy, ethylcarbonyloxy, propylcarbonyloxy, pentylcarbonyloxy or hexylcarbonyloxy, each substituted by formyloxy, optionally substituted in the phenyl part, methyl, ethyl, n- or i-propyl, n -, i-, s- or t-butyl or unsubstituted ethyl, n- or i-propyl, n-, i-, s- or t-butyl, each optionally substituted phenyl, 1-phenethyl in the phenyl part or heterocyclyl part, 2-phenethyl or indolylmethyl or substituted benzyl or
R ²² and R ¹² together with the nitrogen atom to which they are bound represent a pyrrolidine or piperidine ring or
R ²² and R ²¹ together with the carbon atom to which they are bound represent a cyclopentane or cyclohexane ring. 10. Compounds of the formula (IVa),
in which
R ¹² and R ^{13 have} the meaning given in claim 4. 11. Agents containing extenders and / or carriers and, if appropriate surfactants, characterized by a content of at least a compound as defined in claims 4 to 6.   12. A method for controlling pests, characterized in that compounds as in claims 4 to 6 or agents as in Claim 11 defined to act on pests and / or its habitat leaves. 13. Use of compounds as in claims 4 to 6 or agents as defined in claim 11 for pest control. 14. Process for the preparation of pesticides, thereby ge indicates that compounds are defined as in claims 4 to 6 mixed with extenders and / or surfactants. 15. A process for the preparation of compounds of formula (Ia) as defined in claim 4, characterized in that

• a) aminosalicylic acid amides of the general formula (II),
  in which
  R ¹² and R ^{13 have} the meanings given above,
  with an acylating agent of the general formula (III),
  in which
  R ^{11 has} the meaning given above and
  X ^{1 represents} halogen, hydroxy, alkoxy or alkylcarbonyloxy,
  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 further reaction auxiliary, or if
• b) nitrosalicylic acid amides of the general formula (IV)
  in which
  R ¹² and R ^{13 have} the meanings given above, with formic acid, if appropriate in the presence of a catalyst and, if appropriate, in the presence of a further reaction auxiliary.